(Landolt-Börnstein - Group IV Physical Chemistry 11D5 _ Physical Chemistry) Günter Effenberg, Svitlana Ilyenko (Eds.)-Ternary Alloy Systems_ Phase Diagrams, Crystallographic and Thermodynamic Data Cri

Landolt-Börnstein
Numerical Data and Functional Relationships in Science and Technology

New Series / Editor in Chief: W. Martienssen
Group IV: Physical Chemistry

Volume 11
Ternary Alloy Systems

Phase Diagrams, Crystallographic and
Thermodynamic Data
critically evaluated by MSIT®
Subvolume D
Iron Systems
Part 5
Selected Systems from Fe-N-V to Fe-Ti-Zr
Editors
G. Effenberg and S. Ilyenko
Authors
Materials Science and International Team, MSIT®
ISSN 1615-2018 (Physical Chemistry)
ISBN 978-3-540-70885-8 Springer Berlin Heidelberg New York
Library of Congress Cataloging in Publication Data

Zahlenwerte und Funktionen aus Naturwissenschaften und Technik, Neue Serie
Editor in Chief: W. Martienssen
Vol. IV/11D5: Editors: G. Effenberg, S. Ilyenko
At head of title: Landolt-Börnstein. Added t.p.: Numerical data and functional relationships in science and technology.
Tables chiefly in English.
Intended to supersede the Physikalisch-chemische Tabellen by H. Landolt and R. Börnstein of which the 6th ed. began publication in 1950 under title:
Zahlenwerte und Funktionen aus Physik, Chemie, Astronomie, Geophysik und Technik.
Vols. published after v. 1 of group I have imprint: Berlin, New York, Springer-Verlag
Includes bibliographies.
1. Physics--Tables. 2. Chemistry--Tables. 3. Engineering--Tables.
I. Börnstein, R. (Richard), 1852-1913. II. Landolt, H. (Hans), 1831-1910.
III. Physikalisch-chemische Tabellen. IV. Title: Numerical data and functional relationships in science and technology.
QC61.23 502'.12 62-53136
This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation,
reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in other ways, and storage in data banks. Duplication of this
publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and
permission for use must always be obtained from Springer-Verlag. Violations are liable for prosecution act under German Copyright Law.
Springer is a part of Springer Science+Business Media

springeronline.com
© Springer-Verlag Berlin Heidelberg 2009
Printed in Germany
The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement,
that such names are exempt from the relevant protective laws and regulations and therefore free for general use.
Product Liability: The data and other information in this handbook have been carefully extracted and evaluated by experts from the original literature.
Furthermore, they have been checked for correctness by authors and the editorial staff before printing. Nevertheless, the publisher can give no
guarantee for the correctness of the data and information provided. In any individual case of application, the respective user must check the correctness
by consulting other relevant sources of information.
Cover layout: Erich Kirchner, Heidelberg

Typesetting: Materials Science International Services GmbH, Stuttgart
Printing and Binding: AZ Druck, Kempten/Allgäu
SPIN: 1221 0152 63/3020 - 5 4 3 2 1 0 – Printed on acid-free paper

Editors: Günter Effenberg
Svitlana Ilyenko
Associate Editor: Oleksandr Dovbenko
MSI, Materials Science International Services GmbH

Postfach 800749, D-70507, Stuttgart, Germany
http://www.matport.com
Authors: Materials Science International Team, MSIT®

The present series of books results from collaborative evaluation programs performed by MSI and
authored by MSIT®. In this program data and knowledge are contributed by many individuals and
accumulated over almost twenty years, now. The content of this volume is a subset of the ongoing MSIT®
Evaluation Programs. Authors of this volume are:
Nataliya Bochvar, Moscow, Russia Marina Hans Leo Lukas, Stuttgart, Germany
Bulanova, Kyiv, Ukraine Gabriele Pankaj Nerikar, Gainesville, USA Pierre
Cacciamani, Genova, Italy Hailin Chen, Perrot, Lille, France Tatiana Pryadko,
Changsha, China Gautam Ghosh, Evanston, Kyiv, Ukraine Peter Rogl, Vienna, Austria
USA Lesley Cornish, Randburg, South Lazar Rokhlin, Moscow, Russia Hans
Africa Damian M. Cupid, Freiberg, Germany Jürgen Seifert, Freiberg, Germany Elena
Yong Du, Changsha, China Olga Semenova, Kyiv, Ukraine Weihua Sun,
Fabrichnaya, Freiberg, Germany Yulia Changsha, China Jean-Claude Tedenac,
Fartushna, Kyiv, Ukraine Baiyun Huang, Montpellier, France Vasyl Tomashik,
Changsha, China Volodymyr Ivanchenko, Kyiv, Ukraine Lyudmilla Tretyachenko,
Kyiv, Ukraine Jozefien De Keyzer, Heverlee, Kyiv, Ukraine Tamara Velikanova, Kyiv,
Belgium Natalia Kol’chugina, Moscow, Ukraine Andy Watson, Leeds, U.K. Wei
Russia Kostyantyn Korniyenko, Kyiv, Xiong, Changsha, China Honghui Xu,
Ukraine Artem Kozlov, Clausthal-Zellerfeld, Changsha, China Chao Zhang, Changsha,
Germany Viktor Kuznetsov, Moscow, Russia China Lijun Zhang, Changsha, China
Shuhong Liu, Changsha, China Weiwei Zhang, Changsha, China

Institutions
The content of this volume is produced by MSI, Materials Science International Services GmbH and the
international team of materials scientists, MSIT®. Contributions to this volume have been made from the
following institutions:
The Baikov Institute of Metallurgy, Academy of School of Chemical and Metallurgical

Sciences, Moscow, Russia Engineering, The University of the
Witwatersrand, DST/NRF Centre of Excellence
Central South University, Research Institute of for Strong Material, South Afrika
Powder Metallurgy, State Key Laboratory for
Powder Metallurgy, Changsha, China Technische Universität Bergakademie Freiberg,
Institut für Werkstoffwissenschaft, Freiberg,
I.M. Frantsevich Institute for Problems of Germany
Materials Science, National Academy of Sciences,
Kyiv, Ukraine Technische Universität Clausthal, Metallurgisches
Zentrum, Clausthal-Zellerfeld, Germany
Institute for Semiconductor Physics, National
Academy of Sciences, Kyiv, Ukraine
Universita di Genova, Dipartimento di Chimica,
Katholieke Universiteit Leuven, Department Genova, Italy
Metaalkunde en Toegepaste Materiaalkunde,
Heverlee, Belgium Universität Wien, Institut für Physikalische
Chemie, Wien, Austria
G.V. Kurdyumov Institute for Metal Physics,
National Academy of Sciences, Kyiv, Ukraine Universite de Lille I, Laboratoire de Métallurgie
Physique, Villeneuve d’ASCQ, France
Max-Planck-Institut für Metallforschung,
Institut für Werkstoffwissenschaft, Universite de Montpellier II, Laboratorie de
Pulvermetallurgisches Laboratorium, Stuttgart, Physico-chimie de la Materiere Montpellier,
Germany France
Moscow State University, Department of General University of Florida, Department of Materials

Chemistry, Moscow, Russia Science and Engineering, Gainesville, USA
Northwestern University, Department of University of Leeds, Department of Materials,

Materials Science and Engineering, Evanston, School of Process, Environmental and Materials
USA Engineering, Leeds, UK
Preface
The sub-series Ternary Alloy Systems of the Landolt-Börnstein New Series provides reliable and
comprehensive descriptions of the materials constitution, based on critical intellectual evaluations of all
data available at the time and it critically weights the different findings, also with respect to their
compatibility with today’s edge binary phase diagrams. Selected are ternary systems of importance to
alloy development and systems which gained in the recent years otherwise scientific interest. In one
ternary materials system, however, one may find alloys for various applications, depending on the chosen
composition.
Reliable phase diagrams provide scientists and engineers with basic information of eminent
importance for fundamental research and for the development and optimization of materials. So
collections of such diagrams are extremely useful, if the data on which they are based have been
subjected to critical evaluation, like in these volumes. Critical evaluation means: there where
contradictory information is published data and conclusions are being analyzed, broken down to the firm
facts and re-interpreted in the light of all present knowledge. Depending on the information available this
can be a very difficult task to achieve. Critical evaluations establish descriptions of reliably known phase
configurations and related data.
The evaluations are performed by MSIT®, Materials Science International Team, a group of scientists
working together since 1984. Within this team skilled expertise is available for a broad range of methods,
materials and applications. This joint competence is employed in the critical evaluation of the often
conflicting literature data. Particularly helpful in this are targeted thermodynamic and atomistic
calculations for individual equilibria, driving forces or complete phase diagram sections.
Conclusions on phase equilibria may be drawn from direct observations e.g. by microscope, from
monitoring caloric or thermal effects or measuring properties such as electric resistivity, electro-magnetic
or mechanical properties. Other examples of useful methods in materials chemistry are mass-
spectrometry, thermo-gravimetry, measurement of electro-motive forces, X-ray and microprobe analyses.
In each published case the applicability of the chosen method has to be validated, the way of actually
performing the experiment or computer modeling has to be validated as well and the interpretation of the
results with regard to the material’s chemistry has to be verified. Therefore insight in materials
constitution and phase reactions is gained from many distinctly different types of experiments,
calculation and observations. Intellectual evaluations which interpret all data simultaneously reveal the
chemistry of the materials system best.
An additional degree of complexity is introduced by the material itself, as the state of the material
under test depends heavily on its history, in particular on the way of homogenization, thermal and
mechanical treatments. All this is taken into account in an MSIT® expert evaluation.
To include binary data in the ternary evaluation is mandatory. Each of the three-dimensional ternary
phase diagrams has edge binary systems as boundary planes; their data have to match the ternary data
smoothly. At the same time each of the edge binary systems A-B is a boundary plane for many other
ternary A-B-X systems. Therefore combining systematically binary and ternary evaluations increases
confidence and reliability in both ternary and binary phase diagrams. This has started systematically for
the first time here, by the MSIT® Evaluation Programs applied to the Landolt-Börnstein New Series. The
degree of success, however, depends on both the nature of materials and scientists!
The multitude of correlated or inter-dependant data requires special care. Within MSIT® an evaluation
routine has been established that proceeds knowledge driven and applies both, human based expertise and
electronically formatted data and software tools. MSIT® internal discussions take place in almost all
evaluation works and on many different specific questions the competence of a team is added to the work
of individual authors. In some cases the authors of earlier published work contributed to the knowledge
base by making their original data records available for re-interpretation. All evaluation reports published
here have undergone a thorough review process in which the reviewers had access to all the original data.
In publishing we have adopted a standard format that presents the reader with the data for each ternary
system in a concise and consistent manner, as applied in the “MSIT® Workplace Phase Diagrams
Online”. The standard format and special features of the Landolt-Börnstein compendium are explained in
the Introduction to the volume.
In spite of the skill and labor that have been put into this volume, it will not be faultless. All criticisms
and suggestions that can help us to improve our work are very welcome. Please contact us via
effenberg@msiwp.com. We hope that this volume will prove to be as useful for the materials scientist
and engineer as the other volumes of Landolt-Börnstein New Series and the previous works of MSIT®
have been. We hope that the Landolt Börnstein Sub-series, Ternary Alloy Systems will be well received
by our colleagues in research and industry.
On behalf of the participating authors we want to thank all those who contributed their comments and
insight during the evaluation process. In particular we thank the reviewers - Pierre Perrot,
Tamara Velikanova, Hans Leo Lukas, Marina Bulanova, Mikhail Turchanin, Nataliya Bochvar,
Olga Fabrichnaya and Viktor Kuznetsov.
We all gratefully acknowledge the dedicated scientific desk editing by Oleksandra Berezhnytska,
Mariya Saltykova and Oleksandr Rogovtsov.
Günter Effenberg, Svitlana Ilyenko and Oleksandr Dovbenko Stuttgart, March 2008
Foreword
Can you imagine a world without iron and steel? No? I can’t either.
The story of mankind is intimately linked to the discovery and successful use of metals and their
alloys. Amongst them iron and steel - we could define steel as ‘a generally hard, strong, durable,
malleable alloy of iron and carbon, usually containing between 0.2 and 1.5 percent carbon, often with
other constituents such as manganese, Chromium, nickel, molybdenum, copper, tungsten, Cobalt, or
silicon, depending on the desired alloy properties, and widely used as a structural material’, have shaped
our material world.
The story of iron takes us back to the period of the Hittite Empire around 1300 BC, when iron started
to replace bronze as the chief metal used for weapons and tools. Until today the story remains
uncompleted and the social and economic impact of the iron and steel industry is now beyond
imagination. In the year 2005 1.13 billion tons of crude steel were produced. Compared to 2004 this is an
increase of 6.8%. That same year the steel production in China increased from 280.5 to almost 350
million tons. Concerning stainless steel: according to the International Stainless Steel Forum (ISSF), the
global production forecast for 2006 now stands at 27.8 million metric tons of stainless crude steel, up
14.3% compared to 2005.
An English poem from the 19th century tells us
Gold is for the mistress

Silver for the maid
Copper for the craftsman
Cunning at his trade
Good said the baron
Sitting in his hall
But iron, cold iron
Is master of them all
It is still actual and true.
The list of different steel grades and related applications is impressive and still growing: low carbon
strip steels for automotive applications, low carbon structural steels, engineering steels, stainless steels,
cast irons, and, more recently: dual phase steels, TRIP-steels, TWIP-steels, maraging steels, …
The list of applications seems endless: a wide range of properties from corrosion resistance to high
tensile strength is covered. These properties depend on the percentage of carbon, the alloying elements,
and increasingly on the thermo-mechanical treatments that aim at optimizing the microstructure.
Yet many potential improvements remain unexplored, also due to the increasing complexity of the
new steel grades. For instance, a recently patent protected new die steel for hot deformation has the
following composition specifications: C 0.46 – 0.58; Si 0.18 – 0.40; Mn 0.45 – 0.75, Cr 0.80 – 1.20; Ni
1.30 – 1.70; Mo 0.35 – 0.65; V 0.18 – 0.25; Al 0.01 – 0.04; Ti 0.002 – 0.04; B 0.001 – 0.003; Zr 0.02 –
0.04; Fe remaining.
Although many properties of steel are directly related to non-equilibrium states, it remains a fact that
the equilibrium state creates the reference frame for all changes that might occur in any material - and
consequently would effect its properties in use - that is actually not in its thermodynamic equilibrium
state. This is what these volumes in the Landolt-Börnstein series stand for: they have collected the most
reliable data on the possible phase equilibria in ternary iron based alloys. Therefore this first volume of
data, as well as the other ones in a series of four to appear, is of immeasurable value for metallurgists and
materials engineers that improve the properties of existing steels and develop new and more complex
steel grades. It is about materials, it is about quality of life.
The well-recognized quality label of MSIT®, the Materials Science International Team, also applies to
the present volume of the Landolt-Börnstein series. It should be available for every materials engineer,
scientist and student.
Prof. Dr. ir. Patrick Wollants

Chairman - Department of Metallurgy and Materials Engineering
Katholieke Universiteit Leuven
Belgium
Contents
IV/11D5 Ternary Alloy Systems

Phase Diagrams, Crystallographic and Thermodynamic Data
Subvolume D Iron Systems
Part 5 Selected Systems from Fe-N-V to Fe-Ti-Zr
Introduction
Data Covered.......................................................................................................................................XIII
General ................................................................................................................................................XIII
Structure of a System Report ..............................................................................................................XIII
Introduction.................................................................................................................................XIII
Binary Systems ...........................................................................................................................XIII
Solid Phases ................................................................................................................................XIV
Quasibinary Systems.................................................................................................................... XV
Invariant Equilibria ...................................................................................................................... XV
Liquidus, Solidus, Solvus Surfaces ............................................................................................. XV
Isothermal Sections...................................................................................................................... XV
Temperature – Composition Sections ......................................................................................... XV
Thermodynamics.......................................................................................................................... XV
Notes on Materials Properties and Applications......................................................................... XV
Miscellaneous .............................................................................................................................. XV
References ................................................................................................................................ XVIII
General References .............................................................................................................................XIX
Ternary Systems
Fe–N–V (Iron – Nitrogen – Vanadium)..................................................................................................1

Fe–Na–O (Iron – Sodium – Oxygen)....................................................................................................14
Fe–Nb–Ni (Iron – Niobium – Nickel)...................................................................................................33
Fe–Nb–P (Iron – Niobium – Phosphorus) ............................................................................................43
Fe–Nb–Si (Iron – Niobium – Silicon)...................................................................................................55
Fe–Nb–Zr (Iron – Niobium – Zirconium).............................................................................................69
Fe–Nd–Si (Iron – Neodynium – Silicon) ..............................................................................................82
Fe–Ni–P (Iron – Nickel – Phosphorus).................................................................................................96
Fe–Ni–S (Iron – Nickel – Sulfur)........................................................................................................113
Fe–Ni–Sb (Iron – Nickel – Antimony) ...............................................................................................155
Fe–Ni–Si (Iron – Nickel – Silicon) .....................................................................................................171
Fe–Ni–Ti (Iron – Nickel – Titanium)..................................................................................................188
Fe–Ni–V (Iron – Nickel – Vanadium) ................................................................................................212
Fe–Ni–W (Iron – Nickel – Tungsten) .................................................................................................225
Fe–Ni–Zn (Iron – Nickel – Zinc) ........................................................................................................245
Fe–Ni–Zr (Iron – Nickel – Zirconium) ...............................................................................................256
Fe–O–Pb (Iron – Oxygen – Lead).......................................................................................................268
Fe–O–Si (Iron – Oxygen – Silicon) ....................................................................................................281
Fe–O–U (Iron – Oxygen – Uranium)..................................................................................................322
Fe–O–W (Iron – Oxygen – Tungsten) ................................................................................................330
Fe–O–Y (Iron – Oxygen – Yttrium) ...................................................................................................346
Fe–O–Zr (Iron – Oxygen – Zirconium) ..............................................................................................359
Fe–P–Si (Iron – Phosphorus – Silicon)...............................................................................................375
Fe–S–Ti (Iron – Sulfur – Titanium) ....................................................................................................393
Fe–Si–Ti (Iron – Silicon – Titanium)..................................................................................................410
Fe–Si–V (Iron – Silicon – Vanadium) ................................................................................................428
Fe–Si–Zr (Iron – Silicon – Zirconium) ...............................................................................................447
Fe–Sm–Ti (Iron – Samarium – Titanium) ..........................................................................................458
Fe–Sn–Zr (Iron – Tin – Zirconium) ....................................................................................................480
Fe–Ti–V(Iron – Titanium – Vanadium)..............................................................................................493
Fe–Ti–Y (Iron – Titanium – Yttrium).................................................................................................504
Fe-Ti-Zr (Iron – Titanium – Zirconium).............................................................................................518
Introduction 1 1
Introduction
Iron Systems: Phase Diagrams, Crystallographic and Thermodynamic Data
Data Covered
The series focuses on light metal ternary systems and includes phase equilibria of importance
for alloy development, processing or application, reporting on selected ternary systems of
importance to industrial light alloy development and systems which gained otherwise scien-
tific interest in the recent years.
General
The series provides consistent phase diagram descriptions for individual ternary systems.
The representation of the equilibria of ternary systems as a function of temperature results
in spacial diagrams whose sections and projections are generally published in the literature.
Phase equilibria are described in terms of liquidus, solidus and solvus projections, isother-
mal and quasibinary sections; data on invariant equilibria are generally given in the form
of tables.
The world literature is thoroughly and systematically searched back to the year 1900.
Then, the published data are critically evaluated by experts in materials science and
reviewed. Conflicting information is commented upon and errors and inconsistencies
removed wherever possible. It considers those, and only those data, which are firmly estab-
lished, comments on questionable findings and justifies re-interpretations made by the
authors of the evaluation reports.
In general, the approach used to discuss the phase relationships is to consider changes
in state and phase reactions which occur with decreasing temperature. This has influen-
ced the terminology employed and is reflected in the tables and the reaction schemes
presented.
The system reports present concise descriptions and hence do not repeat in the text facts
which can clearly be read from the diagrams. For most purposes the use of the compendium is
expected to be self-sufficient. However, a detailed bibliography of all cited references is given to
enable original sources of information to be studied if required.
Structure of a System Report
The constitutional description of an alloy system consists of text and a table/diagram section
which are separated by the bibliography referring to the original literature (see Fig. 1). The
tables and diagrams carry the essential constitutional information and are commented on in
the text if necessary.
Where published data allow, the following sections are provided in each report:
Landolt‐Börnstein DOI: 10.1007/978-3-540-70890-2_1

New Series IV/11D5 MSIT1 ß Springer 2009
2 1 Introduction
. Fig. 1
Structure of a system report
Introduction
The opening text reviews briefly the status of knowledge published on the system and outlines
the experimental methods that have been applied. Furthermore, attention may be drawn to
questions which are still open or to cases where conclusions from the evaluation work
modified the published phase diagram.
Binary Systems
Where binary systems are accepted from standard compilations reference is made to these
compilations. In other cases the accepted binary phase diagrams are reproduced for the
convenience of the reader. The selection of the binary systems used as a basis for the evaluation
of the ternary system was at the discretion of the assessor.
DOI: 10.1007/978-3-540-70890-2_1 Landolt‐Börnstein
ß Springer 2009 MSIT1 New Series IV/11D5
Introduction 1 3
Solid Phases
The tabular listing of solid phases incorporates knowledge of the phases which is necessary or
helpful for understanding the text and diagrams. Throughout a system report a unique phase
name and abbreviation is allocated to each phase.
Phases with the same formulae but different space lattices (e.g. allotropic transformation)
are distinguished by:
– small letters (h), high temperature modification (h2 > h1)
(r), room temperature modification
(1), low temperature modification (l1 > l2)
– Greek letters, e.g., ε, ε’
– Roman numerals, e.g., (I) and (II) for different pressure modifications.
In the table “Solid Phases” ternary phases are denoted by * and different phases are
separated by horizontal lines.
Quasibinary Systems
Quasibinary (pseudobinary) sections describe equilibria and can be read in the same way as
binary diagrams. The notation used in quasibinary systems is the same as that of vertical
sections, which are reported under “Temperature – Composition Sections”.
Invariant Equilibria
The invariant equilibria of a system are listed in the table “Invariant Equilibria” and, where
possible, are described by a constitutional “Reaction Scheme” (Fig. 2).
The sequential numbering of invariant equilibria increases with decreasing temperature,
one numbering for all binaries together and one for the ternary system.
Equilibria notations are used to indicate the reactions by which phases will be
– decomposed (e- and E-type reactions)
– formed (p- and P-type reactions)
– transformed (U-type reactions)
For transition reactions the letter U (Übergangsreaktion) is used in order to reserve the
letter T to denote temperature. The letters d and D indicate degenerate equilibria which do not
allow a distinction according to the above classes.
Liquidus, Solidus, Solvus Surfaces
The phase equilibria are commonly shown in triangular coordinates which allow a reading of
the concentration of the constituents in at.%. In some cases mass% scaling is used for better
data readability (see Figs. 3 and 4).

4 1
Typical reaction scheme
. Fig. 2
Introduction

Introduction 1 5
. Fig. 3
Hypothetical liqudus surface showing notation employed
In the polythermal projection of the liquidus surface, monovariant liquidus grooves

separate phase regions of primary crystallization and, where available, isothermal lines con-
tour the liquidus surface (see Fig. 3).
Isothermal Sections
Phase equilibria at constant temperatures are plotted in the form of isothermal sections (see
Fig. 4).
Temperature – Composition Sections
Non-quasibinary T-x sections (or vertical sections, isopleths, polythermal sections) show the
phase fields where generally the tie lines are not in the same plane as the section. The notation
employed for the latter (see Fig. 5) is the same as that used for binary and quasibinary phase
diagrams.

6 1 Introduction
. Fig. 4
Hypotheticcal isothermal section showing notation employed
Thermodynamics
Experimental ternary data are reported in some system reports and reference to thermody-
namic modeling is made.
Notes on Materials Properties and Applications

Noteworthy physical and chemical materials properties and application areas are briefly
reported if they were given in the original constitutional and phase diagram literature.
Miscellaneous
In this section noteworthy features are reported which are not described in preceding para-
graphs. These include graphical data not covered by the general report format, such as lattice
spacing – composition data, p-T-x diagrams, etc.

Introduction 1 7
. Fig. 5
Hypothetical vertical section showing notation employed
References
The publications which form the bases of the assessments are listed in the following manner:
[1974Hay] Hayashi, M., Azakami, T., Kamed, M., “Effects of Third Elements on the
Activity of Lead in Liquid Copper Base Alloys” (in Japanese), Nippon Kogyo Kaishi, 90, 51-
56 (1974) (Experimental, Thermodyn., 16)
This paper, for example, whose title is given in English, is actually written in Japanese. It
was published in 1974 on pages 51- 56, volume 90 of Nippon Kogyo Kaishi, the Journal of the
Mining and Metallurgical Institute of Japan. It reports on experimental work that leads to
thermodynamic data and it refers to 16 cross-references.
Additional conventions used in citing are:
# to indicate the source of accepted phase diagrams
* to indicate key papers that significantly contributed to the understanding of the system.
Standard reference works given in the list “General References” are cited using their
abbreviations and are not included in the reference list of each individual system.

8 1 Introduction
General References
[C.A.] Chemical Abstracts - pathways to published research in the world’s journal and patent literature -
http://www.cas.org/
[Curr.Cont.] Current Contents - bibliographic multidisciplinary current awareness Web resource - http://www.
isinet.com/products/cap/ccc/
[E] Elliott, R.P., Constitution of Binary Alloys, First Supplement, McGraw-Hill, New York (1965)
[G] Gmelin Handbook of Inorganic Chemistry, 8th ed., Springer-Verlag, Berlin
[H] Hansen, M. and Anderko, K., Constitution of Binary Alloys, McGraw-Hill, New York (1958)
[L-B] Landolt-Boernstein, Numerical Data and Functional Relationships in Science and Technology (New
Series). Group 3 (Crystal and Solid State Physics), Vol. 6, Eckerlin, P., Kandler, H. and Stegherr, A.,
Structure Data of Elements and Intermetallic Phases (1971); Vol. 7, Pies, W. and Weiss, A., Crystal
Structure of Inorganic Compounds, Part c, Key Elements: N, P, As, Sb, Bi, C (1979); Group 4:
Macroscopic and Technical Properties of Matter, Vol. 5, Predel, B., Phase Equilibria, Crystallographic
and Thermodynamic Data of Binary Alloys, Subvol. a: Ac-Au … Au-Zr (1991); Springer-Verlag,
Berlin.
[Mas] Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, ASM, Metals Park, Ohio (1986)
[Mas2] Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park,
Ohio (1990)
[P] Pearson, W.B., A Handbook of Lattice Spacings and Structures of Metals and Alloys, Pergamon Press,
New York, Vol. 1 (1958), Vol. 2 (1967)
[S] Shunk, F.A., Constitution of Binary Alloys, Second Supplement, McGraw-Hill, New York (1969)
[V-C] Villars, P. and Calvert, L.D., Pearson’s Handbook of Crystallographic Data for Intermetallic Phases,
ASM, Metals Park, Ohio (1985)
[V-C2] Villars, P. and Calvert, L.D., Pearson’s Handbook of Crystallographic Data for Intermetallic Phases,
2nd edition, ASM, Metals Park, Ohio (1991)

Index of Alloy Systems 2 1
Index of Alloy Systems

Index of Ternary Iron Alloy Systems Fe-N-V to Fe-Ti-Zr
Fe–N–V (Iron – Nitrogen – Vanadium)

Fe–Na–O (Iron – Sodium – Oxygen)
Fe–Nb–Ni (Iron – Niobium – Nickel)
Fe–Nb–P (Iron – Niobium – Phosphorus)
Fe–Nb–Si (Iron – Niobium – Silicon)
Fe–Nb–Zr (Iron – Niobium – Zirconium)
Fe–Nd–Si (Iron – Neodynium – Silicon)
Fe–Ni–P (Iron – Nickel – Phosphorus)
Fe–Ni–S (Iron – Nickel – Sulfur)
Fe–Ni–Sb (Iron – Nickel – Antimony)
Fe–Ni–Si (Iron – Nickel – Silicon)
Fe–Ni–Ti (Iron – Nickel – Titanium)
Fe–Ni–V (Iron – Nickel – Vanadium)
Fe–Ni–W (Iron – Nickel – Tungsten)
Fe–Ni–Zn (Iron – Nickel – Zinc)
Fe–Ni–Zr (Iron – Nickel – Zirconium)
Fe–O–Pb (Iron – Oxygen – Lead)
Fe–O–Si (Iron – Oxygen – Silicon)
Fe–O–U (Iron – Oxygen – Uranium)
Fe–O–W (Iron – Oxygen – Tungsten)
Fe–O–Y (Iron – Oxygen – Yttrium)
Fe–O–Zr (Iron – Oxygen – Zirconium)
Fe–P–Si (Iron – Phosphorus – Silicon)
Fe–S–Ti (Iron – Sulfur – Titanium)
Fe–Si–Ti (Iron – Silicon – Titanium)
Fe–Si–V (Iron – Silicon – Vanadium)
Fe–Si–Zr (Iron – Silicon – Zirconium)
Fe–Sm–Ti (Iron – Samarium – Titanium)
Fe–Sn–Zr (Iron – Tin – Zirconium)
Fe–Ti–V (Iron – Titanium – Vanadium)
Fe–Ti–Y (Iron – Titanium – Yttrium)
Fe-Ti-Zr (Iron – Titanium – Zirconium)

Fe–N–V 3 1
Iron – Nitrogen – Vanadium

Pierre Perrot
Introduction
Vanadium has a strong affinity for N and forms fine nitrides and carbonitrides in steels which
improve their strength and the toughness by pinning the grain growth to a considerable extent.
Experimental investigations on phase equilibria and thermodynamics, mainly related to the
nitrogen solubilities in liquid, α and γ phases are gathered in Table 1. Few experimental
information exists in the ternary phase diagram [1978ElS] and Calphad assessments
[1991Oht2] are useful to get an insight to the equilibria between phases. A review on the
phase equilibria in the Fe-N-V system may be found in [1983Rag, 1984Rag, 1987Rag1,
1993Rag]. A Calphad assessment of the Fe-N-V system has been carried out by [1991Oht2].
Binary Systems
The Fe-V has been carefully reviewed by [1984Smi] and the thermodynamic assessment
proposed by [1991Kum] reproduces well the accepted diagram. According to new experimen-
tal works [2005Ust1, 2005Ust2], the σ phase would be unstable and a phase separation would
be observed below 650˚C. A further confirmation is needed to accept this new version of the
Fe-V diagram at low temperatures. The Fe-N phase diagram in the solid state is accepted from
the review of [1987Wri]. The Calphad assessment carried out by [1991Fri] and justified by the
model proposed by [1994Fer] gives an insight on the phase equilibria under high nitrogen
pressures. The N-V phase diagram in the solid state given by [Mas2] is reproduced from the
extensive review of [1989Car]. A Calphad assessment of the N-V system has been carried out
by [1991Oht1], then updated by [1997Du]. These assessments do not take into account the
δ’V32N26 phase but agree to propose for the nitrides V2N and VN incongruent melting points
under 0.1 MPa N2 higher than those accepted by [Mas2]. The N-V diagram accepted in the
present report is that proposed by [1997Du].
Solid Phases
The solid phases are shown in Table 2. Three vanadium nitrides are stable. The most stable,
easily precipitated in steels is VN which presents a large non stoichiometry and may be
obtained under very low nitrogen potential. The hexagonal subnitride V2N, exhibits a
structure εFe3N like, but no solid solutions have been reported between these two phases.
The iron nitride γ’Fe4N is characterized by a high saturation magnetization and a low
coercitivity and many efforts has been devoted to enhance its magnetic properties by metallic
substitution. Many metastable phases of the type Fe4–xMxN have been prepared by mechanical
alloying, but no report seems to exist in which M stands for V. Despite this, self-consistent

2 3 Fe–N–V
band structure calculations were performed for the V4N, V3FeN and VFe3N materials
[2006San]. They were found non magnetic and their crystal structure calculated at 752.9,
742.7 and 704.9 pm respectively, whereas twice lattice parameter for Fe4N gives 757.4 pm.
[2006San] reports for γ’Fe4N a lattice parameter of 717.1 pm.
Isothermal Sections
The nitrogen solubility in liquid (Fe,V) alloys has been considerably investigated as shown in
Table 1, and was shown to increase with the V content, but the increase of the nitrogen
dissolved in the melt may be limited by the precipitation of VN for high V content of the alloy.
A useful empirical expression of the N solubility in liquid alloys at 1580˚C has been proposed
by [1963Kor]:
ðmass% NÞ ¼ 0:043 þ 0:0185 ðmass% VÞ þ 0:00113 ðmass% VÞ2 ð< 6 mass% VÞ
The precipitation is observed when the solubility product (mass% V)(mass% N) is
reached. As liquid Fe can dissolve a large amount of V before precipitating as VN, the
solubility product cannot be precisely represented by the product of concentrations, but by
the product of the activities. Another problem concerns the composition of the VN nitride in
equilibrium with the liquid alloy. [1965Eva] considers that its composition is V1.41N whereas
most authors consider that it is VN. The lattice parameter measurement carried out by
[1987Mor] identifies the precipitated nitride as VN. It is probable that VN in equilibrium
with iron rich (Fe,V) alloys and that the V content of the nitride increases with that of the
alloy. According to [1963ElT], a Fe-8V (mass%) alloy precipitates VN once the N content
reaches 0.20 mass% at 1600˚C under 8 kPa of N2 pressure; a Fe-15V (mass%) alloy preci-
pitates VN once the N content reaches 0.27 mass% at 1600˚C under 77 kPa of N2 pressure.
The nitrogen solubility in liquid alloys seems independent on the temperature for the Fe-1V
(mass%) [1958Kas]. Below 1 mass% V in the alloy, it decreases when the temperature raises,
above 1 mass% V in the alloy, it increases with the temperature [1987Mor].
The solubility of nitrogen generated by H2-NH3 atmospheres at 400-600˚C on α(Fe,V)
alloys up to 0.05 mass% V [1955Tur] seems independent on the V content of the alloy. The
formation of VN is not observed at nitrogen potentials under which iron nitrides are not
formed. The V content of the alloy was probably too small and the nitrogen solubility
measured in α and γ alloys [1958Fou, 1962Kor2] up to 1 mass% V was shown to increase
with the V concentration.
The solubility product of VN in α and γ alloys has been evaluated by [1962Kor2] and
accepted by [2004Ked] to model the nitrogen diffusion profile during nitriding:
In a ðFe; VÞ alloys : log10 ðmass% VÞðmass% NÞ ¼ 2:45 ð7830=TÞ
In g ðFe; VÞ alloys : log10 ðmass% VÞðmass% NÞ ¼ 2:27 ð7070=TÞ
At 700˚C, the solubility product of VN in (αFe) is 2.5 · 10–6 which is in agreement with
the formation of VN observed by [1973Gul] in an alloy Fe-0.18 mass% V-0.04 mass% N. At
1350˚C, the solubility product of VN in (γFe) is 0.0082 which is in agreement with the
observation of [1973Gul] that pure iron may absorb up to 0.2 mass% VN. The solubility
product of VN in (αFe) has been measured at 5.3 · 10–6 and 1.7 · 10–5 at 700 and 800˚C,
respectively, by [1973Koy] using internal friction measurements. The N solubility under

Fe–N–V 3 3
0.1 MPa of N2 pressure in iron rich alloys (< 2 mass% V) at 1200˚C (α and γ solid alloys) and
1600˚C (liquid alloy) is shown in Fig. 1.
Due to the lack of experimental information with the exception of the nitrogen solubilities
in α, γ and liquid phases, the isothermal sections have been calculated. The isothermal sections
at 1200 and 1600˚C, presented in Figs. 2 and 3 respectively, are mainly from [1991Oht2]
slightly modified to take into account the non stoichiometry of the binary compounds and the
solubility of N into (γFe) according to the accepted Fe-N diagram. Although a partial
solubility is probable, it has never been measured.

The vertical section through the Fe-N-V diagram at 3 mass% V calculated by [1991Oht2], is
shown in Fig. 4. The original figure has been slightly modified in order to remove the very
improbable shrinkage present at 900 and 1400˚C in the three-phase field α+γ+VN. It looks like
the binary Fe-N phase diagram calculated by [1991Fri] with an enlarged α domain. The
isobaric curves have not been calculated, but the nitrogen potentials (0.1 MPa at 1600˚C
and 0.044 mass% N) increase strongly with the N content. Below 800˚C, they may be obtained
with H2-NH3 atmospheres, but above this temperature, there is no known mean to impose
such high nitrogen potentials. The vertical section along the Fe-VN path (< 1 mass% VN) is
shown in Fig. 5. The easy precipitation of VN in the α and γ solid phases appears clearly in
both Figs. 4 and 5. In the liquid phase at 1600˚C, VN precipitates under 0.1 MPa N2 for a V
content in the alloys higher than 10 mass%.
Thermodynamics
The interaction coefficient between N and V in liquid iron calculated by [1960Mae] from
solubility measurements was found eN(V) = (∂ log10 fN / ∂ mass% V) = – 0.11 at 1600-1750˚C,
where fN = (mass% N in pure Fe) / (mass% N in the alloy). Such a value, is in a very good
agreement with that calculated from the data of [1958Kas] (–0.095 at 1600˚C) and with
the later measurements carried out by [1960Peh] (–0.10 at 1606˚C), [1961Rao] (–0.094 at
1700˚C), [1962Kor1] (–0.106 at 1580˚C), [1963ElT] (–0.094 at 1600˚C), [1965Eva] (–0.093
at 1600˚C and –0.079 at 1750˚C), [1975Pom] (–0.12 at 1600˚C, –0.099 at 1800˚C and –0.093 at
1900˚C), [1981Wad] (–0.10 at 1600˚C, –0.087 at 1700˚C and –0.076 at 1800˚C) and [1987Mor]
(–0.107 at 1600˚C). [1963Kor] proposes a more precise expression of the interaction para-
meter at 1580˚C, which may be used up to 6 mass% V in the alloy: eN(V) = –0.159 + 0.016
(mass% V), which agrees with the preceding values. [1963ElT] proposes, in the temperature
range 1600-1740˚C the following expression: eN(V) = 0.075 – 317 / T, which is more represen-
tative in a wide temperature range than more recent expressions [1981Wad, 1987Mor]. This
expression, extrapolated at 2200˚C leads to eN(V) = – 0.052 which agrees well with the
experimental value of –0.062 obtained by [1968Uda] at 2140-2240˚C by arc melting or
levitation melting under N2 atmospheres and with the experimental value of – 0.05 obtained
by [1969Wad] with the same method.
The interaction coefficient may be expressed in mole fractions. At 1600˚C [1966Sch,
1987Mor]: εN(V) = (∂ ln γN / ∂ xV) = – 20 at 1600˚C, where γN = (xN pure Fe / xN in the
alloy). For higher V content of the alloy, the preceding primary interaction coefficients cannot
be used and it is necessary to define secondary and sometimes ternary interaction coefficients
4 3 Fe–N–V
and to take into account the auto-interaction coefficient [2001Hut]. Indeed, under high
nitrogen pressure (> 0.1 MPa) and high V content (> 6 mass%), N has a strong effect on its
own activity coefficient. So, [2003Hut] describes the nitrogen solubility in (Fe,V) alloys up to
45 mass% V between 1800 and 2000˚C by using interaction coefficients of high order.
The interaction coefficients between N and V in α and γ iron have been calculated by
[1958Fou] from solubility measurements and found eN(V) = – 2.2, –1.0, –0.47, –0.33 and –0.18
at 750, 850, 950, 1050 and 1200˚C respectively. The slope of the curve does not seem present a
break at the α/γ transition of the alloy. These values are confirmed by the measurements of
[1962Kor2] which proposes eN(V) = – 0.4 at 1000˚C.
A general discussion on the interaction parameters in alloys may be found in [1966Sch].
A method of calculation based on equivalent carbon concentration was developed by
[1967Sch].
Table 3 presents the Gibbs energy of dissolution of N2 in liquid Fe-V alloys measured by
[1975Pom]. The enthalpy of dissolution of N2, positive for pure Fe, decreases when the V
content in the alloy increases, passes through zero for Fe-1V (mass%) then becomes more and
more negative. The nitrogen solubility in the Fe-1V (mass%) does not change with tempera-
ture, an observation already made by [1958Kas].
Main experimental investigations are gathered in Table 4. Vanadium, which in the liquid state
absorbs readily nitrogen, greatly increases its solubility in Fe base alloys without VN precipi-
tation. By solidification, these alloys precipitate VN, leading to a structural hardening of the
steel and an improvement of its tribological behavior, mechanical properties, especially under
fatigue loading and of its corrosion resistance. The easy absorption of N by (Fe,V) liquid alloys
without VN precipitation allows the preparation of HNS (High Nitrogen Steels, that are steels
with more than 0.5 mass% N) by using high nitrogen pressures. For instance, a Fe-12 mass%
V alloy at 1700˚C may absorb 0.503, 0.674, 0.847 and 1.400 mass% N under nitrogen pressures
of 0.372, 0.743, 1.86 and 2.27 MPa, respectively [2003Siw].
Vanadium and nitrogen cosegregation towards the surface has been observed on a Fe-3
mass% V annealed at 570-740˚C under a N2-H2 atmosphere (1 to 10 Pa N2) leading to a
nitrogen content of 4 to 30 ppm inside the alloy [1995Ueb]. N segregation gives a two-
dimensional surface compound whose composition is VN1.0 ±0.1. VN precipitates were also
observed by nitriding Fe-V alloys up to 3.3 at.% in a salt bath at 570˚C [2003Gou]. VN
precipitates as platelets, forming tweed structures, typical of a Guinier-Preston zone, due to a
tetragonal distortion of the matrix.
Miscellaneous
The nitrogen diffusion was investigated in the solid [1966Koe, 1973Bel, 1977Bor] and liquid
[1981Ers] alloys. In solid and liquid alloys, V has for effect to decrease the nitrogen diffusion
coefficient and to increase the activation energy of the diffusion. In pure αFe, the N diffusion
coefficient is given by:
DN / cm2·s–1 = 0.005 exp(–9260 / T), which corresponds to an activation energy of
77 kJ·mol–1. In a V added with 0.75 mass% V, the N diffusion coefficient is given by:
Fe–N–V 3 5
DN / cm2·s–1 = 0.0066 exp(–13 300 / T), which corresponds to an activation energy of

110.9 kJ·mol–1. Using the positron annihilation technique, [1990Wan] observes, on dilute
Fe-V alloys (0.29 mass% V) annealed at 500˚C under a 80H2-20NH3 atmosphere, the forma-
tion of VN clusters inside the Fe matrix. As V does not diffuse in Fe at so low temperature, it is
clear that N greatly enhances the V diffusion in Fe.
The nitrogen diffusion profile during the nitriding of a Fe-V alloy (0.5 and 1.0 mass% V) at
550-580˚C has been modeled by [2000Gou, 2004Ked]. The increase of the V content affects the
thickness of the nitrided layer, due to the formation of VN precipitates. After 70 h of diffusion
at 570˚C, the nitrided layer is 72 μm thick for pure Fe and 215 μm thick for Fe added with
1 mass% V. [2005Kam] presents a trapping model and points out that a realistic diffusion
model must take into account both precipitation and trapping.
The morphologies of the nitrided layers at 580˚C under H2-NH3 atmospheres were
compared by [2005Hos] on two Fe-V alloys (2 and 4 mass% V). The difference observed
was caused by a discontinuous coarsening reaction occurring on the Fe-4%V alloy, caused by
an uptake of excess nitrogen in the nitrided zone. It was observed, on the Fe-2V (mass%)
[2006Hos] that the hydrogen uptake was larger than that necessary to precipitate V as VN and
to saturate the ferrite matrix. Three types of nitrogen were recognized: nitrogen in the
stoichiometric VN, nitrogen adsorbed at the (αFe)/VN interface and nitrogen dissolved
interstitially in the ferrite matrix. The excess nitrogen uptake is partly due to the immobile
nitrogen at the interface (αFe)/VN and partly due to the mobile nitrogen supersaturated in the
(αFe) matrix. The supersaturation of the ferrite is due to the misfit stress field surrounding the
nitride precipitates. The excess nitrogen dissolved at the interface (αFe)/VN was shown to
decrease with increasing temperature [2007Hos].
The presence of V in liquid Fe at 1600˚C was shown to increase the rate of dissolution of
N2 by comparison with pure Fe [1995Ono].
. Table 1
Investigations of the Fe-N-V Phase Relations, Structures and Thermodynamics
Temperature/Composition/Phase Range
Reference Method/Experimental Technique Studied
[1955Tur] Nitrogen solubility in α(Fe,V) alloys, 500-600˚C, < 0.05 mass% V, H2-NH3
sampling method atmospheres
[1958Fou] Nitrogen solubility in α and γ(Fe,V) 750-120˚C, < 0.5 mass% V, < 0.1 MPa of
alloys, Sievert’s method N2 pressures
[1958Kas] Nitrogen solubility in liquid (Fe,V) alloys, 1600˚C, < 10 mass% V, < 0.1 MPa of N2
Sievert’s method pressure
[1960Mae] Nitrogen solubility in liquid (Fe,V) alloys, 1600-1750˚C, < 8 mass% V, 0.1 MPa of N2
Sampling method pressure
[1960Peh] Nitrogen solubility in liquid (Fe,V) alloys, 1606˚C, < 12 mass% V, < 0.1 MPa of N2
[1961Rao] Nitrogen solubility in liquid (Fe,V) alloys, 1687-1760˚C, < 20 mass% V, < 0.1 MPa of
Sievert’s method N2 pressure

6 3 Fe–N–V
. Table 1 (continued)
[1962Kor1] Nitrogen solubility in liquid (Fe,V) alloys, 1580˚C, < 12 mass% V, 0.1 MPa of N2
[1962Kor2] VN solubility in α (Fe,V) alloys, Sievert’s 900-1300˚C, < 1 mass% V, 0.1 MPa of N2
method pressure
[1963ElT] Nitrogen solubility in liquid (Fe,V) alloys, 1600-1750˚C, < 20 mass% V, < 0.1 MPa of
[1963Kor] VN solubility in liquid (Fe,V) alloys, 900-1300˚C, < 1 mass% V, 0.1 MPa of
[1965Eva] Nitrogen solubility in liquid (Fe,V) alloys, 1600-1750˚C, < 16 mass% V, 0.1 MPa of
[1968Uda] Nitrogen solubility in liquid (Fe,V) arc- 2140-2240˚C, < 6 mass% V, < 0.1 MPa of
and levitation melted alloys N2 pressure
[1969Wad] Nitrogen solubility in liquid (Fe,V) 1800-2200˚C, < 50 mass% V, < 0.1 MPa of
levitation melted alloys N2 pressure
[1973Gul] VN solubility in α and γFe, phase analysis 700-1350˚C, < 0.18 mass% V,
by electron microscopy < 0.04 mass% V
[1973Koy] VN solubility in αFe, internal friction, 700-800˚C, < 0.12 mass% V,
chemical analysis < 0.024 mass% N
[1975Pom] Nitrogen solubility in liquid (Fe,V) 1790-2150˚C, < 11 mass% V, < 0.4 mass% N,
melted by plasma < 0.1 MPa of N2 pressure
[1978ElS] XRD, Metallography, Electron Probe 1100-1200˚C, Fe-N-V constitution diagram
Microanalysis (EPMA) (~1 mPa N2)
[1981Wad] Nitrogen solubility in liquid (Fe,V) 1600-1800˚C, < 15 mass% V, < 0.1 MPa of
[1987Mor] Solubility if VN in liquid (Fe,V), XRD, 1600-1700˚C, < 25 mass% V, < 0.35 mass%
chemical analysis N, < 0.1 MPa of N2 pressure
[2001Hut] Nitrogen solubility in liquid (Fe,V) 1900˚C, < 12.2 mass% V, 0.1 to 2.1 MPa of
Levitation melted alloys N2 pressure
[2003Hut] Nitrogen solubility in liquid (Fe,V) 1800-2000˚C, < 45 mass% V, 1 kPa to 2.5
levitation melted alloys MPa of N2 pressure
[2003Siw] Nitrogen solubility in liquid (Fe,V) 1700˚C, < 12 mass% V, < 0.4 MPa of N2
levitation melted alloys pressure, < 1.4 mass% N

Fe–N–V 3 7
. Table 2
Crystallographic Data of Solid Phases
Phase/ Pearson Symbol/

Temperature Space Group/ Lattice Parameters
Range [˚C] Prototype [pm] Comments/References
α, (αFe,αV,δFe) cI2
(αV) Im3m a = 302.40 at 25˚C [Mas2]
< 1910 W dissolves 13 at.% N at 1959˚C
[1997Du]
(δFe) a = 293.15 [Mas2]
1538 - 1394
(αFe) a = 286.65 pure Fe at 20˚C [Mas2]
< 912 dissolves up to 0.4 at.% N at 590˚C
α(Fe0.5V0.5) a = 292.0 [1984Smi]
(γFe) cF4 a = 364.67 at 915˚C [Mas2, V-C2]
1394 - 912 Fm3m dissolves up to 10.3 at.% N at 650˚C
Cu [1987Wri] and 1.4 at.% V at 1150˚C
[1984Smi]
(εFe) hP2 a = 246.8 at 25˚C, 13 GPa [Mas2]
P63/mmc c = 396.0 triple point α-γ-ε at 8.4 GPa, 430˚C
Mg
σ, VFe tP30 29.6 to 60.1 at.% V
< 1252 P42/mnm a = 886.5 at 29.6 at.% V [1984Smi]
σCrFe c = 460.5
a = 895.0 at 50 at.% V [1984Smi]
c = 462.0
a = 901.5 at 60 at.% V [1984Smi]
c = 464.2
α”Fe16N2 tI* a = 572 ordered fcc structure, metastable
I4/mmn c = 629 [1987Wri]
γ’, Fe4N cP5 a = 378.7 19.4 to 20.6 at.% N. Ordered fcc
< 680 Pm3m structure [1987Rag2]
Fe4N
ε, Fe3N hP10 15.8 to 33.2 at.% N [1987Rag2]
< 580 P6322 a = 469.96 ± 0.03 εFe3N at RT [1999Lei]
Fe3N c = 438.04 ± 0.03
a = 471.8 εFe3N1.10 [2001Lei]
c = 438.8 Lattice parameters decrease
slightly with decrease in nitrogen
content [2001Lei]
a = 479.1 εFe3N1.39 [2001Lei]
c = 441.9

8 3 Fe–N–V

Temperature Space Group/ Lattice Parameters
ζFe2N oP12 a = 551.2 at 25˚C [1987Rag2]
< 500 Pbcn b = 482.0
Fe2N c = 441.6
βV2N hP3 24.2 to 32.9 at.% N [1984Rag]
< 2409 P63/mmc a = 283.68 to 284.08 [1984Rag]
(under 0.1 MPa N2) Fe3N c = 454.21 to 455.01
δVN cF8 33 to 50 at.% N [Mas2]
< 2119 Fm3m
(under 0.1 MPa N2) NaCl a = 406.62 at 42 at.% N [1984Rag]
< 3000
(under 1 GPa N2) a = 413.98 at 50 at.% N [1984Rag]
δ’V32N26 tP* - 43 to 46 at.% N [Mas2]
< 520 P42/nmc
-
. Table 3
Thermodynamic Data of Reaction or Transformation
Temperature Quantity, per mol of

Reaction or Transformation [˚C] atoms [J, mol, K] Comments
½ N2 Ð {N} (in Liquid Fe) 2000 ΔrH˚ = + 5600 [1975Pom]

½ N2 Ð {N} (in Liquid Fe + 1 mass% V) 1790-2130 ΔrG˚ = – 340 + 23.0 T [1975Pom]
½ N2 Ð {N} (in Liquid Fe + 2 mass% V) 1790-2110 ΔrG˚ = – 7660 + 25.7 T [1975Pom]
½ N2 Ð {N} (in Liquid Fe + 5.2 mass% V) 1810-2110 ΔrG˚ = – 28700 + 29.7 T [1975Pom]
VN Ð {V} + {N} (Ref: 1 mass% in liquid Fe) 1600-1700 ΔrG˚ = 167000 – 83.7 T [1987Mor]

Fe–N–V 3 9
. Table 4
Investigations of the Fe-N-V Materials Properties
Reference Method / Experimental Technique Type of Property
[1966Koe] Damping capacity, diffusion coefficient < 800˚C, < 4 mass% V, < 0.4 mass% N
[1973Bel] X-Ray and electron diffraction, MEB, 400-700˚C, < 9 mass% V, diffusion layer
hardness measurements formation
[1977Bor] XRD, micrography, thickness and 500-900˚C, < 15.6 mass% V, H2-NH3
hardness measurements atmospheres, layer growth kinetics
[1977Kra] XRD, electron microscopy, crystal < 800˚C, < 2 at.% V, < 3 at.% N, H2-NH3
parameters atmospheres, local atomic arrangements
[1981Ers] Diffusion coefficient of N in liquid alloys, 1600˚C, < 8 mass% V, 0.1 MPa of N2
volumetric method pressure
[1990Wan, Positron annihilation spectroscopy, 500˚C, Fe + 0.29 mass% V, 80H2-20NH3
1993Wan] observation of VN clusters atmosphere
[1995Ono] Isotopic exchange reaction 1600-1750˚C, 0.1 MPa of N2 pressure,
kinetics of dissolution
[1995Ueb] Auger Electron Spectroscopy (AES), low 570-740˚C, Fe-3 mass% V-N (4 to 30 ppm
energy electron diffraction N), 1 to 10 Pa of N2 pressure,
[2003Gou] XRD, TEM, Electron Microprobe Fe-V (< 3.3 at.% V) nitridized at 570˚C in
Microanalysis (EPMA) a nitriding fused salt bath. VN formation.
[2005Hos] XRD, SEM, EPMA, hardness 580˚C, 2 and 4 mass% V, H2-NH3
measurements atmospheres, morphology
[2006Hos] XRD, SEM, EPMA, hardness 580˚C, 2 mass% V, H2-NH3 atmospheres,
measurements excess N uptake
[2007Hos] XRD, SEM, EPMA, hardness 520-600˚C, 2 mass% V, 9H2-91NH3
measurements atmospheres, excess N uptake

10 3 Fe–N–V
. Fig. 1
Fe-N-V. The Fe rich corner at 1200 and 1600˚C under 0.1 MPa of N2 pressure

Fe–N–V 3 11
. Fig. 2
Fe-N-V. Isothermal section at 1200˚C

12 3 Fe–N–V
. Fig. 3
Fe-N-V. Isothermal section at 1600˚C

Fe–N–V 3 13
. Fig. 4
Fe-N-V. Partial vertical section at 3 mass% V

14 3 Fe–N–V
. Fig. 5
Fe-N-V. Calculated Fe-VN partial vertical section

Fe–N–V 3 15
References
[1955Tur] Turkdogan, E.T., Ignatowicz, S., Pearson, J., “The Effect of Alloying Elements on the Solubility of
Nitrogen in Iron. II. The Solubility of Nitrogen in α-Iron Containing up to 0.051% Vanadium”, J. Iron
Steel Inst., 181, 227–231 (1955) (Experimental, Phase Relations, 22)
[1958Fou] Fountain, R.W., Chipman, J., “Solubility and Precipitation of Vanadium Nitride in α- and γ-Iron”,
Trans. Met. Soc. AIME, 212, 737–748 (1958) (Experimental, Phase Relations, Thermodyn., 29)
[1958Kas] Kashyap, V.C., Parlee, N., “Solubility of Nitrogen in Liquid Iron and Iron Alloys”, Trans. Met. Soc.
AIME, 212, 86–91 (1958) (Experimental, Phase Relations, Thermodyn., 19)
[1960Mae] Maekawa, S., Nakagawa, Y., “Solubility of Nitrogen in Liquid Iron and Iron Alloys. II. Effect of Nickel,
Cobalt, Molybdenum, Chromium and Vanadium on the Solubility in Liquid Iron” (in Japanese), Tetsu
to Hagane, 46(9), 972–976 (1960) (Experimental, Phase Relations, Thermodyn., 8)
[1960Peh] Pehlke, R.D., Elliott, J.F., “Solubility of Nitrogen in Liquid Iron Alloys. I. Thermodynamics”, Trans.
Metall. Soc. AIME, 218, 1088–1101 (1960) (Experimental, Phase Relations, Thermodyn., 32)
[1961Rao] Rao, M.M., Parlee, N., “The Solubility of N in Liquid Fe-V and Fe-Ti Alloys and the Equilibrium in
Reaction xTi + N = δTixN” (in French), Mem. Sci. Rev. Met., 58(1), 52–60 (1961) (Experimental, Phase
Relations, Thermodyn., 6)
[1962Kor1] Korolev, L.G., Morozov, A.N., “Solubility of N in Liquid Fe-V Alloys” (in Russian), Izv. Vyss. Uchebn.
Zaved., Chern. Metall., 5(7), 27–30 (1962) (Experimental, Phase Relations, 5)
[1962Kor2] Korolev, L.G., Morozov, A.N., “Equilibrium of N with V in γFe” (in Russian), Izv. Vyss. Uchebn. Zaved.,
Chern. Metall., 5(9), 39–42 (1962) (Experimental, Phase Relations, Thermodyn., 4)
[1963ElT] El Tayeb, N.M., Parlee, N.A.D., “The Solubility of Nitrogen and the Precipitation of Vanadium Nitride
in Liquid Iron-Vanadium Alloys”, Trans. Met. Soc. AIME, 227, 929–934 (1963) (Experimental, Phase
[1963Kor] Korolev, L.G., Morozov, A.N., “Formation of V Nitride in Liquid Fe” (in Russian), Izv. Vyss. Uchebn.
Zaved., Chern. Metall., 6(4), 45–49 (1963) (Experimental, Phase Relations, Thermodyn, 3)
[1965Eva] Evans, D.B., Pehlke, R.D., “Equilibria of Nitrogen with Refractory Metals Titanium, Zirconium,
Columbium, Vanadium, and Tantalum in Liquid Iron”, Trans. Met. Soc. AIME, 233, 1620–1624 (1965)
(Experimental, Phase Relations, Thermodyn., 14)
[1966Koe] K̅ster, W., Horn, W., “Damping Investigation on Nitrided Iron-Molybdenum and Iron-Vanadium
Alloys” (in German), Arch. Eisenhuettenwes., 37, 245–252 (1966) (Experimental, Morphology, Mechan.
Prop., Transport Phenomena, 22)
[1966Sch] Schenck, H., Steinmetz, E., “Activity, Standart Condition and Coeffitient of Activity” (in German),
Stahleisen-Sonderberichte, Düsseldorf: Verlag Stahleisen, (7), 1–36 (1966) (Thermodyn., Review, 161)
[1967Sch] Schεrmann, E., Kunze, H.D., “Equivalent Interaction Parameters fort he N and S Solubilities, Activities
and Activity Coefficients in Three- and Multicomponent Alloys at 1600˚C” (in German), Giesserei-
forschung, 19, 101–108 (1967) (Theory, Calculation, Thermodyn., 10)
[1968Uda] Uda, M., Wada, T., “Solubility of Nitrogen in Arc-Melted and Levitation-Melted Iron and Iron Alloys”,
Trans. Nat. Res. Inst. Met. (Jpn.), 10(2), 79–91 (1968) (Experimental, Phase Relations, Thermodyn., 40)
[1969Wad] Wada, H., “Solubility of Nitrogen in Molten Fe-V Alloy”, Trans. Iron Steel Inst. Jpn., 9, 399–403 (1969),
translated from J. Jpn Inst. Met., 33, 720 (1969) (Experimental, Morphology, Phase Relations, Thermo-
dyn., 8)
[1973Bel] Belotskiy, A.V., Marchevskaya, E.I., Permyakov, V.G., “Nitride-Phase Formation in Fe-V-N System”,
Russ. Metall., (3), 103–105 (1973) (Experimental, Phase Relations, Transport Phenomena, 8)
[1973Gul] Gulyaev, A.P., Anashenko, V.N., Karchevskaya, N.I., Larina, O.D., Matrosov, Yu.I., “Solubility of
Vanadium and Niobium Nitrides in Iron”, Met. Sci. Heat Treat., 15(8), 643–645 (1973), translated from
Metalloved. Term. Obrab. Met., (8), 6-8 (1973) (Experimental, Kinetics, Morphology, Phase Relations, 4)
[1973Koy] Koyama, S., Ishii, T., Narita, K., “Solubility of Vanadium Carbide and Nitride in Ferritic Fe” (in
Japanese), J. Jpn. Inst. Met., 37(2), 191–196 (1973) (Experimental, Phase Relations, 23)
[1975Pom] Pomarin, Yu.M., Grigorenko, G.M., Lakomskiy, V.I., “Solubility of Nitrogen in Liquid Iron Alloys with
Vanadium or Niobium”, Russ. Metall., (5), 61–65 (1975), translated from Izv. Akad. Nauk SSSR, Met.,
(5), 74-77 (1975) (Experimental, Phase Relations, Thermodyn., 15)
[1977Bor] Bor, S., Atasoy, Ö.E., “The Nitriding of Fe-V Alloys”, Metall. Trans. A, 8A(6), 975–979 (1977) (Experi-
mental, Morphology, Kinetics, Surface Phenomena, 14)

16 3 Fe–N–V
[1977Kra] Krawitz, A., “X-Ray Studies of Fe-Mo and Fe-V Alloys Nitrided by Constant Activity Aging”, Scr.
Metall., 11(2), 117–122 (1977) (Crys. Structure, Experimental, 17)
[1978ElS] El-Shahat, M.F., Holleck, H., “The Constitution of the Systems V-(Fe,Co,Ni,)-N” (in German),
Monatsh. Chem., 109(1), 193–207 (1978) (Crys. Structure, Experimental, Morphology, Phase Diagram,
Phase Relations, 14)
[1981Ers] Ershov, G.S., Kasatkin, A.A., “Influence of Alloying Elements on the Diffusion of Nitrogen in Liquid
Iron”, Russ. Metall., (3), 24–27 (1981) (Experimental, Transport Phenomena, 13)
[1981Wad] Wada, H., Pehlke, R.D., “Nitrogen Solubility in Liquid Fe-V and Fe-Cr-Ni-V Alloys”, Metall. Trans. B,
12B, 333–339 (1981) (Experimental, Phase Relations, Thermodyn., 10)
[1983Rag] Raghavan, V., “The Fe-N-V (Iron-Nitrogen-Vanadium) System”, Trans. Ind. Inst. Met., 36(4/5), xvii-
xxiii (1983) (Crys. Structure, Phase Diagram, Phase Relations, Review, 36)
[1984Rag] Raghavan, V., “The Fe-N-V (Iron-Nitrogen-Vanadium) System”, Bull. Alloy Phase Diagrams, 5(2),
194–198 (1984) (Crys. Structure, Phase Diagram, Phase Relations, Review, 36)
[1984Smi] Smith, J.P., “The Fe-V (Iron-Vanadium) System”, Bull. Alloy Phase Diagrams, 5(2), 184–194 (1984)
(Crys. Structure, Phase Diagram, Review, Thermodyn., 99)
[1987Mor] Morita, Z., Tanaka, T., Yanai, T., “Equilibria of Nitride Forming Reactions in Liquid Iron Alloys”,
Metall. Trans. B, 18B, 195–202 (1987) (Crys. Structure, Experimental, Phase Relations, Thermodyn., 29)
[1987Rag1] Raghavan, V., “The Fe-N-V (Iron-Nitrogen-Vanadium) System” in “Phase Diagrams of Ternary Iron
Alloys”, Ind. Inst. Techn., Delhi, 1, 211–216 (1987) (Crys. Structure, Phase Diagram, Phase Relations,
Review, 32)
[1987Rag2] Raghavan, V., “The Fe-N (Iron-Nitrogen) System” in “Phase Diagrams of Ternary Iron Alloys”, Ind. Inst.
Techn., Delhi, 1, 143–144 (1987) (Crys. Structure, Experimental, Phase Diagram, Phase Relations, 7)
[1987Wri] Wriedt, H.A., Gokcen, N.A., Nafziger, R.H., “The Fe-N (Iron-Nitrogen) System”, Bull. Alloy Phase
Diagams, 8(4), 355–377 (1987) (Crys. Structure, Phase Diagrams, Phase Relations, Thermodyn.,
Review, *, #, 126)
[1989Car] Carlson, O.N., Smith, J.F., Nafziger, R.H., “The V-N (Vanadium-Nitrogen) System” in “Phase Diagams
of Binary Vanadium Alloys”, ASM Int., Materials Park, OH, 148–158 (1989) (Phase Diagram, Phase
Relations, Crys. Strucrure, Thermodyn., Review, 59)
[1990Wan] Wang, X.-G., Zhang, H., “A Vacancy Complex in the Dilute Fe-V-N Alloy Identified by Positron
Annihilation Spectroscopy”, Phys. Status Solidi A, 119(1), K15-K19 (1990) (Crys. Structure, Experi-
mental, Transport Phenomena, 7)
[1991Fri] Frisk, K., “A Thermodynamic Evaluation of the Fe-Ni-N System”, Z. Metallkd., 82, 59–66 (1991) (Phase
Diagram, Assessment, Thermodyn., 36)
[1991Kum] Kumar, K.C.H., Raghavan, V., “A Thermodynamic Reassessment of the Fe-V System”, Calphad, 15(3),
307–314 (1991) (Phase Diagram, Thermodyn., Assessment, 24)
[1991Oht1] Ohtani, H., Hillert, M., “A Thermodynamic Assessment of the V-N System”, Calphad, 15(1), 11–24
(1991) (Phase Diagram, Assessment, Thermodyn., 27)
[1991Oht2] Ohtani, H., Hillert, M., “A Thermodynamic Assesment of the Fe-N-V System”, Calphad, 15(1), 25–39
(1991) (Calculation, Experimental, Phase Diagram, Phase Relations, Thermodyn., 24)
[1993Rag] Raghavan, V., “Fe-N-V (Iron-Nitrogen-Vanadium)”, J. Phase Equilib., 14(5), 631–632 (1993) (Phase
Diagram, Phase Relations, Review, 7)
[1993Wan] Wang, X.-G., Zhang, H., “Precipitation in Dilute Fe-V-N Alloy”, Acta Metall. Sin., 29(5), A199-A202
(1993) (Crys. Structure, Experimental, Transport Phenomena, 12)
[1994Fer] Fernandez-Guillermet, A., Du, H., “Thermodynamic Analysis of the Fe-N System Using the
Compound-Energy Model with Prediction of the Vibrational Entropy”, Z. Metallkd., 85(3), 154–163
(1994) (Phase Diagrams, Theory, Assessment, 75)
[1995Ono] Ono, H., Morita, K., Sano, N., “Effect of Ti, Zr, V and Cr on the Rate of Nitrogen Dissolution
into Molten Iron”, Met. Mat. Trans. B, 26B(5), 991–995 (1995) (Experimental, Kinetics, Surface
Phenomena, 11)
[1995Ueb] Uebing, C., “Cosegregation-Induced Phase Transition on Fe-3%V-N (110): The Formation of a VN
Surface Compound”, Surf. Sci., 341(1-2), L1125–L1130 (1995) (Experimental, Interface Phenomena,
[1997Du] Du, Y., Schmid-Fetzer, R., Ohtani, H., “Thermodynamic Assessment of the V-N System”, Z. Metallkd.,
88(7), 545–556 (1997) (Assessment, Experimental, Phase Relations, Review, Thermodyn., 72)

Fe–N–V 3 17
[1999Lei] Leineweber, A., Jacobs, H., Hüning, F., Lueken, H., Schilder, H., Kockelmann, W., “ε-Fe3N:
Magnetic Structure, Magnetization and Temperature Dependent Disorder of Nitrogen”, J. Alloys
Compd., 288(1-2), 79–87 (1999) (Experimental, Crys. Structure, 40)
[2000Gou] Goune, M., Belmonte, T., Fiorani, J.M., Michel, H., “Modelling of Diffusion-Precipitation in Nitrided
Alloyed Iron”, Thin Solid Films, 377, 543–549 (2003) (Calculation, Interface Phenomena, Phase Rela-
tions, 27)
[2001Hut] Hutny, A., Siwka, J., “Investigation of Nitrogen Solubility in Liquid Fe-V Alloy with the Use of
Levitation Technique”, Arch. Metall., 46(2), 197–206 (2001) (Experimental, Phase Relations, Thermo-
dyn., 12)
[2001Lei] Leineweber, A., Jacobs, H., Hünning, F., Luecken, H., Kockelmann, W., “Nitrogen Ordering and
Ferromagnetic Properties of ε-Fe3N1+x (0.10 < x < 0.39) and ε-Fe3(N0.80C0.20)1.38”, J. Alloys Compd., 316,
21–38 (2001) (Experimental, Crys. Structure, 47)
[2003Gou] Goune, M., Belmonte, T., Redjaimia, A., Weisbecker, P., Fiorani, J.M., Mochel, H., “Thermodynamic
and Structure Studies on Nitrided Fe-1.62%Mn and Fe-0.56%V Alloys”, Mater. Sci. Eng. A, 351, 23–30
(2003) (Crys. Structure, Experimental, Interface Phenomena, Phase Diagram, Phase Relations, 22)
[2003Hut] Hutny, A., Siwka, J., “The Dependence of Activity Coefficient on Intensive Thermodynamic Parameters
in a Liquid Fe-N-V Alloy”, Mater. Sci. Forum, 426-432, 963–968 (2003) (Experimental, Phase Relations,
Thermodyn., 10)
[2003Siw] Siwka, J., Kaputkina, L.M., Shaidurova, E.S., Hutny, A., “The Crystallization, Structure and Work
Hardening of Casting Fe-N-V Alloys”, Mater. Sci. Forum, 426-432, 4405–4410 (2003) (Experimental,
Mechan. Prop., Phase Relations, 15)
[2004Ked] Keddam, M., Djeghlal, M.E., Barrallier, L., Hadjadj, R., “A Computer Simulation of Nitrogen Profiles in
Fe-V-N Ternary System”, J. Alloys Compd., 378(1-2), 163–166 (2004) (Calculation, Transport Phenom-
ena, Kinetics, 10)
[2005Hos] Hosmani, S.S., Schacherl, R.E., Mittemeijer, E.J., “Nitriding Behavior of Fe-4 wt% V and Fe-2 wt% V
Alloys”, Acta Mater., 53(7), 2069–2079 (2005) (Experimental, Interface Phenomena, Mechan. Prop.,
Morphology, 31)
[2005Kam] Kamminga, J.D., Janssen, G.C.A.M., “Calculation of Nitrogen Depth Profiles in Nitrided Fe-Mn and
Fe-V”, Surf. Coat. Technol., 200(1-4), 909–912 (2005) (Calculation, Transport Phenomena, Kinetics, 10)
[2005Ust1] Ustinovshchikov, Yu.I., Pushrarev, B.E., Sapegina, I.V., “Mechanism of Sigma-Phase Formation in the
Fe-V System”, Inorg. Mater. (Engl. Trans.), 41(8), 822–826 (2005), translated from Neorg. Mater., 41(8),
938-943 (2005) (Crystal Structure, Experimental, Mechan. Prop., Morphology, Phase Diagram, Phase
Relations, 12)
[2005Ust2] Ustinovshikov, Y., Pushkarev, B., Sapegina, I., “Phase Transformations in Alloys of the Fe-V System”,
J. Alloys Compd., 398(1-2), 133–138 (2005) (Crystal Structure, Experimental, Mechan. Prop., Phase
Diagram, Phase Relations, 9)
[2006Hos] Hosmani, S.S., Schacherl, R.E., Mittemeijer, E.J., “Nitrogen Uptake by an Fe-V Alloy: Quantitative
Analysis of Excess Nitrogen”, Acta Mater., 54(10), 2783–2792 (2006) (Experimental, Interface Phenom-
ena, Kinetics, Morphology, 38)
[2006San] Dos Santos, A.V., Krause, J.C., Kuhnen, C.A., “Electronic Structure Calculations and Ground State
Properties of V4N, FeV3N and VFe3N Nitrides and Ordered FeV3 and VFe3 Compounds”, Physica B, 382
(1-2), 290–299 (2006) (Crys. Structure, Electronic Structure, Calculation, 43)
[2007Hos] Hosmani, S.S., Schacherl, R.E., Mittemeijer, E.J., “Kinetics of Nitriding Fe-2 wt% V Alloy: Mobile and
Immobile Excess Nitrogen”, Metall. Mater. Trans. A, 38A(1), 7–16 (2007) (Experimental, Kinetics, 28)
[Mas2] Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park, Ohio
(1990)
[V-C2] Villars, P. and Calvert, L.D., Pearson’s Handbook of Crystallographic Data for Intermetallic Phases, 2nd
edition, ASM, Metals Park, Ohio (1991)

Fe–Na–O 4 1
Iron – Sodium – Oxygen

Kostyantyn Korniyenko, Hans Leo Lukas
Introduction
Knowledge of the phase equilibria in the iron-sodium-oxygen system and free energies of
formation of sodium ferrites at elevated temperatures is necessary, in the first instance, with a
view to analyze the corrosion behavior of sodium in nuclear reactors and to address the problem
of scabbing and scaffolding in blast furnaces that is due to high alkali content. Information about
phase relations in the Fe-Na-O system is presented in literature by the Fe3O4-NaFeO2 quasibin-
ary section [1984Dai2], liquidus surface of the partial FeO-Fe2O3-NaFeO2 system [1984Dai2],
isothermal sections and phase relations at different temperatures and composition ranges
[1975Cla, 1976Bal2, 1977Kni, 1981Lin, 1984Dai2, 1986Igu, 1993Sri, 1999Kal, 2003Hua2,
2003Lyk] and temperature-composition sections [1940Kni, 1960The, 1962The, 1984Dai1,
1984Dai2]. Crystal structure data obtained by powder- or single crystal X-ray diffraction are
published by [1959Col, 1960The, 1962Roo, 1962The, 1963Sch, 1967Rom, 1970Gro, 1971Tsc,
1974Bar, 1974Rie, 1975Cla, 1975Kol, 1976Bal1, 1976Bal2, 1977Bra, 1977Kni, 1978Bra1,
1978Bra2, 1978Bra3, 1980Kes, 1981Kes, 1981Oka, 1985Fru, 1986Igu, 1997Ded, 2002Ama,
2003Sob1, 2003Sob2]. Thermodynamic aspects of the Fe-Na-O system are reflected in
[1970Gro, 1977Kni, 1977Sha, 1981Lin, 1984Ban, 1984Dai1, 1984Dai2, 1985Ban1, 1985Ban2,
1987Yam, 1988Bha, 1996Zha, 1999Kal, 2003Hua1, 2003Hua2, 2003Lyk]. The applied experi-
mental techniques as well as the studied temperature and composition ranges are listed in
Table 1. Reviews of literature data present information concerning phase equilibria and crystal
structures [1989Rag], thermodynamics [1981Lin, 1999Kal] as well as systematics of crystal
structures of the Fe-Na-O phases [1978Zve, 1982Bau, 1998Wu, 2000Mat, 2003Mue].
In future further studies are desirable on the liquidus and solidus surfaces in the area FeO-
Na2O-NaO3-Fe2O3 as well as on invariant equilibria. More details of isothermal sections at
different temperatures would be useful. New informations may help to find new practical
applications of sodium ferrites.
Binary Systems
The Fe-Na, Fe-O and Na-O binary systems are accepted as compiled in [Mas2]. The assess-
ment of the Na-O system is published with more details by [1987Wri].
Solid Phases
Crystallographic data of all known unary, binary and ternary solid phases are compiled in
Table 2. Compositions of the all reported ternary phases, except the τ9 and τ12 phases, lie along
the Na2O-FeO or Na2O-Fe2O3 sections. The composition of the τ6 phase, established by
[1959Col, 1962The, 1999Kal] as “Na10Fe16O29”, was later refined by [1962Roo, 1967Rom,
2 4 Fe–Na–O
1987Yam, 1996Zha, 1999Kal] to be “Na3Fe5O9”. For the τ2 phase the standard Gibbs energy of
formation was determined by [1984Dai1] using emf, but no crystal structure data are known.
For many of the ternary phases the temperature range of stability is not known, except the
temperature of preparation. The crystal structures of the phases τ11, τ12 and τ13 also are
unknown and need further experimental clarification.
Quasibinary Systems
The section Fe2O3-Na2O is quasibinary, at least in solid state at lower temperatures. In the
range Fe2O3-NaFeO2 [1940Kni, 1984Dai1] assume a simple eutectic near 1150˚C and Na/(Na
+Fe) = 0.36, whereas [1960The, 1962The] found in solid state the τ6 phase, stable between
1100 and 755˚C. Additionally they found a metastable solid solution of Na2O in γFe2O3,
decomposing on heating above 650˚C. The pure Fe2O3 before melting decomposes into Fe3O4
and O2 gas. Thus the two-phase field L + Fe2O3 must end before it reaches the Fe2O3 side of the
section. The liquidus temperature of NaFeO2 is assumed as 1330˚C [1940Kni, 1984Dai1].
Between NaFeO2 (τ1´´´-τ1´) and Na2O there are at least five more phases in this quasibinary
section, well established by the determination of their crystal structures: Na4Fe2O5 (τ4),
Na14Fe6O16 (τ8), Na3FeO3 (τ10), Na8Fe2O7 (τ5) and Na5FeO4 (τ7). On the temperature ranges
of stability and on equilibria with melt no experimental data are published for these phases. A
further phase, τ13, between τ6 and τ1´, postulated by [1981Lin], was denied by [1962The,
1999Kal]. In Fig. 1 the Fe rich part of this section is constructed. The equilibria between gas,
liquid, Fe2O3 and Fe3O4 must be taken as tentative only. The Fe rich liquid, due to Fe+2 ions
does not reach the section and Na rich liquid may dissolve more O than corresponding to the
section, due to peroxide or ozonide ions known in the binary Na-O liquid. On the transition
between both cases data are lacking.
The section FeO-Na2O is quasibinary in the range Na2FeO2-Na2O [1984Dai1, 1984Dai2].
Between Na2FeO2 and FeO it is clearly a not quasibinary isopleth, Fig. 2. At lower tempera-
tures also the range Na2O to Na4FeO3 looses the quasibinary character. [2003Hua2] calculated
an invariant reaction: Na(liq) + Na4FeO3 Ð Na2O + (αFe) at 421˚C. This temperature may be
a reasonable estimate. [1993Sri] found this reaction experimentally and located it somewhere
between 353 and 487˚C.
The Fe3O4-NaFeO2 section is approximately quasibinary. The Fe3O4 phase has some
homogeneity range towards a composition NaFe5O8, corresponding to the spinel structure
of γFe3O4, in which the divalent Fe+2 ions may be replaced by 0.5(Fe+3 + Na+1). Due to the
difference between this direction and the section plane the tie lines of the two-phase fields
containing γFe3O4 are slightly outside the section plane. Contrary to a strictly quasibinary
section all these fields contain a trace of FeO and thus are three-phase fields. Figure 3 shows
this approximately quasibinary section as published by [1984Dai2] with correction of a typing
error. The horizontal lines at ca. 1150 and 980˚C correspond to the invariant four-phase
equilibria L Ð γFe3O4 + αFeO + τ1´´´ and τ1´´´ Ð τ1´´, γFe3O4, αFeO, respectively.
[1984Dai2] constructed the liquidus surface of the FeO-Fe2O3-NaFeO2 partial system. These
authors mention four invariant four-phase reactions. In Fig. 4 the corresponding reaction
Fe–Na–O 4 3
scheme is tentatively constructed. It covers the area Fe-Na2FeO2-NaFeO2-Fe2O3. The τ6 phase

is tentatively included, assuming no participation in an invariant equilibrium. The three-phase
equilibria of the quasibinary part Na2O-Na2FeO2 can be approximated as degenerate four-
phase equilibria with Fe in equilibrium. By this consideration the congruent melting point of
Na2FeO2 in the quasibinary part of the Na2O-FeO section is also a degenerate maximum of the
three-phase equilibrium L + Fe + Na2FeO2. Thus only the formation of the three-phase
equilibrium L + τ1 + τ2 remains unsolved in the reaction scheme. The compositions of liquid
in the invariant equilibria are too unprecise to justify a tabulation. In Fig. 4 the polymorphic
transformations of (Fe) and NaFeO2 (τ1) are neglected. As at both compositions all phases are
nearly stoichiometric, all these transformations are degenerate with the equations (δFe) Ð
(γFe), (γFe) Ð (αFe), τ1´´´ Ð τ1´´ or τ1´´ Ð τ1´. All other phases participating remain in
equilibrium at higher and lower temperatures without taking part at the reactions. Phase τ12
was not mentioned by [1984Dai2] and is not implemented in Fig. 4.
Outside the range of Fig. 4 the existence of the invariant four-phase equilibrium
L(Na) + Na4FeO3 Ð (Fe) +Na2O is well established, its temperature is inside the interval
487-353˚C [1993Sri], but could not be located more precisely.
Liquidus, Solidus and Solvus Surfaces
The liquidus surface projection of the partial FeO-Fe2O3-NaFeO2 system is shown in Fig. 5,
based on [1984Dai2]. Isotherms at the temperatures of 1300, 1400 and 1500˚C are plotted. No
data concerning solidus or solvus surfaces were found in literature.
Isothermal Sections
The isothermal section of the partial Fe-Fe2O3-NaFeO2 system at 1000˚C is shown in Fig. 6, as
constructed by [1986Igu], based on experimental studies of the FeO-Na2O solid solution in
equilibrium with Ar-H2-H2O mixtures. The shapes of the single phase fields of the FeO-Na2O
and Fe3O4-Na2O solid solutions agree well with the findings of [1975Cla, 1976Bal2, 2003Lyk],
except, that [1976Bal2, 2003Lyk] postulate the existence of τ12, which is not mentioned by
[1975Cla, 1984Dai2, 1986Igu]. [1986Igu] also ignored the τ6 phase, which is reported to be
stable at 1000˚C [1962The, 1999Kal].
Participation of the τ6 phase in equilibria at 1000˚C was also reported in the works of
[1960The] and [1962The, 1999Kal] devoted to constitution of the NaFeO2-Fe2O3 tempera-
ture-composition section. The partial isothermal section at 1000˚C in the FeO-Fe3O4-
NaFe5O8-NaFeO2 range was also experimentally constructed by [2003Lyk]. These authors
report the τ13 phase, but do not show the τ6 phase. In general, their data conform to the data of
[1986Igu] satisfactorily. In their studies of corrosion of steel by liquid Na [1977Kni] found at
650˚C the τ3 phase in equilibrium with (αFe) and liquid sodium, while at 400˚C the tie line Na-
τ3 is replaced by an equilibrium between Na2O and (αFe). In the calculations of [2003Hua2]
the corresponding four-phase reaction was located at 421˚C. [1993Sri] experimentally con-
firmed this four-phase reaction to happen between 353 and 487˚C. [1981Lin] used the
SOLGAMIX-PV computer program to calculate phase equilibria in the temperature range
from 447 to 607˚C in the partial Na-Na2O-Fe2O3-Fe system. They reported the ternary phases
τ1, τ2, τ3, τ5, τ6, τ7, τ10 and τ13 to take part in equilibria in this temperature interval. However,
4 4 Fe–Na–O
they do not mention the eutectoid decomposition of FeO at 570˚C, due to which FeO should
not take part in equilibria far below 570˚C. The 595˚C isothermal section, constructed by
[1984Dai2] from their experimental data (Fig. 7), differs as far as the three iron oxides FeO,
Fe3O4 and Fe2O3 all are in equilibrium with NaFeO2 (τ1), whereas [1981Lin] show them in
equilibrium with Na3Fe5O9 (τ6) or Na4Fe6O11 (τ13). [1984Dai2] left the phases τ4, τ8, τ10, τ5
and τ7 outside their investigated range. [2003Hua2] published six calculated isothermal
sections between 25 and 727˚C. In this calculation they did not include the phases τ2, τ4, τ6,
τ8, τ9, τ11, τ12 and τ13. The thermodynamic dataset used for the calculation is published. Apart
from the excluded phases these sections agree well with Fig. 7. The phase τ5 appears to be
stable only above 364˚C and the invariant reaction L(Na) + Na4FeO3 Ð Fe +Na2O is located at
421˚C. Some of the dashed lines in the O rich part of Fig. 7 may be replaced by equilibria with
Na- and O rich liquid.

Besides the partially or approximately quasibinary sections shown in Figs. 1 to 3 the tempera-
ture-composition section NaFeO2-FeO is shown in Fig. 8 based on data of [1984Dai1,
1984Dai2]. The authors qualify this section as qualitative representation of the phases in
this section.
Thermodynamics
Information about thermodynamic properties of the Fe-Na-O alloys is widely represented in
the literature. Data concerned the reactions are listed in Table 3. The chemical equilibria of
gas-slag reactions have been studied by [1984Ban, 1985Ban1, 1985Ban2] to clarify the effect of
soda on the thermodynamic properties of slags in the hot metal treatment. The FeO-Na2O
slags were studied at 1610˚C being equilibrated with pCO2 = 1.013 bar by using a platinum
crucible. The influence of slag composition on the activity of iron oxide and the Fe3+/Fe2+
ratios has been determined. It has been clarified, that the results can be expressed in terms of
the Lumsden’s regular solution model over a wide range of compositions. [1984Dai1], besides
the results presented in Table 3, also have estimated the standard Gibbs energies of formation
of the compounds Na2FeO4, Na2FeO2 and Na4FeO3 referred to the pure elements iron, sodium
and oxygen.
Table 4 presents results of vapor pressure measurements. The oxygen and sodium partial
pressures were calculated by [1984Dai1] from the Gibbs energy functions. [1984Dai2]
obtained an expression for the oxygen partial pressure of the three-phase equilibrium α +
(Fe) + Na2Fe2O4 in the temperature range 760 to 910˚C. Oxygen and sodium potential ranges
at 650˚C for the stability of selected equilibria in the Fe-Na-O system were determined by
[1977Kni].
[2003Lyk] proposed a thermodynamic model for solid solutions of sodium in the α phase,
that provides a possibility to establish a relation between the equiliubrium oxygen pressure,
composition of the α phase and temperature.
Thermodynamic calculations of isothermal sections of the Fe-Na-O system at the tem-
peratures up to 727˚C were carried out by [2003Hua2] using the Thermo-Calc code. Thermo-
dynamic data of the ternary phases Na4FeO3(s), Na3FeO3(s), Na5FeO4(s) and Na8Fe2O7(s)
Fe–Na–O 4 5
have been assessed and compiled to a database by reviewing literature data together with DSC
and vapor pressure measurements conducted by the authors themselves.
Sodium ferrites have been used, in particular, as reference electrodes in conjunction with
sodium-iron-conducting solid electrolytes and, more recently, in sodium and antimony
sensors, because of their good electronic conductivity [1996Kal, 1996Zha, 1999Kal], which
produces a rapid response of the sensor. Literature data about properties of the Fe-Na-O alloys
concern mainly the magnetic properties (Table 5). The magnetic interaction in the structural
units {Fe2O7}8–, built of two corner-sharing FeO4 tetrahedra, in the τ5 phase was studied by
[1981Kes] in the temperature range from 4.2 to 500 K (–269 to 227˚C). The hypothesis of
magnetically isolated {Fe2O7}8 groups was corroborated by Mössbauer spectroscopy between
1.5 and 77 K (–271.7 and –196˚C). Authors of [1967Rom] have determined that the τ6 phase
crystals possess antiferromagnetic properties and a possible arrangement of magnetic spins
was discussed. Magnetic properties of the τ7 phase are reported in [1980Kes] and [1985Fru].
The susceptibility obeys a Curie-Weiss law down to 4.2 K, within experimental error, with
effective magnetic moment μeff = 5.83·μB, very close to the spin-only value 5.92·μB, and the
Curie temperature is θ = –13 K. At low temperature the magnetic ordering takes place (the
Néel temperature TN = 5.40 K). Authors of [1975Cla] and [1976Bal2] have investigated
magnetic properties of alloys from the Fe-Fe2O3-NaFeO2 partial system annealed at 1000˚C.
It was established, in particular, that with increasing sodium content of the alloys the Néel
temperature values decrease. In opinion of [1997Ded], the Fe-Na-O system is prospective for
the study of derivatives of iron in higher oxidation states. The use of oxidizer in abundance in
solid-state oxidation synthesis can get novel information about valent possibilities of transi-
tion metals. For the first time the data about quadrupole and magnetic interactions of iron in
higher oxidation state in the Fe-Na-O system (the Na2O2-Fe2O3 section) were obtained by
[1997Ded].
Miscellaneous
The mechanism of iron transport by liquid sodium in non-isothermal loop system was studied
by [1975Kol]. The loop system was constructed from an AISI Type 316 steel. The sodium was
heated from 400˚C to 700˚C in the heated zone of the system and cooled down reversibly in the
cooled zone. In the cooled zone four specimen holders were invariably mounted, the exposi-
tion temperatures being 650, 600, 500 and 400˚C. Based on the obtained results a model for
the transport of iron from the heated zone to the cooled zone was proposed.

6 4 Fe–Na–O
. Table 1
Investigations of the Fe-Na-O Phase Relations, Structures and Thermodynamics
Temperature/Composition/Phase
Reference Method/Experimental Technique Range Studied
[1940Kni] as Thermal analysis The NaFeO2-Fe2O3 section

quoted by
[1984Dai1]
[1960The] X-ray diffraction 300-700˚C, NaFeO2-Fe2O3 section
[1962Roo] as Crystal structure studies Na3Fe5O9
quoted by
[1999Kal]
[1962The] Dilatometry, X-ray diffraction ≤ 1300˚C, NaFeO2-Fe2O3 section
[1963Sch] X-ray diffraction, solubility tests Room temperature, NaFeO2-Fe2O3
section
[1967Rom] X-ray diffraction (single crystals, 1100˚C, room temperature,
Weissenberg goniometer), Patterson complete crystal structure of
methods, heavy-atom technique Na3Fe5O9
[1970Gro] X-ray diffraction, solution calorimetry 500-600˚C, ΔH of Na4FeO3
[1971Tsc] X-ray diffraction 450˚C, 650˚C, three phases in the
Na2O-NaFeO2 section
[1974Bar] X-ray diffraction > 600˚C, Na4FeO3 as corrosion
product of Na steel
[1974Rie] Guinier X-ray diffraction Crystal structure of Na4FeO3
[1975Cla] X-ray diffraction, chemical analysis 1000˚C, Fe-Fe2O3-NaFeO2 partial
system
[1976Bal1] as Crystal structure studies NaFe2O3
quoted by
[2003Lyk]
[1976Bal2] X-ray diffraction, chemical analysis 1000˚C, the Fe-Fe2O3-NaFeO2
partial system
[1977Bra] X-ray diffraction Crystal structure of Na4Fe2O5
[1977Kni] Bendix “time of flight” mass Partial pressures of Na and O, 350-
spectrometer vapor pressure 600˚C, 0 to 60 at.% O
measurements (Knudsen cell unit
attachment)
[1977Sha] as Emf 522-775˚C, NaFeO2
quoted by
[1981Lin, 1999Kal]
[1978Bra1] X-ray Guinier-Simon diffraction Crystal structure of Na5FeO4
technique (single crystals)

Fe–Na–O 4 7
[1978Bra2] X-ray diffraction (rotation of single Crystal structure of Na14Fe6O16

crystal, Weissenberg, precision filming
techniques)
[1978Bra3] X-ray Guinier-Simon diffraction Crystal structure of Na8Fe2O7
technique (single crystals)
[1981Oka] X-ray diffraction, kinetics of NaFeO2
transformation
[1984Ban] Slag-iron equilibria studies FeO-Fe2O3-Na2O partial system
[1984Dai1] Emf, acid-solution calorimetry 500-1400˚C, whole range of
compositions
[1984Dai2] X-ray diffraction, DTA, high-temperature 500-1400˚C, whole range of
microscopy, emf compositions, phase diagram and
thermodynamics
[1985Ban1] Gas-slag reactions studying 1610˚C, FeO-Fe2O3-Na2O partial
system
[1985Ban2] Gas-slag reactions studying 1610˚C, FeO-Fe2O3-Na2O partial
system
[1985Fru] Magnetic structure by neutron ≤ –173˚C, Na5FeO4
diffraction
[1986Igu] Reduction and fire flame techniques 1000˚C, FeO-Fe2O3-Na2O partial
system
[1987Yam] Emf 577-1227˚C, Fe2O3-Na2O section
[1988Bha] Emf 350-600˚C, Na4FeO3
[1993Sri] Pseudo-isopiestic equilibrations, in- < 700˚C, 0 to 60 at.% O
sodium equilibrations, DTA, solid state
reactions, X-ray diffraction
[1996Zha] as Emf ≤ 1050˚C, Fe2O3-Na3Fe5O9 section
quoted by
[1999Kal]
[1997Ded] Mössbauer spectroscopy, EPR, X-ray ≤ 480˚C, Na2O2-Fe2O3 section
diffraction
[1999Kal] Emf, isothermal equilibration, X-ray NaFeO2-Fe2O3 section
diffraction
[2002Ama] X-ray diffraction (rotation of single Na9Fe2O7
crystal)

8 4 Fe–Na–O
[2003Hua1] High temperature mass spectrometry 25-447˚C, Na4FeO3

(Knudsen effusion), X-ray diffraction
[2003Lyk] Emf 827-1027˚C, FeO-Fe3O4-NaFeO2
partial system
[2003Sob1] X-ray diffraction (single crystal) Na3FeO3
[2003Sob2] X-ray diffraction (single crystal) Complete crystal structure of
Na3FeO3
. Table 2
Phase/ Pearson Symbol/ Lattice

Temperature Space Group/ Parameters
(δFe) (h2) cI2 a = 293.15 T = 1390˚C [Mas2],

1538 - 1394 Im3m dissolves 0.029 at.% O at 1528˚C
W
(γFe) (h1) cF4 a = 364.67 T = 915˚C [Mas2],
1394 - 912 Fm3m dissolves 0.0098 at.% O at 1392˚C
Cu
(αFe) (r) cI2 a = 286.65 T = 25˚C [Mas2], dissolves
< 912 Im3m 0.00008 at.% O at 912˚C
W
(εFe) (I) hP2 a = 246.8 T = 25˚C [Mas2]
> 1.3·105 bar P63/mmc c = 396 High pressure phase
Mg
(βNa) (r) cI2 a = 428.865 T = 25˚C [1987Wri]
97.8 - (–233) Im3m
W
(αNa) (l) hP2 a = 376.7 T = −268˚C [1987Wri]
< –233 P63/mmc c = 615.4
Mg

Fe–Na–O 4 9

α, Fe1–xOx cF8 x = 0.5126 to 0.5457 [Mas2], dissolves
(wüstite)
1424 - 570 Fm3m 8 at.% Na (as Na2O) at 1000˚C [1976Bal]
NaCl
a = 430.88 Fe48.5O51.5, 20˚C [E]
a = 428.00 Fe47.2O52.8, 20˚C [E]
a = 431 Fe47.35O52.65, 1000˚C,
pO2 = 1.2·10–15 bar [1975Cla]
Nay(Fe1–xOx)1–y a = 433 x = 0.5265, y = 0.0537, T = 1000˚C,
pO2 = 1.2·10–15 bar [1975Cla]
a = 434.5 x = 0.5265, y = 0.1020, T = 1000˚C,
pO2 = 1.2·10–15 bar [1975Cla]
γFe3O4 (h) cF56 57.1 to 58.02 at.% O [Mas2]
1596 - 580 Fd3m a = 843.96 at 25˚C [V-C2]
MgAl2O4 Fe replaced by 0 to 3.5 at.% Na, at 1000˚C in
equilibrium with Ar-H2-H2O mixture
[1986Igu]
βFe3O4 (r) mC224 - ~57.1 at.% O [Mas2]
< 580 Cc
βFe3O4
αFe3O4 (hp) m*14 - ~57.1 at.% O [Mas2]
> 2.5·105 bar High pressure phase
β, Fe2O3 hR30 a = 503.42 59.82 to ~60 at.% O [Mas2]
< 1457 R3c c = 1374.73 p = 1 bar [V-C2]
Al2O3 a = 503.5 [1981Oka]
c = 1372
ε (Fe-O) c** - metastable; ~51.3 to ~53.5 at.% O [Mas2];
labelled as “P´ (wüstite)” [Mas2]
η (Fe-O) mP500? - metastable; ~52 to ~54 at.% O [Mas2];
P21/m labelled as “P´´ (wüstite)” [Mas2]
κ (Fe-O) hR6 - metastable; 51.3 to 53.2 at.% O [Mas2];
R3 labelled as “wüstite (low-temperature)”
NiO (l) [Mas2]
λ (Fe-O) cI80 - metastable; ~60 at.% O; labelled as
Ia3 “βFe2O3” [Mas2]
Mn2O3
γFe2O3 tP60 metastable; ~60 at.% O; labelled also as
P43212 μ (Fe-O)
a = c = 833 [1981Oka]
a = c = 833.9 T = 300˚C [1960The]
a = c = 840.7 T = 380˚C [1960The]

10 4 Fe–Na–O

ν (Fe-O) m*100 metastable; ~60 at.% O; labelled as “εFe2O3”
[Mas2]
a = 1299 [S]
b = 1021
c = 844
β = 95.33˚
γ, Na2O cF12 33.3 at.% O [Mas2]
< 1134 ± 4 Fm3m
CaF2 a = 556 [E]
βNa2O2 (h) cF12 ~50 at.% O; labelled as “Na2O2-II” [Mas2]
675 - (~512) Fm3m
CaF2 a = 666 [1989Rag]
c = 993
αNa2O2 (r) hP9 ~50 at.% O; labelled as “Na2O2-I” [Mas2]
≲ 512 P62m
Fe2 P a = 620.7 [E]
c = 447.1
a = 620.8 [1989Rag]
c = 446.9
γNaO2 (r) cF8 ~66.7 at.% O; labelled as “NaO2 (I)” [Mas2]
552 - (–50) Fm3m
NaCl a = 549 T = 25˚C [E]
βNaO2 (l1) cP12 ~66.7 at.% O; labelled as “NaO2 (II)” [Mas2]
(–50) - (–77) Pa
3
FeS2 (pyrite) a = 546 T = –70˚C [E]
αNaO2 (l2) oP6 ~66.7 at.% O; labelled as “NaO2 (III)” [Mas2]
< –77 Pnnm
FeS2 (marcasite) a = 426 T = –100˚C [E]
b = 554
c = 344
θ (Na-O) oP6 - metastable; ~50 at.% O; labelled as “Na2O2-
< –77 Pnnm Q” [Mas2]
FeS2 (marcasite)
ρ, NaO3 tI* ~75 at.% O [Mas2]
I4/mmm a = 1043 [1962Kuz]
c = 688
a = 1165 [1964Kuz]
c = 766

Fe–Na–O 4 11

τ1´´´, NaFeO2 (h2) - - by dilatometry distinguished from τ1´´
1330 - 1010 [1962The]
τ1´´, βNaFeO2 (h1) oP16 a = 567.2 [1981Oka]
1010 - 760 Pna21 b = 731.6
c = 537.7
τ1´, αNaFeO2 (r) hR12 a = 301.9 [1981Oka]
< 760 R3m c = 1593.4
CsICl2 a = 302.5 [2000Mat]
c = 1609.4
τ2, Na2FeO2 - - [1984Dai1]
< 801
τ3, Na4FeO3 mC32 a = 1096 single crystals prepared at 630˚C, 10 d
Cc b = 582 [1974Rie]
Na4FeO3 c = 822
β = 114˚
τ4, Na4Fe2O5 mP44 a = 1187 single crystals prepared at 600˚C, 6 d
P21/n b = 567 [1977Bra]
Na4Fe2O5 c = 917
β = 104.5˚
τ5, Na8Fe2O7 mP68 a = 872 [1977Bra]
P21/c b = 1102
Na8Ga2O7 c = 1010
β = 107.7˚
a = 870 single crystals prepared at 600˚C, 7 d
b = 1101 [1978Bra1]
c = 1009
β = 107.6˚
τ6, Na3Fe5O9 mC68 a = 1339 single crystals prepared at 1100˚C
1100 - 755 C2/c b = 1207 [1967Rom]
Na3Fe5O9 c = 529
β = 89.17˚ labelled as “Na10Fe16O29” [1959Col,
1962The, 1999Kal]
τ7, Na5FeO4 oP80 a = 1033 single crystals prepared at 650˚C, 7 d
Pbca b = 597 [1978Bra2]
Na5FeO4 c = 1808
a = 1026.7 T = –173˚C [1985Fru]
b = 591.3
c = 1780
a = 1027.9 T = –270.5˚C [1985Fru]
b = 592.3
c = 1791.4

12 4 Fe–Na–O

τ8, Na14Fe6O16 aP36 a = 1142 single crystals prepared at 650˚C, 7 d
P1 b = 827 [1978Bra3]
Na14Fe6O16 c = 595
α = 109.3˚
β = 87.7˚
γ = 111.4˚
τ9, Na9Fe2O7 oP72 a = 956.2 single crystals prepared at 450˚C
Pca21 b = 999.1 [2002Ama]
Na9Fe2O7 c = 1032.3
τ10, Na3FeO3 mP28 a = 579.9 single crystals prepared at 650˚C, 14 d, no
P21/n b = 1265.9 single phase product available [2003Sob1,
Na3FeO3 c = 582.8 2003Sob2]
β = 116.02˚
τ11, NaFe5O8 cF56 ? - [1975Cla, 1976Bal2, 1986Igu]. Inside
Fd3m ? metastable solid solution of γFe2O3 after
MgAl2O4 ? [1960The]
τ12, NaFe2O3 - - [1976Bal1, 2003Lyk]
< 1047
τ13, Na4Fe6O11 - - [1981Lin]. Phase does not exist after
[1999Kal]
. Table 3
Thermodynamic Data of Reactions or Transformations
Temperature Quantity, per mole of

Reaction or Transformation [˚C] atoms [kJ, mol, K] Comments
FeO(s) + 2Na2O(s) → 25˚C ΔH = – 13.12 ± 0.3 [1970Gro] acid solution

Na4FeO3(s) kJ·mol–1 calorimetry
3Na2O(s) + Fe(s) → Na4FeO3(s) 500-600 ΔG = 49.89 – 0.07·T [1970Gro] derived from
+ 2Na(l) acid solution calorimetry
Na4FeO3(s) → NaFeO2(s) + 500-600 ΔG = 93.02 – 0.01·T [1970Gro] derived from
Na2O(s) + Na(l) acid solution calorimetry
Ca(s) + 2NaF(s) + 2FeO(s) → 522-775 ΔG = –776.6 + 0.208·T [1977Sha, 1981Lin,
Na2FeO2(s) + CaF2(s) + Fe(s) 1999Kal] emf

Fe–Na–O 4 13
Temperature Quantity, per mole of

Reaction or Transformation [˚C] atoms [kJ, mol, K] Comments
Na2O(s) + Fe2O3(s) → 522-775 ΔG = –171.970 – [1977Sha, 1999Kal] emf

Na2Fe2O4(s) 0.009456·T
500-1400 ΔG = –86 – [1984Dai1] emf
61.89·10–3·T
657-774 ΔG = –160.2 – [1987Yam] emf
0.003909·10–3·T
774-1005 ΔG = –157.2 – [1987Yam] emf
1.332·10–3·T
1005-1132 ΔG = –147.3 – [1987Yam] emf
13.37·10–3·T
362-512 ΔG = –237.425 + [1996Zha, 1999Kal] emf
83.1·10–3·T
561-731 ΔG = –247.086 + [1996Zha, 1999Kal] emf
89.435·10–3·T
657-725 ΔG = –232.582 + [1999Kal] emf
69.61·10–3·T
FeO(s) + Na2O(s) → 500-1400 ΔG = –119.106 + [1984Dai1] acid-solution
Na2FeO2(s) 0.114·T calorimetry
FeO(s) + 2Na2O(s) → 500-1400 ΔG = –147.998 + [1984Dai1] acid-solution
Na4FeO3(s) 0.165·T calorimetry
1/2 {5Fe2O3(s) + 3Na2O(s)} → < 1132 ΔG = –(248.6 ± 1.1) – [1987Yam] emf
Na3Fe5O9(s) (2.447 ± 1.188)·10–3·T
752-864 ΔG = –153.978 + [1999Kal] emf
32.32·10–3·T
4Na(l) + Fe(s) + 3/2O2(g) → 450-600 ΔG = –1212.202 + [1988Bha] emf
Na4FeO3(s) 0.3511·T
Na4FeO3(s) → Na3FeO3(s) + 317-444 ΔG (Na4FeO3) = [2003Hua1] Knudsen cell
Na(g) –11168.629 + effusion
0.33834·T

14 4 Fe–Na–O
. Table 4
Vapor Pressure Measurements
Phase(s) Temperature [˚C] Pressure [bar] Comments
Fe(s), FeO(s), Na2Fe2O4(s) 600 log10 (pO2) = –25.27 [1984Dai1] tabulated

data
600 log10 (pNa) = –7.14
900 log10 (pO2) = –19.6
900 log10 (pNa) = –1.24
Fe(s), Na2Fe2O4(s), Na2FeO2(s) 600 log10 (pO2) = –29.85
600 log10 (pNa) = –2.56
Fe(s), Na2FeO2(s), Na4FeO3(s) 600 log10 (pO2) = –29.95
log10 (pNa) = –2.50
Na2Fe2O4(s), Na4FeO3(s), 600 log10 (pO2) = –29.69
Na2FeO2(s)
log10 (pNa) = –2.56
Fe(s), Na(l), Na4FeO3(s) 600 log10 (pO2) = –32.55
log10 (pNa) = –1.53
. Table 5
Investigations of the Fe-Na-O Materials Properties
Reference Method/Experimental Technique Type of Property
[1967Rom] Magnetic property studies, Magnetic susceptibility, magnetic ordering of the

Mössbauer spectroscopy τ6 phase
[1975Cla] Faraday magnetic technique Magnetic susceptibility of the Fe-Fe2O3-NaFeO2
partial system phases
[1976Bal2] Faraday magnetic technique Magnetic susceptibility of the Fe-Fe2O3-NaFeO2
partial system phases
[1980Kes] Magnetic property studies, Magnetic susceptibility, magnetic ordering of the
[1981Kes] Magnetic property studies, Magnetic susceptibility, magnetic ordering of the
[1985Fru] Neutron diffraction Magnetic structure of the τ7 phase
[1997Ded] Mössbauer spectroscopy Magnetic structure of Na2O2-Fe2O3 section
phases, quadrupol interactions

Fe–Na–O 4 15
. Fig. 1
Fe-Na-O. The partially quasibinary section NaFeO2 - Fe2O3

16 4 Fe–Na–O
. Fig. 2
Fe-Na-O. The partially quasibinary section Na2O – FeO

Fe–Na–O 4 17
. Fig. 3
Fe-Na-O. The approximately quasibinary section Fe3O4-NaFeO2

. Fig. 4
18
Fe-Na-O. Reaction scheme of the partial system Fe-Fe2O3-NaFeO2-Na2FeO2. The phases (αFe), (γFe) and (δFe) are not distinguished and called Fe.
Also τ 1’, τ 1’’ and τ 1’’’ are not distinguished and called NaFeO2 4
ß Springer 2009
Fe–Na–O
DOI: 10.1007/978-3-540-70890-2_4
MSIT1
Landolt‐Börnstein
New Series IV/11D5
Fe–Na–O 4 19
. Fig. 5
Fe-Na-O. Liquidus surface projection of the partial FeO-Fe2O3-NaFeO2 system

20 4 Fe–Na–O
. Fig. 6
Fe-Na-O. Isothermal section of the partial Fe-Fe2O3-NaFeO2 system at 1000˚C; equilibrated with
Ar-H2-H2O mixtures

Fe–Na–O 4 21
. Fig. 7
Fe-Na-O. Isothermal section at 595˚C

22 4 Fe–Na–O
. Fig. 8
Fe-Na-O. Temperature - composition section NaFeO2-FeO

Fe–Na–O 4 23
References
[1940Kni] Knick, R., Kohlmeyer, E.J., “About the Melting Properties of the Soda-Iron Oxide Mixtures” (in
German), Z. Anorg. Allg. Chem., 244, 67–84 (1940) (Phase Diagram, Experimental, *) as quoted by
[1984Dia1]
[1959Col] Collonques, R., Thery, J., “Preparation and Properties of Sodium Ferrites”, Bull. Soc. Chim. Fr., 1959,
1141–1144 (1959) (Crys. Structure, Experimental) as quoted by [1999Kal]
[1960The] Thery, J., Collongues, R., “The Fe2O3-Na2O System” (in French), Compt. Rend., 250, 1070–1072 (1960)
(Crys. Structure, Phase Diagram, Experimental, *, 9)
[1962Kuz] Kuznetsov, V.G., Tokareva, S.A., Dobrolyubova, M.S., “X-ray Diffraction Investigation of the Sodium
Ozonide NaO3” (in Russian), Zh. Neorg. Khim., 7(5), 967–970 (1962) (Crys. Structure, Experimental, 7)
[1962Roo] Rooymans, C.J.M., “New Compound in the Na2O-Fe2O3 System”, J. Phys. Soc. Jpn., 17, 722–723 (1962)
(Crys. Structure, Experimental) as quoted by [1999Kal]
[1962The] Thery, J., “Alkali Metal Ferrates and Their Hydrolysis Products”, Ann. Chim. (Paris), 7, 207–238 (1962)
(Crys. Structure, Phase Diagram, Experimental, 42)
[1963Sch] Scholder, R., Mansmann, M., “Compounds of the So-Called β-Alumina Type” (in German), Z. Anorg.
Allg. Chem., 321(5-6), 246–261 (1963) (Crys. Structure, Experimental, 19)
[1964Kuz] Kuznetsov, V.G., Bakulina, V.M., Tokareva, S.A., Zimina, A.N., “X-ray Diffraction Investigation of the
Sodium Ozonide NaO3” (in Russian), Zh. Struct. Khim., 5(1), 142–144 (1964) (Crys. Structure,
Experimental, 8)
[1967Rom] Romers, C., Rooymans, C.J.M., de Graaf, R.A.G., “The Preparation, Crystal Structure and Magnetic
Properties of Na3Fe5O9”, Acta Cryst., 22(6), 766–771 (1967) (Crys. Structure, Experimental, Review,
Magn. Prop., 21)
[1970Gro] Gross, P., Wilson, G.L., “Composition and Heat of Combination of a Double Oxide of Iron and
Sodium”, J. Chem. Soc. (A), 11, 1913–1916 (1970) (Crys. Structure, Phase Relations, Thermodyn.,
Experimental, 10)
[1971Tsc] Tschudy, A., Kessler, H., “The Na2O-NaFeO2 System. Characterization of Three Ternary Compounds”
(in French), Compt. Rend., Ser. C., 273(21), 1435–1437 (1971) (Crys. Structure, Experimental, 4)
[1974Bar] Barker, M.G., Wood, D.J., “The Corrosion of Chromium, Iron and Stainless Steel in Liquid Sodium”,
J. Less-Com. Met., 35, 315–323 (1974) (Crys. Structure, Morphology, Phase Relations, Experimental, 16)
[1974Rie] Rieck, H., Hoppe, R., “The First Oxoferrate (II): Na4{FeO3}” (in German), Naturwissenschaften, 61(3),
126–127 (1974) (Crys. Structure, Experimental, 9)
[1975Cla] Claude, J.M., El Balkhi, A.M., Jeannot, F., Gleitzer, C., Aubry, J., “The Fe-Fe2O3-NaFeO2 System. I. The
Solubility of Na in Wustite at pO2 = 1.2·10–15 bar and 1000˚C” (in French), Mem. Sci. Rev. Met., 72(7-8),
599–603 (1975) (Crys. Structure, Phase Diagram, Phase Relations, Experimental, Magn. Prop., *, 12)
[1975Kol] Kolster, B.H., “Mechanism of Fe and Cr Transport by Liquid Sodium in Non-Isothermal Loop
Systems”, J. Nucl. Mater., 55(2), 155–168 (1975) (Crys. Structure, Morphology, Experimental, Transport
Phenomena, 19)
[1976Bal1] El Balkhi, A.M., Zanne, M., Gleitzer, C., “Preparation and Properties of the Sodium-Ferrite (II, III)
Oxide. NaFe2O3” (in French), J. Solid State Chem., 18, 293–297 (1976) (Crys. Structure, Experimental)
as quoted by [2003Lyk]
[1976Bal2] El Balkhi, A.M., Zanne, M., Gleitzer, C., Aubry, J., “The Fe-FeO-NaFeO2 System. II. Equilibrium Limits
and Properties of Wustite Containing Na” (in French), Mem. Sci. Rev. Metall., 73(2), 761–768 (1976)
(Crys. Structure, Phase Diagram, Phase Relations, Experimental, Magn. Prop., *, 5)
[1977Bra] Brachtel, G., Hoppe, R., “The First Oxoferrate (III) with Single Layer Structure: Na4Fe2O5”
(in German), Naturwissenschaften, 64(5), 271–272 (1977) (Crys. Structure, Experimental, 8)
[1977Kni] Knights, C.F., Phillips, B.A., “Phase Diagrams and Thermodynamic Studies of the Cs-Cr-O, Na-Cr-O
and Na-Fe-O Systems and their Relationships to the Corrosion of Steels by Caesium and Sodium”,
Special Publ. Chem. Soc., 30, 134–145 (1977) (Crys. Structure, Phase Diagram, Phase Relations,
Thermodyn., Experimental, *, 43)
[1977Sha] Shaiu, B.J., Wu, P.C.S., Chiotti, P., “Thermodynamic Properties of Double Oxides of Sodium Oxide
with Oxides of Chromium, Nickel and Iron”, J. Nucl. Mater., 67, 13–23 (1977) (Thermodyn., Experi-
mental) as quoted by [1981Lin] and [1999Kal]
[1978Bra1] Brachtel, G., Hoppe, R., “On Oxoferrate with "Isolated" Anions: Na8Fe2O7” (in German), Z. Anorg.
Allg. Chem., 438, 15–24 (1978) (Crys. Structure, Experimental, 36)

24 4 Fe–Na–O
[1978Bra2] Brachtel, G., Hoppe, R., “New Oxoferrates (III). On the Knowledge of Na5FeO4” (in German),
Z. Anorg. Allg. Chem., 446, 77–86 (1978) (Crys. Structure, Experimental, 18)
[1978Bra3] Brachtel, G., Hoppe, R., “New Oxoferrates (III). On the Knowledge of Na14{Fe6O16}” (in German),
Z. Anorg. Allg. Chem., 446, 87–96 (1978) (Crys. Structure, Experimental, 18)
[1978Zve] Zvezdinskaya, L.V., Smirnova, N.L., Belov, N.V., “System of Polymorphic Transition Between
Structural Types of Ternary ABX2 Compounds”, Sov. Phys.-Crystallogr. (Engl. Transl.), 23(3), 293–296
(1978) (Crys. Structure, Review, 22)
[1980Kes] Kessler, H., Son, L., “Study of the Magnetic Interactions between Na5FeO4 and {FeO4}5– Discrete
Anions” (in French), Rev. Chimie Miner., 17(6), 541–547 (1980) (Crys. Structure, Experimental, Magn.
Prop., 13)
[1981Kes] Kessler, H., Ly, S., “Magnetic Interactions of {Fe2O7}8– Groups in Na8Fe2O7” (in French), J. Solid State
Chem., 39, 22–28 (1981) (Crys. Structure, Experimental, Magn. Prop., 20)
[1981Lin] Lindemer, T.B., Besmann, T.M., Johnson, C.E., “Thermodynamic Review and Calculations - Alkali-
Metal Oxide Systems with Nuclear Fuels, Fission, Products and Structural Materials”, J. Nucl. Mater.,
100(1-3), 178–226 (1981) (Phase Diagram, Phase Relations, Thermodyn., Calculation, Review, 280)
[1981Oka] Okamoto, S., “Crystallization and Phase Transformation Sodium Orthoferrites”, J. Solid State Chem.,
39, 240–245 (1981) (Crys. Structure, Phase Relations, Experimental, 10)
[1982Bau] Baur, W.H., McLarnan, T.J., “Observed Wurtzite Derivatives and Related Dipolar Tetrahedral
Structures”, J. Solid State Chem., 42, 300–321 (1982) (Crys. Structure, Review, 93)
[1984Ban] Ban-ya, S., Hino, M., Takezoe, H., “Thermodynamics of FetO-Na2O, FetO-SiO2-Na2O, FetO-P2O5-
Na2O and FetO-P2O5-SiO2-Na2O Slags in Equilibrium with Solid Iron”, Second Int. Symp. Metal. Slags
and Fluxes (Proc. Conf.), Lake Tahoe, Nevada, U.S.A., 1984, The Metall. Soc. AIME, Warrendale,
Pennsylvania, 395–416 (1984) (Phase Relations, Thermodyn., Experimental, 42)
[1984Dai1] Dai, W., Seetharaman, S., Staffansson, L.-J., “A Thermodynamic Study of the System Fe-Na-O”, Scand.
J. Metall., 13(1), 32–38 (1984) (Phase Diagram, Phase Relations, Thermodyn., Experimental, #, 20)
[1984Dai2] Dai, W., Seetharaman, S., Staffanson, L.-J., “Phase Relationships in the System Fe-Na-O”, Metall. Trans.
B, 15B, 319–327 (1984) (Morphology, Phase Diagram, Thermodyn., Experimental, #, 24)
[1985Ban1] Ban-Ya, S., Hino, M., Takezoe, H., “Activities of the Constituents and Fe3+ / Fe2+ Equilibrium in FetO-
Na2O and FetO-SiO2-Na2O Slags” (in Japanese), Tetsu To Hagane, 15, 1765–1772 (1985) (Phase
Diagram, Phase Relations, Thermodyn., Calculation, Experimental, 42)
[1985Ban2] Ban-Ya, S., Hino, M., Takezoe, H., “Thermodynamic Properties of FetO-Na2O, FetO-SiO2-Na2O, FetO-
P2O5-Na2O and FetO-P2O5-SiO2-Na2O Slags”, Trans. Iron Steel Inst. Jpn., 25(11), 1122–1131 (1985)
(Phase Diagram, Phase Relations, Thermodyn., Experimental, 42)
[1985Fru] Fruchart, D., Soubeyroux, J., Kessler, H., Lassalle, J.-M., “Magnetic Structure of Na5FeO4” (in French),
J. Solid State Chem., 57, 191–196 (1985) (Crys. Structure, Experimental, Magn. Prop., 8)
[1986Igu] Iguchi, Y., Amahiro, Y., Hirao, J., “Equilibrium Between FeO-M2O (M = Na, Li) Solid Solution and
Oxygen in Gas Phase at 1273 K” (in Japanese), J. Jpn. Inst. Met., 50(3), 282–287 (1986) (Crys. Structure,
Phase Relations, Thermodyn., Experimental, #, 27)
[1987Wri] Wriedt, H.A., “The Na-O (Sodium-Oxygen) System”, Bull. Alloy Phase Diagrams, 8(3), 234–246 (1987)
(Assessment, Review, Phase Diagram, Phase Relations, Crys. Structure, 100)
[1987Yam] Yamaguchi, S., Kaneko, Y., Iguchi, Y., “Activity Measurements of Na2O in Na2O-Fe2O3 System by EMF
Method Using Sodium β Alumina as a Solid Electrolyte”, Trans. Jpn. Inst. Met., 28(12), 986–993 (1987)
(Thermodyn., Experimental, 10)
[1988Bha] Bhat, N.P., Borgstedt, H.U., “Thermodynamic Stability of Na4FeO3 and Threshold Oxygen Levels in
Sodium for the Formation of this Compound on AISI 316 Steel Surfaces”, J. Nucl. Mater., 158, 7–11
(1988) (Thermodyn., Calculation, Experimental, 20)
[1989Rag] Raghavan, V., “The Fe-Na-O (Iron-Sodium-Oxygen) System” in “Phase Diagrams of Ternary Iron
Alloys”, Indian Inst. Met., Calcutta, 5, 206–212 (1989) (Crys. Structure, Phase Diagram, Review, 17)
[1993Sri] Sridharan, R., Gnanasekaran, T., Mathews, C.K., “Phase Equilibrium Studies in the Na-Fe-O System”,
J. Alloys Compd., 191, 9–13 (1993) (Phase Relations, Phase Diagram, Experimental, *, 14)
[1996Kal] Kale, G.M., Davidson, A.J., Fray, D.J., “Solid State Sensor for Measuring Antimony in Non-Ferrous
Metals”, Solid State Ionics, 86-88, 1101–1105 (1996) (Phase Relations, Thermodyn., Experimental) as
quoted by [1999Kal]
[1996Zha] Zhang, L., Fray, D.J., Dekeyser, J.C., De Schutter, F., “Reference Electrode of Simple Galvanic Cells for
Developing Sodium Sensors for Use in Molten Aluminium”, Metall. Mater. Trans. B., 27B, 794–800
(1996) (Phase Relations, Thermodyn., Experimental) as quoted by [1999Kal]

Fe–Na–O 4 25
[1997Ded] Dedushenko, S.K., Kholodkovskaya, L.N., Perfiliev, Yu.D., Kiselev, Yu.M., Saprykin, A.A., Kamozin,
P.N., Lemesheva, D.G., “On the Possible Existence of Unusual Higher Oxidation States of Iron in
the Na-Fe-O System”, J. Alloys Compd., 262-263, 78–80 (1997) (Crys. Structure, Experimental, Magn.
Prop., 6)
[1998Wu] Wu, E.J., Tepesch, P.D., Ceder, G., “Size and Charge Effects on the Structural Stability of LiMO2 (M =
Transition Metal) Compounds”, Philos. Mag. B, 77(4), 1039–1047 (1998) (Crys. Structure, Review, 22)
[1999Kal] Kale, G.M., Srikanth, S., “Electrochemical Determination of the Gibbs Energy of Formation of
Na2Fe2O4 and Na3Fe5O9 Employing Na-β-Al2O3 Solid Electrolyte”, J. Am. Ceram. Soc., 83(1), 175–180
(1999) (Phase Relations, Thermodyn., Experimental, 24)
[2000Mat] Mather, G.C., Dussarrat, C., Etourneau, J., West, A.R., “A Review of Cation-Ordered Rock Salt
Superstructure Oxides”, J. Mater. Chem., 10, 2219–2230 (2000) (Crys. Structure, Review, 55)
[2002Ama] Amann, P., Moeller, A., “Na9{FeO3}{FeO4} a Mixed Valent Oxoferrat (II, III) with Isolated {FeO3}4– and
{FeO4}5– Anions”, Z. Anorg. Allg. Chem., 628, 917–919 (2002) (Crys. Structure, Experimental, 12)
[2003Hua1] Huang, J., Furukawa, T., Aoto, K., “Thermodynamic Study of Sodium-Iron Oxides. Part I. Mass
Spectrometric Study of Na-Fe Oxides”, Thermochim. Acta, 405(1), 61–66 (2003) (Thermodyn., Exper-
imental, 20)
[2003Hua2] Huang, J., Furukawa, T., Aoto, K., “Thermodynamic Study of Sodium-Iron Oxides. Part II. Ternary
Phase Diagram of the Na-Fe-O System”, Thermochim. Acta, 405(1), 67–72 (2003) (Phase Diagram,
Thermodyn., Assessment, Calculation, *, 15)
[2003Lyk] Lykasov, A.A., Pavlovskaya, M.S., “Phase Equilibria in the Fe-Na-O System Between 1100 and 1300 K”,
Inorg. Mater., 39(10), 1088–1091 (2003) translated from Neorg. Mater., 39(10), 1260-1263, (2003)
(Phase Diagram, Phase Relations, Thermodyn., Calculation, Experimental, *, 6)
[2003Mue] Mueller-Buschbaum, H., “The Crystal Chemistry of AM2O4 Oxometallates”, J. Alloys Compd., 349,
49–104 (2003) (Crys. Structure, Review, 476)
[2003Sob1] Sobotka, B.M., Moeller, A., “Crystal Structure of Na3FeO3” (in German), Anorg. Kristallstr. Kristall-
chem., 20, 153 (2003) (Crys. Structure, Experimental, 2)
[2003Sob2] Sobotka, B.M., Moeller, A., “Synthesis of Na3FeO3, a Ternary Oxoferrate (III) with a Chain Structure”
(in German), Z. Anorg. Allg. Chem., 629, 2063–2065 (2003) (Crys. Structure, Experimental, 21)
(1990)

Fe–Nb–Ni 5 1
Iron – Niobium – Nickel

Volodymyr Ivanchenko, Tetyana Pryadko
Introduction
Nickel steels and superalloys have found an increasing use in applications that required a
combination of high strength, ductility and corrosion resistance at high temperatures. These
applications have led to interest in the precipitation hardening characteristics of nickel base
alloys. It has been established that in Nb bearing austenitic steels the Laves phase NbFe2 can
produce considerable precipitation hardening.
[1975Pan] investigated alloys on the Nb2Fe-NbNi3 section and found it to be a quasibinary
one of the simple eutectic type. Crystal structures of phases formed in the ternary alloys at 950˚
C along NbFe-NbNi and NbFe2-NbNi2 joins have been studied by [1981Var]. Growth crystal-
lography of directionally solidified (αFe)+(Nb,Ni)Fe2 eutectic alloy was investigated by
[1980Tew].
The phase relations in alloys obtained by quenching directly from the melt were studied by
[1982Osi, 1984Ska, 1989Sav]. [1989Sav] gives the phase distribution on the composition
triangle for cast alloys quenched from liquid state at different cooling rates, up to 106 ˚C·s–1.
When the alloys were quenched directly from the melt at cooling rates up to 104-106 ˚C·s–1, all
the three Laves forms C14 (λ1), C15 (λ2), and C36 (λ3) appeared. Using the electron concen-
tration considerations and comparisons with the isothermal sections in the related Co-Fe-Nb
and Co-Nb-Ni systems, [1989Sav] comes to the unusual conclusion that the phase distribu-
tion obtained by quenching directly from the melt is closer to the equilibrium conditions and
proposed the isothermal section at 1200˚C. This section was reproduced by [1992Rag1], but
with a comment, that it clearly required confirmation and should be considered purely
tentative. [2001Tak] and [2005Tak] studied phase equilibria among γ, NbNi3 and NbFe2
phases. Isothermal section at 1200˚C was presented. It was redrawn by [2004Rag] from
[2001Tak]. An attempt to estimate the concentration stability of topologically closed-packed
phases was performed by [1992Mes] by calculation of the change in the factor of the electron
concentration.
The works on the phase relations, structures and thermodynamics are summarized in
Table 1.
Binary Systems
The Fe-Nb system is accepted from [1993Bej]. The Fe-Ni system is taken from the recent
assessment of [2008Kuz]. The Nb-Ni system is accepted according to [1998Oka].

2 5 Fe–Nb–Ni
Solid Phases
The isostructural phases Nb6Fe7 and Nb7Fe6 form a continuous solid solution μ [1981Var,
1989Sav, 2001Tak, 2005Tak]. The composition dependences of cell parameters obey the
Vegard’s law [1981Var].
The effects of Ni content on the lattice parameters of the stoichiometric λ1 (NbFe2) phase
and the Fe rich λ1 phase in equilibrium with γ phase are shown in Fig. 1, together with their
calculated values (thin lines) based on Vegard’s law according to [2005Tak].
A new ternary intermetallic phase was found at the composition around Ni-22Nb-20Fe
(at.%) by [2001Tak]. It’s crystal structure has been identified as ordered hexagonal (hP24 with
stacking sequence of abcbcb).
The amorphous state can be formed in alloys located along line parallel to the Fe-Ni side of
the composition triangle with 25-50 at.% Nb under quenching from the liquid state with a
cooling rate of ~106 K·s–1 [1984Ska].
Under ordering of (NbxFe1–x)Ni3 compound atoms of Nb are distributed in the both
sublattice of Fe and Ni [1985Val]. Nb atoms try to set places to form a maximal number of Nb-
Nb pairs [1987Val]. [1993Zhi] reported, that under annealing of quenched by spinning Ni-16
Fe-6Nb (at.%) and Ni-16Fe-4Nb (at.%), ordering of the γ phase occurs. Nucleation and
growth of the ordered γ’’- and γ’ phases proceed in an accelerated manner, although the
mechanisms of nucleation are different. The fact that the density of quench-induced defects is
relatively low is probably due to their relaxation and migration to sinks such as Nb rich areas.
This can promote an accelerated phase transformation and ordering processes in the γ-matrix.
The formation of tetrahedral stacking faults in the matrix during annealing also points to the
relaxation of quench-induced defects. Thus the main factor accelerating phase transforma-
tions from the γ- into the γ’ phase is an excessive vacancy density. In the transformation from
the γ- into the γ" phase, two more factors are operative: (1) dendritic segregation, that is, a
higher Nb and Fe content in the interbranch spaces of dendritic cells; and (2) stresses, resulting
from melt quenching, which promote the development of a sub-grain structure.
[1989Sav] reported about the formation under rapid crystallization of C15 (λ2) and C36
(λ3) Laves phases in the Fe-Nb-Ni system and based on the electron concentration consider-
ation contended that they are equilibrium phases. These results are in contradiction with the
results of [2001Tak] and [2005Tak]. Therefore the C15 (λ2) and C36 (λ3) Laves phases
discovered by [1989Sav] must be regarded as metastable. Crystal structures of solid phases
formed in the Fe-Nb-Ni system are presented in Table 2.
Quasibinary Systems
According to [1975Pan] the NbFe2-NbNi3 section is quasibinary of the eutectic type. The
eutectic reaction is at 1290˚C and 70 mol% NbNi3 (16.2Fe-27Nb-56.8Ni (at.%) [1975Pan]. No
phase diagram was presented by [1975Pan]. Presented values are in good accordance with
[2001Tak, 2005Tak].

Fe–Nb–Ni 5 3
Only one three-phase invariant equilibrium was experimentally recorded in the Fe-Nb-Ni
system by [1975Pan]. It is presented in Table 3.

The solubility of Nb in Fe-30 mass% Ni (29.6 at.%) austenite at 1250˚C is about 3.4 mass%
(2.1 at.%) and at 800˚C is about 1 mass% (0.6 at.%) [1971Lei].
Isothermal Sections
The isothermal section at 1200˚C presented in Fig. 2 is taken from [2005Tak]. In the Fe rich
corner a three-phase domain (λ1+(δFe)+γ) is drawn tentatively to account for the (δFe) phase
which exists at this temperature. The section at the same temperature constructed by
[1989Sav] is omitted here since it obviously presents metastable state, see above section
“Introduction”.
On aging at 800˚C of the Fe-30Ni-5Nb (mass%) alloy quenched from 1250˚C the hardness
increases from 150 to 220 HV (1.471 to 2.158GPa).The precipitation of NbFe2 is a heteroge-
neous process occurring mainly on dislocations on (111)γ planes and on grain boundaries. The
rate of growth of NbFe2 precipitate beyond the peak hardness is very slow and as a result no
overaging was observed after aging at 800˚C for 250 h and at 700˚C for 1000 h [1971Lei]. The
rate of solid solution hardening per 1 at.% Nb in Ni-Fe matrix alloys is larger than in Ni matrix
alloys [1990Cho].
Magnetically soft alloys of the Fe-Ni system are used extensively in instrument building.
This is connected with a favorable combination of a number of properties: single phase alloys
in a stable condition over a wide concentration range, absence of allotropic transformations
which cause development of internal stresses, existence of ordering and the possible effect of
alloying on the degree of ordering, and passage of the constants for magnetic crystallographic
anisotropy KI and magnetostriction is through a zero value in the range 70-80% Ni. However,
alloys of the Fe-Ni system have low strength and wear resistance which limit their use for
example as magnetic recording heads.
One of the most widespread methods for improving the mechanical properties of these
alloys is alloying with elements which form solid solutions. Nb is one from such elements. His
solid solution strengthening is observed which causes a specific increase in mechanical
properties.
The origin of high magnetic permeability in “Hardperm” of the Fe-Nb-Ni system was
studied by [1976Hin]. The effect of structure on the hardness and permeability of Fe-Nb-Ni
alloys was presented by [1979Wen]. Magnetic properties of intermetallic phases have been
studied by [1982Osi].

4 5 Fe–Nb–Ni
Magnetic properties, electrical resistivity and hardness of Ni-based alloys were studied by
[1974Mas, 1978Mas]. Alloys with a very high permeability were proposed.
An investigation of the structures of Fe-Nb-Ni alloys has been carried out by means of
TEM supplemented by electron diffraction and X-ray diffraction analysis [1979Wen]. As the
proportion of modulated structures increases, the hardness of the alloy also increases, but vice
versa in the case of its magnetic permeability. The introduction of solute atoms of Nb would
lower the degree of ordering in Ni3Fe alloy, but fortunately only certain degree of ordering was
sufficient to yield conditions for high permeability. A preprecipitating phase possessing the fcc
(ordered) Ni3Nb (γ’) structure and being coherent with the matrix, was observed in the Fe-
Nb-Ni alloy. This phase appears to promote the formation of modulated structures and exert a
strengthening effect on matrix.
Examination of the temperature dependence of the magnetic susceptibility of the Laves
phase NbFe2 has shown it to be a temperature-independent paramagnetic (χ = 9.6 · 10–6
m3·kg–1). Substitution of the iron atoms by nickel ones along the section NbFe2-NbNi3 causes
a smooth increase in magnetic susceptibility which reaches 1.82 · 10–5 m3·kg–1 for an alloy with
46.67 at.% Fe + 22.5 at.% Ni + 30.83 at.% Nb (70 mol% NbFe2, 30 mol% NbNi3). The Nb6Fe7
and Nb7Ni6 compounds are temperature-independent paramagnetics with magnetic suscept-
ibilities of 1.85 · 10–5 and 0.6 · 10–5 m3·kg–1, respectively, i.e. the 3d band for these compounds
is completely filled and the magnetic properties are determined by the S conductivity electrons
which have temperature-independent susceptibility [1982Osi].
A strengthening effect is observed for microcrystalline alloys of the system Fe-Nb-Ni
prepared by quenching from the melt with low-temperature heat treatment. Strengthening
of these alloys is due to the effect of crystallite refinement in the initial stages of primary
recrystallization and precipitation of the NbNi3 phase. Low-temperature heat treatment
provides preparation of the most effective magnetic permeability in the frequency range
0.5-1 MHz for alloys Ni-16Fe-4Nb (at.%); Ni-16Fe-6Nb (at.%). Use of the rapid quenching
method makes it possible to achieve a marked increase in mechanical properties of alloys of
the system Fe-Nb-Ni compared with the properties of alloys prepared by traditional technol-
ogy with retention of a high level of magnetic characteristics at frequencies of 0.5-1 MHz
[1992Sos].
Phase hardening during martensite transformation as well as the hard particles of NbNi3
and NbFe2-type have the effect of increasing the degree of recovery of shape and partially
constrict transformation hysteresis in Fe-Nb-Ni alloys due to effective prevent dislocation
movement [1985Kov1, 1985Kov2, 1989Kov]. In Fe-30.5Ni-(2.9-4.3)Nb (at.%) alloys, the
γ00 -particles having a mean dimension more than 10 nm do not transform to another
structure. However, the particle deformation takes place, providing an effect equivalent to
inhomogeneous deformation of the martensite. The stored strain level causes a small tetrago-
nal distortion of the martensite. The tetragonality is not a consequence of the ordered
structure of the precipitates (D022) but rather is due to the tetragonal symmetry of the Bain
strain. The particles can be considered as memory elements which are responsible for the
shape memory effect in the steels, despite the relatively small tetragonality of α phase and the
relatively wide thermal hysteresis [1993Kov].
Investigations of the Fe-Nb-Ni materials properties are summarized in Table 4.

Fe–Nb–Ni 5 5
Miscellaneous
[1980Rus] studied martensite aging in Fe-13.4Ni-2.6Fe (at.%) alloy. It proceeds in two stages.
At the preisolation stage (300-450˚C) there occure the formation of Ni and Nb enriched
submicroregions and Fe atomic ordering. The second stage heating temperature 450˚C results
in isolation of disperse particles of Ni- and Nb-based intermetallic phases. The first stage
produces the main strengthening. Aligned lamellar microstructure was obtained on alloy with
a nominal composition of Fe-12Nb-17.7Ni (at.%) directionally solidified at a growth rate of
0.5 cm·h–1 with the temperature gradient in the liquid-solid interface of about 200˚C·cm–1.
The orientation relationship between (αFe) matrix phase and lamellas of ε(Nb,Ni)Fe2 inter-
metallic phase has been expressed as {111}α //{001}ε growth direction and (112) α//(010)ε at
the α-ε interface.
It was shown by [1993Zhi] that upon heat treatment of rapidly quenched alloys,
γ00 (superstructure of the D022 type)- and γ’ (superstructure of the L12 type)- phase precipita-
tion precedes the formation of the stable NbNi3 phase. Fine precipitates of the Ll2 type ordered
phase observed upon annealing in the alloys with 6 and 8 at.% Nb result from ordering
processes in the Ni base γ solid solution. The processes develop actively upon annealing at
900 - 1100˚C in the alloy where the long-range order in the initial state has been suppressed by
rapid quenching.
. Table 1
Investigations of the Fe-Nb-Ni Phase Relations, Structures and Thermodynamics
[1975Pan] Optical metallography, X-ray NbFe2 - NbNi3 join, quasibinary section

diffraction, DTA
[1980Rus] NGR, DSC, dilatometry, resistivity, Fe-2.6 at.% Nb 13.4 at.% Ni, water quenching
Vickers hardness from 1200˚C, annealed for 1 h at 250-750˚C
[1980Tew] SEM, TEM, electron diffraction Directionally solidified Fe-12 at.% Nb-17.7 at.% Ni
alloy, (αFe)+NbFe2
[1981Var] Optical metallography, X-ray 950˚C, then quenched. NbFe-NbNi and NbFe2-
diffraction, EDAX NbNi2 joins
[1984Ska] XRD 35 to 50 at.% Nb, < 85 at.% Ni, quenched with
rates from 102 to 106 K·s–1
[1985Val] XRD, Neutron diffraction, resistivity Ni3Fe1–xNbx, water quenched from 1100˚C with
measurements tempering at 900˚C
[1987Val] Neutron diffraction on alloy with Nb0.3Fe0.7Ni3 annealed at 850˚C and slow cooled
different Ni isotopic composition to room temperature
[1989Sav] X-ray diffraction Ni-Nb and Fe-Nb quenched from the melt at
cooling rates up to 104-106 ˚C·s–1
[1992Sos] Optical microscopy, TEM, XRD, 16 at.% Fe, < 8 at.% Nb, rapid quenching by
microhardness, crystallographic spinning, heat treatment in the temperature
texture range 300-1000˚C for 1 h

6 5 Fe–Nb–Ni
[1993Zhi] SEM, XRD, electron microdifraction, Ni85–xFe15Nbx (x = 4, 6, 8); rapid quenching by

phase ordering investigation spinning, annealed 200-1200˚C
[1993Kov] X-ray diffraction, TEM, shape 100 h at 1200˚C then water quenched, aged at
memory effect investigation 650˚C for 6 to 100 h., 31 mass % Ni, 4.6 to 6.8
mass% Nb. Shape memory effect
[2001Tak] SEM, TEM, XRD, EPMA (Electron 1200-1250˚C, 15 to 25 at.% Nb, 5 to 25 at.% Fe,
Probe Microanalysis) phase diagram
[2005Tak] SEM, TEM, XRD, EPMA 1200˚C, 15 to 40 at.% Ni, 15 to 35 at.% Nb, phase
diagram
. Table 2
Pearson
Symbol/
Phase/ Space
Temperature Group/ Lattice Parameters
(δFe) cI2 a = 293.15 pure Fe at 1394˚C [V-C2, Mas2]

1538 - 1190 Im3m 0-3.27 at.% Nb at 1370˚C [1993Bej]
W
0-3.8 at.% Ni at 1514˚C [2008Kuz]
(αFe) cI2 a = 286.65 pure Fe at 25˚C [Mas2]
< 912 Im3m 0-0.73 at.% Nb at 960˚C [1993Bej]
W 0-4.7 at.% Ni at 347˚C [2008Kuz]
γ, (γFe,Ni) cF4 a = 354 Ni-10 at.% Fe
Fm3m a = 355.2 Ni-10 at.% Fe-2 at.% Nb [1990Cho]
Cu
(γFe) a = 364.67 pure Fe at 915˚C [Mas2]
1394 - 912 0-1.0 at.% Nb at 1190˚C [1993Bej]
(Ni) a = 352.40 pure Ni at 25˚C [Mas2]
< 1455 0-12.4 at.% Nb at 1282˚C [1998Oka]
(Nb) cI2 a = 330.04 pure Nb at 25˚C [Mas2]
< 2469 Im3m 0-4.2 at.% Ni at 1295˚C [1998Oka]
W 0-7.0 at.% Fe at 1500˚C [1993Bej]
P63/mmc c = 396.0
Mg

Fe–Nb–Ni 5 7
Pearson
Symbol/
Phase/ Space
λ1, Nb1–y(Fe1–xNix)2 hP12 Laves Phase

P63/mmc x < 0.45, - 0.23 < y < 0.26
MgZn2 [2005Tak]
NbFe2 32-37 at.% Nb [1993Bej]
< 1630 a = 483.8 33.3 at.% Nb [2005Tak]
c = 788.9
a = 481.0 27.1 at.% Nb [2005Tak]
c = 785.2
μ, (Fe,Nb,Ni) hP13
Nb6Fe7
R3m a = 492.8 48-52 at.% Nb [1993Bej]
< 1520 Fe7W6 c = 2683
Nb7Ni6 a = 489.6 Nb49.6Ni50.4 [2002Jou]
< 1295 c = 2661.4
a = 495.9 Nb56..9Ni43.1 [2002Jou]
c = 2699.8
FeNi3 cP4 a = 355.23 63 to 85 at.% Ni [2008Kuz]
< 517 Pm3m
AuCu3
FeNi (metastable) tP2 a = 357.9 [2008Kuz]
P4/mmm c = 357.9
AuCu
NbNi3 oP8 22.7-27.5 at.% Nb [1998Oka]
< 1402 Pmmm a = 511.6 [1991Gup]
βCu3Ti b = 425.9
c = 456.5
NbNi8 tI* a = 1080 11.1 at.% Nb [1991Gup]
< 535 - c = 360
* τ, (Fe,Nb,Ni) hP24 - Fe-22Nb-58Ni [2001Tak]
λ2, Nb1–y(FexNi1–x)2 cF24 - Laves phase. Probably metastable
Fd
3m [1989Sav]
MgCu2 0.35 < x < 0.67; y < 0.25
λ3, Nb(FeNi)2 hP24 - Laves phase. Probably metastable
P63/mmc [1989Sav]
MgNi2 ~ 40 at.% Fe and 40 at.% Ni

8 5 Fe–Nb–Ni
Pearson
Symbol/
Phase/ Space
γ’ cP4 Nearly the same Metastable phase formed by aging a

Pm3m parameters as those of rapid quenched melt Ni-16at.%
AuCu3 the mother γ phase Fe-(6, 8) at.% Nb [1993Zhi]
γ ’’ tI8 a = 361.4 Metastable [1993Kov, 1993Zhi]
I4/mmm c = 757.6
TiAl3 ?
. Table 3
Composition (at.%)
Reaction T [˚C] Type Phase Fe Nb Ni
L Ð NbFe2 + NbNi3 1290 e L 16.2 27 56.8

NbFe2 38.8 29.9 31.3
NbNi3 5.1 25.6 69.3
. Table 4
Investigations of the Fe-Nb-Ni Materials Properties
[1971Lei] XRD, electron diffraction technique, Fe67.3Ni29.6Nb3.1 (in at.%), quenched from
TEM, hardness measurements 1250˚C, aged at 700-800˚C, hardening
[1972Mas, Electrical resistivity, initial 950-1350˚C, 73-85 mass% Ni, 6-25 mass% Fe,
1974Mas] permeability, coercive force, high permeability alloys
hardness
[1976Hin] Electrical resistivity, crystal 80 mass% Ni, 10 to 20 mass % Fe, alloys with
anisotropy, magnetostriction, high magnetic permeability
[1978Mas] Magnetric permeability, coercive Initial and maximum permeability
force

Fe–Nb–Ni 5 9
[1979Wen] TEM, X-ray diffraction, magnetic Effect of modulated structure on hardness

properties, Vickers hardness and magnetic permeability
[1981Tai] X-ray diffraction, Vickers hardness, 79Ni-8Nb-13Fe (mass%) alloy; after cold
rolling texture rolling with reduction of 50 and 94%
[1982Osi] Magnetic susceptibility, Curie points 20-800˚C, NbFe2 - NbNi3 join.
Magnetic properties of the Laves
phase λ1
[1985Kov1] Optical microscopy, XRD, resistivity, Mechanical properties and the degree of
[1985Kov2] tensile test, bending deflection recovery of shape (shape memory alloys)
[1989Kov] Optical microscopy, resistivity, The degree of recovery of shape
bending deflection measurements
[1990Cho] Instron type testing machine 10 to 20 mass % Ni, < 4 mass% Nb,
compressive flow stress at 77 K.
[1992Sos] Coercive force, magnetic 16 mass% Fe, < 4 mass% Nb, mechanical
permeability, microhardness properties after rapid quenching

10 5 Fe–Nb–Ni
. Fig. 1
Fe-Nb-Ni. Change in lattice parameters of the λ1-NbFe2 Laves phase with Ni content (line -
calculation; empty circles - stoichiometric composition, filled circles - Fe-rich compositions

Fe–Nb–Ni 5 11
. Fig. 2
Fe-Nb-Ni. Isothermal section at 1200˚C

12 5 Fe–Nb–Ni
References
[1971Lei] Leitch, K., Chaturvedi, M., “Aging Behavior of Fe-30Ni Alloys Containing Niobium”, Metall. Trans.,
2(5), 1407-1413 (Crys. Structure, Morphology, Phase Relations, Experimental, Kinetics, Mechan.
Prop., 25)
[1972Mas] Masumoto, H., Murakami, Y., Hinai, M., “Magnetic Characteristics of Ni-Fe-Nb Alloys”, Trans. Jpn.
Inst. Met., 13(3), 182-185 (1972), translated from J. Jpn. Ins. Met., 35(10), 985-988 (1971) (Experimen-
tal, Electr. Prop., Magn. Prop., 23)
[1974Mas] Masumoto, H., Murakami, Y., Hinai, M., “Magnetic Properties of High Permeability Alloys Hardperm
in the Ni-Fe-Nb System”, J. Jpn. Inst. Met., 38(3), 238-241 (1974) (Phase Relations, Electr. Prop., Magn.
Prop., Experimental, 4)
[1975Pan] Panteleimonov, L.A., Aleshina, L.V., “Alloys of the Fe2Nb-Ni3Nb System” (in Russian), Vestn. Moskov.
Univ., (Khim), 16(5), 630-634 (1975) (Crys. Structure, Morphology, Phase Diagram, Experimental, #, 3)
[1976Hin] Hinai, M., “The Origin of High Magnetic Permeability in Hardperm of the Ni-Fe-Nb System”, Trans.
Jpn. Inst. Met., 17(11), 693-698 (1976), translated from J. Jpn. Ins. Met., 40(7), 682-686 (1976) (Phase
Relations, Experimental, Magn. Prop., 21)
[1978Mas] Masumoto, H., Hinai, M., Murakami, Y., “The Influence of Sheet Thickness and Heat Treatment on the
Magnetic Properties of Hardperm Alloys in the Ni-Fe-Nb System”, Trans. Jpn. Inst. Met., 19(7), 385-389
(1978) (Phase Relations, Experimental, Magn. Prop., 8) cited from abstract
[1979Wen] Wenchong, X., Junjian, W., Xiujin, S., Zhihua, L., “An Investigation of Magnetic Ni-Fe-Mo and Ni-Fe-
Nb Alloys” (in Chinese), Acta Metall. Sin., 15(2), 252-258 (1979) (Phase Relations, Experimental,
Magn. Prop., 8) cited from abstract
[1980Rus] Rusanenko, V.V., Perkas, M.D., Shaposhnikov, N.G., Edneral, A.F. “Ageing of Fe-Ni-Nb and Fe-Ni-Nb-Co
Alloys Martensite” (in Russian), Metallofizika, 2(6), 56-62 (1980) (Phase Relations, Experimental, Electr.
Prop., Mechan. Prop., 12)
[1980Tew] Tewari, S.N., “Growth Crystallography of Directionally Solidified Fe-Nb-Ni Eutectic Alloy”, Metallog-
raphy, 13(4), 379-381 (1980) (Crys. Structure, Morphology, Phase Relations, Experimental, 2)
[1981Tai] Tai, L.C., Tan, Z.J., “A Note on the Rolling Texture of Nickel-Iron-Niobium Alloy”, Texture of
Crystalline Solids, 4(3), 153-157 (1981) (Morphology, Experimental, Mechan. Prop., 7)
[1981Var] Varli, K.K., Druzhinia, T.I., D’yakonova, N.P., Pirogova, S.E., Rutman, A.M., “The Influence of Alloying
with Cobalt and Nickel on the Phase Stability of the Fe-Nb System” (in Russian), Izv. Vys. Ucheb. Zaved.
Chern. Metall., (9), 116-118 (1981) (Crys. Structure, Phase Relations, Experimental, 3)
[1982Osi] Osipova, L.V., Panteleymonov, L.A., “Magnetic Properties of Fe-Ni-Zr and Fe-Ni-Nb Alloys”, Russ.
Metall., (3), 183-185 (1982), translated from Izv. Akad. Nauk, Met., (3), 205-207 (1982) (Experimental,
Magn. Prop., 8)
[1984Ska] Skakov, Y.A., Dyakonova, N.P., Savin, V.V., Semina, V.K., Sharshatkina, A.V., “Influence of Cooling
Rate of Melt on Structure of Phases in Fe-Co-Nb and Fe-Ni-Nb Systems” (in Russian), Izv. Vys. Ucheb.
Zaved. Chern. Metall., (5), 85-90 (1984) (Crys. Structure, Phase Relations, Experimental, 6)
[1985Kov1] Koval’, Yu.N., Kozlov, A.P., Monastyrskii, G.E., “Martensitic Transformation and Memory Shape Effect
in Fe-Nb-Ni Alloys”, Akad. Nauk Ukr. SSR, Metallofizika, 7(4), 53-59 (1985) (Crys. Structure, Mor-
phology, Phase Relations, Experimental, Mechan. Prop., 15)
[1985Kov2] Koval’, Yu.N., Kozlov, A.P., Monastyrskii, G.E., “The Effect of Phase Hardening on the Shape-Memory
Effect in Fe-Ni-Nb Alloys” (in Russian), Akad. Nauk Ukr. SSR Metallofizika, 7(5), 95-99 (1985)
(Morphology, Phase Relations, Experimental, Mechan. Prop., 5)
[1985Val] Valiyev, E.Z., Men’shikov, A.Z., Panakhov, T.M., “The Structural State of Alloys Ni3(Fe1–xTix) and
Ni3(Fe1–xNbx) During Atomic Ordering”, Phys. Met. Metallogr., 59(1), 123-129 (1985) (Crys. Structure,
Phase Relations, Experimental, Electr. Prop., 14)
[1987Val] Valiev, E.Z., Menshikov, A.Z., “Nature of K State in Alloyed Permalloys” (in Russian), Fiz. Met.
Metolloved., 63(5), 1030-1032 (1987) (Experimental, Crys. Structure, Phase Relations, 6)
[1989Kov] Koval, Yu.N., Kozlov, A.P., Monastyrskii, G.E., “Influence of Work Hardening Caused by Martensitic
Transformation on the Shape Memory Effect in Fe-Ni-Nb Alloys”, Scr. Metall., 23(10), 1731-1734
(1989) (Morphology, Phase Relations, Experimental, Mechan. Prop., 3)
[1989Sav] Savin, V.V., “Formation and Stability of Laves Phases in the System Ni-Fe-Nb”, Phys. Met. Metallogr.,
68, 140-146 (1989), translated from Fiz. Met. Metalloved., 68(1), 143-149 (1989) (Crys. Structure, Phase
Diagram, Phase Relations, Experimental, 16)

Fe–Nb–Ni 5 13
[1990Cho] Choi, G., Shinoda, T., Mishima, Y., Suzuki, T., “Solid Solution Hardening in Ternary Ni-Y(Y:Co, Pd,
Fe)-Nb Alloys”, ISIJ Int., 30(9), 780-785 (1990) (Thermodyn., Experimental, Kinetics, 20)
[1991Gup] Gupta, K.L., “The Nb-Ni (Niobium-Nickel) System” in “Phase Diagrams of Ternary Nickel Alloys”,
Indian Inst. Met., Calcutta, Part 2, 151 (1991) (Phase Diagram, Review, 1)
[1992Mes] Meshkov, L.L., Nesterenko, S.N., Uskova, E.N., “The Laws of Phase Equilibria in Ternary Systems of
Refractory Transition Metals with Group VIIIB Metals”, Russ. Metall., (6), 140-144 (1992), translated
from Izv. Ross. Akad. Nauk. Met., (6), 153-157 (1992) (Phase Relations, Calculation, 10)
[1992Rag1] Raghavan, V., “The Fe-Nb-Ni (Iron-Niobium-Nickel) System” in “Phase Diagrams of Ternary Iron
Alloys”, Indian Inst. Met., Calcutta, 6B, 1025-1027 (1992) (Crys. Structure, Phase Diagram, Review, 11)
[1992Rag2] Raghavan, V., “The Fe-Nb (Iron-Niobium) System” in “Phase Diagrams of Ternary Iron Alloys”, Indian
Inst. Met., Calcutta, 6A, 38 (1992) (Crys. Structure, Phase Diagram, Review, 2)
[1992Sos] Sosnin, V.V., Glezer, A.M., Zhigalina, O.M., “Structure and Properties of Microcrystalline Alloys of the
System Ni-Fe-Nb(Mo)”, Met. Sci. Heat Treat., 34(3-4), 195-202 (1992) (Crys. Structure, Morphology,
Experimental, Magn. Prop., Mechan. Prop., 12)
[1993Bej] Bejarano, J.M.Z., Gama, S., Ribeiro, C.A., Effenberg, G., “The Iron-Niobiun Phase Diagram”, Z.
Metallkd., 84(3), 160-164 (1993) (Crys. Structure, Morphology, Phase Diagram, Experimental, #, 6)
[1993Kov] Koval, Yu.N., Monastyrsky, G.E., “Reversible Martensite Transformation and Shape Memory Effect in
Fe-Ni-Nb”, Scr. Metall. Mater., 28(1), 41-46 (1993) (Morphology, Experimental, Kinetics, 15)
[1993Zhi] Zhigalina, O.M., Sosnin, V.V., Glezer, A.M., “The Effects of Heat Treatment on Phase Transformations
in Rapidly Quenched Ni-Fe-Nb Alloys”, Phys. Met. Metallogr., 75(2), 205-209 (1993), translated
from Fiz. Met. Metallov., 75(2), 132-139 (1993) (Crys. Structure, Morphology, Phase Relations, Experi-
mental, 12)
[1998Oka] Okamoto, H., “Nb-Ni (Niobium-Nickel)”, J. Phase Equilib., 19(3), 289 (1998) (Phase Diagram,
Review, #, 7)
[2001Tak] Takeyama, M., Morita, S., Yamauchi, A., Yamanaka, M., Matsuo, T., “Phase Equilibria Among γ,
Ni3Nb-δ and Fe2Nb-ε Phases in Ni-Nb-Fe and Ni-Nb-Fe-Cr Systems at Elevated Temperatures”, Proc.
Int. Sympos., TMS-Miner. Metals & Mater. Soc., 333-344 (2001) (Crys. Structure, Morphology, Phase
Diagram, Phase Relations, Experimental, #, 17)
[2002Jou] Joubert, J.-M., Feutelais, Y., “Contribution of the Rietveld Method to Non-Stoichiometric Phase
Modeling. Part II: γ - Tl5Te3 and μ - Nb-Ni as Experimental Examples”, Calphad, 26(3), 427-438 (2002)
(Crys. Structure, Calculation, Experimental, 15)
[2004Rag] Raghavan, V., “Fe-Nb-Ni (Iron-Niobium-Nickel)”, J. Phase Equilib. Diffus., 25(6), 552 (2004) (Phase
[2005Tak] Takeyama, M., Gomi, N., Morita, S., Matsuo, T., “Phase Equilibria and Lattice Parameters of Fe2Nb
Laves Phase in Fe-Ni-Nb Ternary System at Elevated Temperatures”, Mater. Res. Soc. Symp. Proc., 842,
461-466 (2005) (Experimental, Morphology, Phase Diagram, Phase Relations, #, 11)
[2008Kuz] Kuznetsov, V., “Fe-Ni (Iron-Nickel)”, MSIT Binary Evaluation Program, in MSIT Workplace, Effenberg,
G. (Ed.), MSI, Materials Science International Services, GmbH, Stuttgart; to be published (2008) (Crys.
Structure, Phase Diagram, Phase Relations, Assessment, 41)
(1990)

Fe–Nb–P 6 1
Iron – Niobium – Phosphorus

Gabriele Cacciamani, Lesley Cornish, Damian M. Cupid, Jozefien De Keyzer
Introduction
The Fe-Nb-P system is only partially known. The main work on this system was done in the
sixties by [1962Vog] who investigated the Fe rich corner. [1962Vog] prepared 250 alloy
compositions in the Fe-FeP-Nb region from pure iron, red phosphorus and sheet niobium
(purities not stated). The phase equilibria were studied by thermal analysis (cooling rate of 0.5
to 2˚C·s–1), metallography, ray diffraction, hardness and magnetic measurements. Even though
[1962Vog] presented a liquidus surface covering the Fe-FeP-NbP2-Nb region of the system,
their experimental measurements were limited to the Fe-FeP-Nb region. This is also the most
important corner since niobium is used as a strengthening element in steels and phosphorus is
a common impurity in steels [1987Gra]. The system was reviewed by [1988Rag].
Binary Systems
The accepted binary Fe-Nb phase diagram is that from [1993Bej]. A thermodynamic calcula-
tion of the Fe-Nb system is from [2000Tof]. It incorporates many data points and is preferred
to the earlier calculation of [1994Sri]. Both of these show the peritectic formation of the μ
phase, rather than the earlier reported congruent formation [1986Pau].
The Fe-P system is accepted from the critical assessment of [2002Per].
The Nb-P phase diagram is not known, except for the partial diagram postulated by
[1962Vog] to accommodate the NbP and NbP2 phases [1931Hei].
Solid Phases
Crystal structure data on unary, binary and ternary phase are summarized in Table 1.
Since the Nb-P phase diagram not known, all binary Nb-P structures found in literature
have been reported here, but it is not clear which are stable phases in the system.
Three ternary compounds were identified by [1962Vog] in the Fe-FeP-Nb region. FeNbP
(τ1) is a well-established, congruently melting phase with the Co2Si type structure [1962Vog,
1966Run, 1965Kan1, 1973Mae]. The other two compounds melt incongruently and corre-
spond to the formulae FeNb2P (τ2) and FeNb4P (τ3). The crystal structure of FeNb4P has been
determined by [1977Pal].
Quasibinary Systems
In the Fe-FeP-Nb region, [1962Vog] found three quasibinary systems of the simple eutectic
type: Fe-τ1 (Fig. 1), Fe2Nb-τ1 (Fig. 2), and FeP-τ1, together with two quasibinaries of the

2 6 Fe–Nb–P
simple peritectic type: Fe2P-τ1 (Fig. 3), and τ1-τ2, which they drew schematically. Three of these
quasibinary sections are included in the FeP-Nb section. However, the quasibinary character of
the FeP-Nb section does not extend to pure FeP because, at higher temperatures, this phase is
in equilibrium with liquid and gas and tie lines are presumably not in the plane of the section.
Additionally, [1965Kan1] reported a wider solubility range in τ1 at 800˚C. These data are given
in Table 2.
The reaction scheme shown in Fig. 4 is based on the work of [1962Vog]. The temperature and
composition of the U2 reaction (see Table 2), which was added by [1988Rag], were changed to
be consistent with the currently accepted Fe-Nb binary system [1993Bej]. In the solid state, the
three-phase univariant line arising from the eutectoid reaction in the Fe-Nb system at 1190˚C
passes through the ternary region to return to the Fe-Nb side and culminate in the peritectoid
reaction at 960˚C. This situation arises, as the γ phase (γFe) in the Fe-P system is fully enclosed by
a loop.
Liquidus Surface
Even though [1962Vog] presented a liquidus surface covering the Fe-FeP-NbP2-Nb region of
the system, their experimental measurements were limited to the Fe-FeP-Nb region. The rest
of the system was inferred from the known binary and ternary compounds, and using
compatibility triangles. The surface for the Fe-FeP-Nb region has been redrawn in Fig. 5
using the currently accepted binary data. Reaction U2 was introduced by [1988Rag] to account
for the presence of the μ phase in the Fe-Nb system (not included by [1962Vog]), and altered
here to be consistent with the currently accepted Fe-Nb binary of [1993Bej].
[1997Vav] studied the metastable (rapidly-cooled) liquidus around Fe3P in order to obtain
amorphous phases.
Isothermal Sections
[1988Rag] has drawn isothermal sections (at.% and mass%) at 25˚C using the data of
[1962Vog] and adding μ, and this is redrawn here to be consistent with the currently accepted
Fe-Nb binary system (Fig. 6). [1965Kan1] determined an isothermal section for the iron rich
region at 800˚C. Their results indicated a wider homogeneity range for FeNbP (τ1) extending
towards Fe3P, rather than the line compound of [1962Vog] at room temperature. Niobium
drastically lowers the solubility of phosphorus in (αδFe) at 1000˚C [1965Kan2].
For non-equilibrium alloys (annealed rapidly-cooled specimens), [1997Vav] showed that
Fe2P extends further into the ternary than Fe3P, and there was a (αδFe) + Fe3P + Fe2P three-
phase field at 1.1 at.% Nb.

Fe–Nb–P 6 3
[1962Vog] has drawn a number of vertical sections, including those between Fe3P-NbFeP (Fig.
7) (with some apparently unresolved data points at about 1050˚C); Fe3Nb-Nb4FeP, at 2 mass%
Nb (Fig. 8) and at 2 mass% P. The latter is inconsistent with the currently accepted Fe-Nb
binary diagram because of μ in the latter, but [1962Vog] only had one alloy in that region.
A small region of amorphous phases was found in the Fe3P region and a metastable Fe2P
phase was identified [1989Bab, 1997Vav].
Thermodynamics
The vapor pressure of phosphorus on liquid Fe-Nb-P alloys has been measured by the
transportation method at 1400˚C by [1984Ban] (Table 3) and by Knudsen effusion method
by [1979Yam, 1983Yam] at 1600˚C.
The two authors calculated an interaction coefficient eNb
P defined as:
Nb

@IngP
eNb
P ¼
@xNb Xp!0
on the basis of the Chipman interstitial solution model.

According to [1984Ban] eNb P = –16.1±1.6 while according to [1979Yam, 1983Yam] it is
eNb
P = –5.4±1.2. A calculation performed by [1993Din] at 1600˚C produced a value of
eNb
P = –6.92.
Phosphorous is a glass-forming element and is used in the manufacture of iron-based

amorphous magnetically soft materials [1997Vav]. Unfortunately, phosphorus is also one of
the most harmful elements for steel products so that efforts have been made to remove
phosphorus from molten iron in the steelmaking process, or employ alloying additions
(e.g. Nb) that react to form precipitates and thus tie up P [1987Gra]. Iron phosphides may
improve resistance to scale formation, but, unless rectified, phosphorous segregates to the
grain boundaries, and also forms low melting point eutectics. These result in the impairment
of mechanical properties from reduced grain boundary cohesion and temper embrittlement
[1984Moe]. High Fe content alloys were studied [1984Moe], and P was consistently enriched
at the grain boundaries, usually with Nb, but not in equilibrium conditions. Increased Nb
decreased the grain boundary P segregation, as did increasing tempering temperature. The
influence of various elements on the segregation of phosphorus atoms in iron was examined
by Mössbauer spectroscopy [1999Vav], and ranked in decreasing influence as: Mn > Si > V >
Nb > Mo.
Experimental studies of properties are summarized in Table 4.

4 6 Fe–Nb–P
Miscellaneous
Crystallization kinetics were derived by [1990Bab1] using DTA and electrical resistance under
isothermal conditions. Mössbauer measurements undertaken by [1973Mae] indicated that Fe
atoms only occupied the smaller lattice positions. Similar work by [1990Bab2, 1999Vav,
2000Vav] on rapidly-quenched alloys, showed that metastable Fe2P made the stable formation
of amorphous Fe3P difficult. Metastable Fe2P was anti-ferromagnetic [1999Vav]. [1962Vog]
found that alloys containing (αδFe) were ferromagnetic; their other compositions were
paramagnetic.
. Table 1
Pearson
Symbol/
Phase/ Space Lattice
Temperature Group/ Parameters
αδ, (αδFe) cI2 up to 4.9 at.% P at 1048˚C [1997Hin]

Im3m up to 3.2 at.% Nb at 1373˚C [1986Pau]
W up to 0.7 at.% Nb at 961˚C [1986Pau]
(δFe) a = 293.15 pure Fe at 1390˚C [V-C2, Mas2]
1538 - 1394
< 912
(γFe) cF4 a = 364.67 pure Fe at 915˚C [V-C2, Mas2]
< 1394 - 912 Fm3m up to 0.6 at.% P at 1150˚C [1997Hin]
Cu up to 0.9 at.% Nb at 1210˚C [1986Pau]
P63/mmc c = 396.0
Mg
(Nb) cI2 a = 330.04 at 25˚C [Mas2]
< 2469 Im3m
W
(P) (I) cP1 a = 220 to 227 10 to 32 GPa [V-C2]
Pm3m
αPo
(P) (II) hR6 a = 337.7 high pressure phase,
R3m c = 880.6 5 to 11.1 GPa [V-C2]
As
(P) (red) c*66 a = 1131 sublimation at 1 bar triple point at 576˚C, > 36.3
< 417 bar; triple point at 589.6˚C at 1 atm [Mas2, V-C2]
(P) (white) c** a = 718 at 25˚C [Mas2]
< 44.14 ? common form of elemental P, probably less stable
P (white) than P (red) at 25˚C [Mas2]

Fe–Nb–P 6 5
Pearson
Symbol/
(P) (black) oC8 a = 331.36 at 25˚C [Mas2, V-C2]

Cmca b = 1047.8
P (black) c = 437.63
ε, NbFe2 hP12 a = 483.8 32 to 37 at.% Nb [1993Bej]
< 1630 P63/mmc c = 788.9
MgZn2
μ, Nb6Fe7 hR39 a = 492.8 48.0-52.0 at.% Nb [1993Bej]
≲ 1520 R3m c = 268.3 “FeNb” [1986Pau]
Fe7W6
Nb3Fe2 - - metastable [1991Bej]
1490 - 1460
Fe3P tI32 a = 910.8 25 at.% P [Mas2, V-C2]
< 1166 I4 c = 445.5
Ni3P a = 917.4 at 678˚C [2002Per]
c = 452.99
Fe2P hP9 a = 586.4 33.3 at.% P
< 1370 P62m c = 346.0 [Mas2, V-C2]
Fe2P
Fe2P (I) oP12 a = 577.5 at 800˚C and 80 kbar [Mas2, V-C2]
Pnma b = 357.1
Co2Si c = 664.1
FeP oP8 a = 520.8 [V-C2]
< 1370 Pnma b = 316
MnP c = 581.2
FeP2 oP6 a = 497.29 [1934Mei]
Pnnm b = 565.68
FeS2 c = 272.3
(marcasite)
FeP4 mP30 a = 461.9 [1978Jei]
P21/c b = 1367.0
FeP4 c = 700.2
β =101.48˚
FeP4 (I) oC20 a = 500.5 at 1100˚C and 60 kbar [1978Sug]
C2221 b = 1021.3
FeP4 c = 553.0
Nb3P tP32 a = 1012.8 [V-C2]
P42/n c = 508.9
Ti3P

6 6 Fe–Nb–P
Pearson
Symbol/
Nb2P oP54 a = 1807.9 [V-C2]

Pmma b = 342.5
Nb2P c = 1385.8
Nb7P4 mC44 a = 1495.0 [V-C2]
C2/m b = 344.0
Nb7P4 c = 1384.8
β = 104.74˚
Nb5P3 oP64 a = 2538.4 [V-C2]
Pnma b = 343.3
Nb5As3 c = 1148.3
Nb8P5 oP54 a = 2620.0 [V-C2]
Pbam b = 946.5
Nb8P5 c = 346.4
NbP tI8 a = 333.4 [V-C2]
I41md c = 1137.6
NbAs
Nb4P7 tP29 a = 746.8 [V-C2]
P4m2 c = 764.9
V4P7
NbP2 mC12 a = 887.15 [V-C2]
C2 b = 326.63
NbSb2 c = 751.94
β = 119.10˚
Nb2P5 oP28 a = 1674.2 prepared at 5 GPa [V-C2]
Pnma b = 335.0
Nb2P5 c = 791.2
* τ1, NbFeP oP12 a = 613.9 [1966Run, V-C2]
< 1820 Pnma b = 358.5 Congruent melting point [1962Vog]
Co2Si c = 700.6
* τ2, Nb2FeP - - Incongruent melting point [1962Vog]
≲ 1585
* τ3, Nb4FeP tP12 a = 613.0 [V-C2]
≲ 1545 P4/mcc c = 500.6 Incongruent melting point [1962Vog]
CoNb4Si

Fe–Nb–P 6 7
. Table 2
Composition (at.%)
Reaction T [˚C] Type Phase Fe Nb P
L + τ1 Ð τ2 ~1750 p1 L 21.3 57.8 20.9

L + τ2 Ð τ3 1660 p2 L 10.1 80.0 9.9
L Ð τ3 + (Nb) ~1600 e1 L 9.2 82.4 8.4
L Ð ε + τ1 1555 e2 L 52.6 33.3 14.1
L + τ1 Ð ε + τ2 1537 U1 L 38.9 48.6 12.5
L + ε Ð μ + τ2 ~1510 U2 L ~41 ~51.5 ~7.5
L + τ2 Ð μ + τ3 1503 U3 L 39.5 56.8 3.7
L Ð μ + τ3 + (Nb) 1489 E1 L 36.3 61.2 2.5
L + τ1 Ð Fe2P 1405 p4 L 64.7 2.0 33.3
L Ð τ1 + FeP ~1400 e4 L 46.5 7.7 45.8
L Ð τ1 + (αδFe) ~1303 e6 L 83.5 8.2 8.3
L Ð ε + τ1 + (αδFe) 1295 E2 L 84.0 9.3 6.7
L + τ1 Ð FeP + Fe2P 1275 U4 L 58.9 1.8 39.3
L + Fe2P Ð τ1 + Fe3P 1125 U5 L 76.0 0.5 23.5
L Ð μ + τ3 + (Nb) 1045 E3 L 82.6 0.7 16.7
. Table 3
Vapor Pressure Measurements
Phase(s) Temperature [˚C] Pressure [bar] Comments
Liquid (xNb = 0.032, 1400 pP = 4.9·10–5 [1984Ban] transportation

xP = 0.164) method
xP = 0.196) method
xP = 0.200) method
xP = 0.209) method

8 6 Fe–Nb–P
. Table 4
Investigations of the Fe-Nb-P Materials Properties
Method / Experimental
Reference Technique Type of Property
[1973Mae] Mössbauer Site occupancy; ordering

[1984Moe] Auger electrons P grain boundary enrichment
[1990Bab1] DTA, electrical resistance, TEM Kinetics; time dependence of crystallization
volume
[1990Bab2] Mössbauer Site occupancy; ordering
[1999Vav] Mössbauer Phase identification; magnetic studies

Fe–Nb–P 6 9
. Fig. 1
Fe-Nb-P. The (αδFe) - τ1 quasibinary system

10 6 Fe–Nb–P
. Fig. 2
Fe-Nb-P. The NbFe2 - τ1 quasibinary system

Fe–Nb–P 6 11
. Fig. 3
Fe-Nb-P. The Fe2P - τ1 quasibinary system

12 6 Fe–Nb–P
. Fig. 4
Fe-Nb-P. Partial reaction scheme in the Fe-FeP-Nb region

Fe–Nb–P 6 13
. Fig. 5
Fe-Nb-P. Partial liquidus projection in the Fe-FeP-Nb region

14 6 Fe–Nb–P
. Fig. 6
Fe-Nb-P. Partial isothermal section at 25˚C

Fe–Nb–P 6 15
. Fig. 7
Fe-Nb-P. Vertical section τ1 - Fe3P

16 6 Fe–Nb–P
. Fig. 8
Fe-Nb-P. Section at 2 mass% Nb, plotted in at.%

Fe–Nb–P 6 17
References
[1931Hei] Heinerth, E., Biltz, W., (in German) Z. Anorg. Allg. Chem., 198, 168-177 (1931) (Phase Diagram,
Experimental, 12) quoted in [1962Vog]
[1934Mei] Meisel, K., “Crystal Structure of FeP2” (in German), Z. Anorg. Chem., 218(4), 360-364 (1934) (Phase
Diagram, Crys. Structure, Experimental, 5)
[1962Vog] Vogel, R., Bleichroth W., “The Iron-Phosphorus-Niobium Ternary System” (in German), Arch.
Eisenhuttenwesen., 33(1), 195-210 (1962) (Phase Diagram, Experimental, #, *, 27)
[1965Kan1] Kaneko, H., Nishizawa, T., Tamaki, K., “Phosphide-Phases in Ternary Alloys of Fe, P and Other
Elements” (in Japanese), Nippon Kinzoku Gakkai-shi, 29(2), 159-165 (1965) (Phase Diagram, Morphol-
ogy, Experimental, 24)
[1965Kan2] Kaneko, H., Nishizawa, T., Tamaki, K., Tanifuji, A., “Solubility of Phosphorus in α and γ Iron” (in
Japanese), Nippon Kinzoku Gakkai-shi, 29(2), 166-170 (1965) (Experimental, 20)
[1966Run] Rundqvist, S., Nawapong, P.C., “The Crystal Structure of ZrFeP and Related Compounds”, Acta Chem.
Scand., 20(8), 2250-2254 (1966) (Crys. Structure, Experimental, 9)
[1973Mae] Maeda, Y., Takashima, Y., “Mössbauer Studies of FeNiP and Related Compounds”, J. Inorg. Nucl.
Chem., 35(6), 1963-1969 (1973) (Crys. Structure, Thermodyn., Experimental, Electronic Structure, 12)
[1977Pal] Palfii, Ya.F., Kuzma, Yu.B., “New Ternary Phosphides with the Nb4CoSi Type Structure”, Dopov. Akad.
Nauk Ukrain. RSR, A(3), 262-265 (1977) (Experimental, 3)
[1978Jei] Jeitschko, W., Baun, D.J., “Synthesis and Crystal Structure of the Iron Polyphosphide FeP4”, Acta
Crystallogr., 34B, 3196-3201 (1978) (Phase Diagram, Crys. Structure, Experimental, 30)
[1978Sug] Sugitani, M., Kinomura, N., Koizumi, M., “Preparation and Properties of a New Iron Phosphide FeP4”,
J. Solid State Chem., 26(2), 195-201 (1978) (Crys. Structure, Experimental, 14)
[1979Yam] Yamada, K., Kato, E., “Mass Spectrometric Determination of Activities of Phosphorus in Liquid
Fe-P-Si, Al, Ti, V, Cr, Co, Ni, Nb and Mo Alloys” (in Japanese), Tetsu to Hagane (J. Iron Steel Inst. Jpn.),
65(2), 273-280 (1979) (Experimental, Thermodyn., 40)
[1983Yam] Yamada, K., Kato, E., “Effect of Dilute Concentrations of Si, Al, Ti, V, Cr, Co, Ni, Nb and Mo on the
Activity Coefficient of P in Liquid Fe”, Trans. Iron Steel Inst. Jpn., 23(1), 51-55 (1983) (Experimental,
Thermodyn., 16) translated from [1979Yam]
[1984Ban] Ban-Ya, S., Maruyama, N., Kawase, Y., “Effects of Ti, V, Cr, Mn, Co, Ni, Cu, Nb, Mo and W on the
Activity of Phosphorus in Liquid Iron” (in Japanese), Tetsu to Hagane, 70(1), 65-72 (1984) (Thermo-
dyn., Experimental, 21)
[1984Moe] Moeller, R., Grabke, H.J., “Grain Boundary Segregation of Phosphorus in Fe-Nb-P and Fe-Nb-C-P
Alloys”, Scr. Metall., 18, 527-530 (1984) (Experimental, Kinetics, 7)
[1986Pau] Paul, E., Swartzendruber, L.J., “The Fe-Nb (Iron-Niobium) System”, Bull. Alloy Phase Diagrams, 7(3),
248-254 (1986) (Assessment, Crys. Structure, Magn. Prop., Phase Diagram, Review, Thermodyn., 83)
[1987Gra] Grabke, H.J., Moller, R., Erhart, H., Brenner, S.S., “Effects of the Alloying Elements Ti, Nb, Mo and V
on the Grain Boundary Segregation of P in Iron and Steels”, Surf. Interface Anal., 10, 202-209 (1987)
(Experimental, Phys. Prop., 20)
[1988Rag] Raghavan, V., “The Fe-Nb-P (Iron-Niobium-Phosphorus) System” in “Phase Diagrams of Ternary Iron
Alloys”, Indian Inst. Met., Calcutta, 3, 111-119 (1988) (Crys. Structure, Phase Diagram, Phase Relations,
Review, 7)
[1989Bab] Babaeva, R.M., Vavilova, V.V., Kovneristyi, Yu.K., “Metastable Phase Equilibria and Inclination to
Amorphization of the Alloys in the Systems Fe-P-M (M: Mo, Nb, V)” (in Russian), Dokl. Akad. Nauk
SSSR, 304(1), 139-142 (1989) (Experimental, Phase Diagram, Phase Relations, 5)
[1990Bab1] Babaeva, R.M., Vavilova, V.V., Kovneristyi, Y.K., Musin, V.R., “Kinetics of Crystallization
of Amorphous-Alloys of Fe-P-M (M = Mo, Nb, V) Systems”, Russ. J. Inorg. Chem. (Engl. Transl.),
35(8), 1224-1226 (1990), translated from Zh. Neorg. Khim., 35, 2147-2150 (1990) (Experimental,
Morphology, Thermodyn., 7)
[1990Bab2] Babaeva, R.M., Baldokhin, Yu.V., Kolotyrkin, P.Ya., Vavilova, V.V., “Mössbauer Study of Rapidly
Quenched Alloys of the Systems Fe-P-M (M: Mo, Nb, V)” (in Russian), Dokl. Akad. Nauk SSSR, 310(2),
366-371 (1990) (Crys. Structure, Experimental, Phase Relations, 7)
[1991Bej] Bejarano, J.M.Z., Gama, S., Ribeiro, C.A., Effenberg, G., Santos, C., “On the Existence of the Fe2Nb3
Phase in the Fe-Nb System”, Z. Metallkd., 82(8), 615-620 (1991) (Assessment, Experimental, Phase
Diagram, 8)

18 6 Fe–Nb–P
[1993Bej] Bejarano, J.M.Z., Gama, S., Ribeiro, C.A., Effenberg, G., “The Iron-Niobium Phase Diagram”,
Z. Metallkd., 84(3), 160-164 (1993) (Experimental, Phase Diagram, 6)
[1993Din] Ding, X., Wang, W., Han, Q., “Thermodynamic Calculation of Fe-P-j System Melt”, Acta Metall. Sin.
(China), 29(12), B527-B532 (1993) (Calculation, Theory, Thermodyn., 7)
[1994Sri] Srikanth, S., Petric, A., “A Thermodynamic Evaluation of the Fe-Nb System”, Z. Metallkd., 85, 164-170
(1994) (Calculation, Thermodyn., 49)
[1997Hin] Hino, M., Nagasaka, T., Ban-Ya, S., “Activity of Phosphorus in α-Fe and Phase Diagram of Fe-Fe2P
System Above 1273 K”, Z. Metallkd., 88(12), 938-944 (1997) (Thermodyn., Phase Diagram, Experimen-
tal, 34)
[1997Vav] Vavilova, V.V., Kovneristyi, Y.K., “Preparation and Thermal Stability of Fe-P-M (M = Mo, V, Nb, Mn,
Si) Amorphous Alloys”, Inorg. Mater. (Engl. Trans.), 33(3), 275-281 (1997), translated from Neorgan.
Mater., 33(3), 333-339 (1997) (Experimental, Phase Relations, Thermodyn., 15)
[1999Vav] Vavilova, V.V., Baldokhin, Yu.V., “Mössbauer Study of Rapidly Quenched Fe-P-E Alloys (E = V, Nb,
Mo, Mn, Si)”, Russ. Metall., (1), 132-139, (1999), translated from Russ. Akad. Nauk, Met., (1), 103-112
(1999) (Experimental, Phase Relations, 20)
Si) Amorphous Alloys”, Inorg. Mater., 33(3), 275-281 (1997) (Experimental, Phase Relations, 13)
[2000Tof] Toffolon, C., Servant, C., “Thermodynamic Assessment of the Fe-Nb System”, Calphad, 24(2), 97-112
(2000) (Assessment, Calculation, Phase Relations, Thermodyn., #, *, 40)
[2002Per] Perrot, P., Batista, S., Xing X., “Fe-P (Iron-Phosphorus)”, MSIT Binary Evaluation Program, in MSIT
Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services, GmbH, Stuttgart; Docu-
ment ID: 20.16107.1.20, (2002) (Phase Diagram, Assessment, Crys. Structure, Phase Relations, #, 23)
(1990)

Fe–Nb–Si 7 1
Iron – Niobium – Silicon

Ludmila Tretyachenko
Introduction
Only a few experimental works were performed to determine phase equilibria in the Fe-Nb-Si
system. [1956Gol] noted an extreme complexity of the phase diagram of this system and an
existence of numerous ternary compounds. The isothermal section at 1000˚C was published
by [1960Gol]. At least six compounds were found to exist in this system. Their exact
compositions and crystal structures were not determined. A possibility of three more com-
pounds was suggested. The compositions and crystal structure of six ternary compounds were
established as a result of further investigations [1963Spi, 1965Gla, 1967Mar, 1969Yar, 1969Jei,
1975Ste, 1980Ste, 1982Mal, 1983Mal].
The homogeneity range boundary of the Laves phase at 1300˚C was determined by
[1967Den]. The regions of the Laves and μ phases at 1100˚C were studied by [1972Sin].
[1982Mal] investigated the phase equilibria in the range of 30 to 50 at.% Si at the temperature
interval from 1000 to 1200˚C.
Solid solutions based on the binary Laves phase NbFe2 were studied by [1963Bar, 1967Den,
1972Sin, 1985Tro, 1986Bla].
Literature data on the phase equilibria and the ternary compounds were used by [1984Rag,
1987Rag] to construct a tentative liquidus surface projection and the isothermal section at
1150˚C.
Investigations performed during last years concerned the structure and properties, such as
magnetic, amorphous and nanocrystalline niobium alloys [1993Gao, 1994Gao, 2001Rix,
2001Tur, 2005Bar, 2005Pen, 2005Tur, 2006Tur1, 2006Tur2].
The only investigation of thermodynamic properties of the Fe-Nb-Si alloys was carried out
by [1989Sud].
The experimental investigations of the structure of alloys and the phase equilibria in the
Fe-Nb-Si system are listed in Table 1.
Binary Systems
The binary phase diagrams are accepted from [1993Bej] (Fe-Nb), [1982Kub] (Fe-Si) and
[Mas2] (Nb-Si).
Solid Phases
Data on solid phases pertinent to the Fe-Nb-Si system are listed in Table 2.
Significant solubility of the third element in the binary compounds was found only for the
NbFe2 (λ) and Nb19Fe21 (μ) phases.

2 7 Fe–Nb–Si
The λ phase homogeneity range reaches 25 at.% Si at 1300˚C [1967Den] and at 1100˚C
[1972Sin]. [1960Gol] reported the silicon solubility in NbFe2 at 1000˚C to be 25 at.% Si at 38
at.% Nb. However, in the isothermal section at 1000˚C presented by [1960Gol] the homoge-
neity range of the λ phases is extended up to ~ 34 at.% Si.
Silicon additions to the λ phase replace iron atoms rather than niobium and decrease
the c parameter whereas the a parameter remains nearly constant along the isopleth ~33 at.%
Nb. [1972Sin] did not reveal the c parameter to change along the constant niobium line
30 at.% Nb.
The μ phase was considered to be σ phase by [1960Gol].
The solubility in other binary phases does not exceed 1 at.% Nb or Si.
The homogeneity ranges of the ternary phases E, V, τ1, τ3 and τ4 are insignificant, about 1
at.%. The single phase τ2 was found in the range of 38.4 to 40.4 at.% Nb at 40.4 at.% Si
[1979Ste]. The Nb4FeSi phase (τ4) was detected by [1965Gla]. However, [1972Sin] did not
reveal this phase. [1980Ste] reported an existence of two modifications of the τ3 compound.
The high temperature βNb4Fe3Si5 phase (Nb4Fe3Si5 type crystal structure [1982Mal]) was
found to transform at 1130 ± 10˚C into a low temperature modification αNb4Fe3Si5, for which
the MgZn2 crystal structure type was detected. The relation of the αNb4Fe3Si5 to the NbFe2
Laves phase, which has the same crystal structure, is not clear.
The ternary phase Nb6Fe16Si7 (Cu6Mg16Si7 type, D8a) was obtained after annealing of an
amorphous material prepared by mechanical alloying [2001Rix]. For the first time Nb6Fe16Si7
was identified by [1992Rix] in an annealed melt spun Fe73.5Cu1Nb3Si13.5B9 alloy and was
supposed to be stabilized by a certain B content. It was considered to be metastable. The alloy
of the stoichiometric composition Nb:Fe:Si = 6:16:7 analyzed by [2001Rix] after a heat
treatment at 900˚C for 1 h contained mainly the Nb6Fe16Si7 phase. The Nb6Fe16Si7 phase
persisted after the heat treatment at 1050˚C for 90 h. The crystalline Nb6Fe16Si7 also could be
synthesized by melting pressed tablets of the elemental powders [2001Rix].
It should be noted that [1960Gol] reported a phase with unknown structure in the region
near the composition of Nb6Fe16Si7 in the section at 1000˚C.
Liquidus Surface
Melting temperatures of investigated alloys have been determined in argon arc furnace using
an optical pyrometer [1960Gol]. The results are shown in the concentration triangle but fields
of primary crystallization of phases were not delimited.
[1978Hao] found a eutectic, which had the composition 2.16Nb-74.61Fe-22.23Si (in at.%,
4.5Nb-83.5Fe-12Si mass%) and melted at 1360˚C. The compositions of phases in the eutectic
were not determined but [1978Hao] proposed the phase composition of the eutectic to be
NbSi2 + Fe(Si), what is impossible. The eutectic may be composed from NbFe2 + (Fe).
A tentative liquidus surface projection was constructed by [1984Rag] using the data of
[1960Gol] and [1978Hao] as well as an assumption that none of the ternary compounds has a
primary solidification field. The phase diagram of the Fe-Nb accepted by [1984Rag] does not
correspond to the last version of this system [1993Bej]. Moreover, the eutectic reported by
[1978Hao] is a three-phase eutectic, but not a four-phase, as assumed by [1984Rag]. So, the
liquidus surface is not given here.

Fe–Nb–Si 7 3
Isothermal Sections
The isothermal section at 1000˚C was reported by [1960Gol]. Phase equilibria involving six
ternary phases were shown in this section. However, the compositions of the ternary phases
were not determined exactly. Additionally three possible ternary phases not included in the
presented equilibria were shown tentatively. The binary phase diagrams accepted by [1960Gol]
do not correspond to the up to date versions [1993Bej, Mas2]. The λ phase field was found to
be very wide (~ 15 - 40 at.% Nb) and to extend up to ~ 34 at.% Si.
The isothermal section at 1000˚C reported by [1960Gol] was redrawn in the review by
[1961Eng].
[1967Den] determined the boundaries of the λ phase field at 1300˚C. It was shown that
this field is smaller than that by [1960Gol] at 1000˚C. [1967Den] reported also that the size of
the λ field was smaller by up to 2 at.% Nb at 1000˚C than at 1300˚C.
A partial isothermal section in the region of the λ and μ phases at 1100˚C was published by
[1972Sin]. The size of the λ phase field was found to be close to that determined by [1967Den],
from ~ 25 to ~ 35 at.% Nb and up to 25 at.% Si.
Both the λ and μ phase fields extend along constant niobium lines [1960Gol, 1963Bar,
1967Den, 1972Sin]. Bewilderment arises from the statement of [1986Bla] that the homogene-
ity range of the phase with the MgZn2 type crystal structure (Friauf - Laves phase) extends
from NbFe2 up to Nb0.2Si0.8Fe2, that is along the line of constant Fe content of 66.7 at.% at Si
content from 0 up to 26.7 at.%.
[1982Mal] published the partial section in the region of silicon content above 30 at.%,
which shows the phase equilibria in the temperature range of 1000 - 1200˚C. The phase
equilibria in this region involve NbFeSi2, Nb4Fe4Si7, NbFe3Si5, NbFeSi2 and NbFeSi ternary
phases.
The data by [1967Den, 1972Sin, 1982Mal] as well as those by [1965Gla, 1975Ste, 1979Ste,
1980Ste, 1985Gle1, 2001Ito, 2005Tur, 2006Tur1] were used to construct the isothermal section
at ~ 1150˚C (Fig. 1).
Calculations of the α - γ (bcc - fcc) phase equilibria were performed by [1989Kum]. The
calculated partial isothermal sections are shown in Figs. 2 to 5.
Thermodynamics
Partial and integral enthalpies of dissolution (ΔHd) and mixing (ΔHmix, ΔHi) were determined
by calorimetry [1989Sud] and are given in Table 3. A thermodynamic model used for
calculation of the bcc - fcc equilibrium in the ternary system Fe-Nb-Si is presented by
[1989Kum].
Notes on Materials Properties and Application
Mechanical properties of Fe-Si alloys with additions of niobium were investigated by

[1985Gle1, 1985Gle2]. It was found that alloying of the high-silicon iron containing 11 at.%
Si with niobium (up to 3 at.%) decreased the transition temperature from ductile to brittle
fracture and extended a temperature range of plasticity.

4 7 Fe–Nb–Si
Investigations of magnetic and electric properties of these alloys were carried out by
[1985Gle2]. It was revealed that niobium does not cause practically any change in magneto-
striction, specific magnetic losses, magnetic induction and coercive force of high-silicon iron.
A number of works concerned magnetic properties of Fe-Si alloys with addition of
niobium rapidly quenched by melt spinning [2001Tur, 2005Bar, 2005Tur, 2006Tur1,
2006Tur2] (amorphous or nanocrystalline materials). [2001Tur] revealed Nb to enhance the
coercivity (about 10 times) in the alloys Fe100–(x+y)SixNby . However, the coercive force is nearly
temperature independent up to about 400˚C in Fe76Si20Nb2. An increase in the local magnetic
stiffness with increasing Nb content was found by [2005Bar]. An increase of the coercive field,
Hc, and the Curie temperature, TC, for Fe80–xSi20Nbx (0 ≤ x ≤ 10) were reported [2005Tur].
The temperature dependence of the coercive field in the melt-spun alloys was reported by
[2006Tur1]. Magnetic transitions in the nanocrystalline alloy were investigated by [2006Tur2].
Magnetic properties of the Laves phases were examined by [1960Gol]. He reported that a
boundary exists, which divides the Laves phase field into two parts in accordance with
magnetic properties of the alloys. However, the ferromagnetism of the alloys in the region of
the Laves phase shown by [1960Gol] seems more probable to be explained by the presence of
Fe based phases in these alloys.
Microhardness of the alloys Nb1–xSixFe2 was measured by [1986Bla] (for Nb0.8Si0.2Fe2 also
by [1985Tro]). Microhardness values were found to decrease from 10418 N·mm–2 to 7853
N·mm–2 for Nb0.2Si0.8Fe2. However, it should be reminded that all the alloys from NbFe2 up to
Nb0.2Si0.8Fe2 were considered to be continuous solid solutions of the MgZn2 type that contra-
dicts to other available data.
The influence of Nb doping on thermoelectric properties of βFeSi2 has been studied by
[2001Ito]. The electrical resistivity, thermoelectric power and thermal conductivity were
measured in the range from room temperature to 900˚C.
Resistance to oxidation of some Fe-Nb-Si alloys has been studied by [1960Gol] at 1000˚C
in still air. Only negligible oxidation was observed for the 55Fe-20Nb-25Si (at.%) alloy. That is
the composition where [2001Rix] has found the new compound Nb6Fe16Si7.
An oxidation study in slowly flowing oxygen was carried out at 1150˚C by [1978Hao]. The
85Fe-8.5Nb-6.5Si (mass%) (80.3Fe-3.7Nb-16Si (at.%)) was found to be oxidized at a cata-
strophic rate. Resistance to oxidation of the eutectic found by [1978Hao] at the composition
of 83.5Fe-4.5Nb-12Si (mass%) (75.9Fe-2.4Nb-21.7Si (at.%)) was poor. The specific gravity of
this eutectic was detected to be 8000 kg·m–3.
Miscellaneous
Alloys Fe-(1 to 3)Nb-11Si (at.%) have been studied after a stepped heat treatment from
1000˚C, 1 h down to 500˚C, 100 h and further cooling to room temperature [1985Gle1,
1985Gle2]. It was revealed that niobium changed neither an ordering temperature nor an
equilibrium degree of atomic order. Precipitations of NbFe2 phase were observed, their
quantity increased with Nb content.
Thermal stability of a nanocrystalline alloy (Fe3Si)0.95Nb0.05 was studied by [1993Gao].
The alloy prepared using high energy ball milling consisted of disordered bcc solid solution
and had grain size of 7-9 nm. During annealing at 450˚C the alloy containing Nb was
considerably more stable against grain growth than the binary Fe3Si alloy. It was somewhat

Fe–Nb–Si 7 5
more stable against ordering. Niobium segregation away from the D03 (α1) ordered domains
was observed.
A structural study [2005Pen] of Fe80–xNbxSi20 (0 ≤ x ≤ 20) ribbons prepared by melt
spinning has revealed that these alloys were composed of amorphous, cubic bcc (Fe) and
hexagonal NbFe2–xSix (λ) phases. The ordered α2 (D03) and α1 (B2 CsCl type) also were
formed in the alloys with low Nb content and disappeared in the alloys with higher
(10-12 at.%) Nb content. During annealing at 850˚C the λ phase decomposes into two
hexagonal phases with similar structures. Nb atoms hindered growth of grains in the alloys.
The grain size in as cast and annealed alloys at x = 0.5 was large, about 1 μm. However,
the addition of 3 at.% Nb caused a decrease in grain size, which abruptly diminished to about
100 nm and reached 37 nm for Fe68Nb12Si20. There was no evidence that Nb atoms enter the
cubic bcc (Fe) lattice, as it was supposed earlier [2001Tur].
Similar results were obtained by [2005Bar, 2005Tur, 2006Tur1, 2006Tur2] in structural
studies of melt-spun Fe-Nb-Si alloys. The grain size of 18 nm was obtained for Fe60Nb20Si20
[2006Tur2].
Crystallization of mechanically alloyed 55Fe-21Nb-24Si (at.%) was studied by [2001Rix].
As-milled material was found to be amorphous. A crystallization peak was determined at
750˚C. An isothermal heat treatment at 900˚C resulted in the formation of a D8a phase with a
small amount of the hexagonal λ phase (NbFe2). The Mössbauer spectroscopy did not reveal
magnetic ordering down to 77 K.
. Table 1
Investigations of the Fe-Nb-Si Phase Relations, Structures and Thermodynamics
Temperature / Composition / Phase

Reference Method / Experimental Technique Range Studied
[1960Gol] Arc melting, XRD, melting point 1000˚C, 250 alloys, 15 binary and six (or
determination, magnetic properties, nine) ternary phases
oxidation resistance
[1963Bar] Arc melting, optical microscopy (OM), XRD 1100˚C, Nb(Fe1–xSix)2 (x = 0, 0.165, 0.330)
(λ)
[1963Spi] Arc melting, OM, XRD 1100˚C, NbFeSi (E)
[1965Gla] XRD 1100˚C, Nb4FeSi (66.7 at.% Nb
isoconcentrate)
[1967Den] Arc melting, OM, XRD 800, 1000, 1300˚C, Laves phase
[1967Mar] Arc melting, XRD 800˚C, ~ NbFeSi2
[1969Jei] Arc melting, XRD, OM 1200˚C, NbFeSi (E), Nb4Fe4Si7 (V)
[1969Yar] Arc melting, XRD NbFeSi
[1972Sin] Arc melting, OM, XRD 1100˚C, 30 alloys, λ, μ
[1975Ste] OM, Electron microprobe analysis (EMPA), 1200˚C, NbFeSi2
electron microdiffraction (EMD)

6 7 Fe–Nb–Si

[1978Hao] Induction melting; DTA, scanning electron 3 alloys, 73Fe-15.5Nb-11.5Si, 80Fe-10Nb-

microscopy (SEM), oxidation studies at 10Si, 85Fe-8.5Nb-6.5Si (mass%), eutectic
1150˚C, specific gravity measurement composition
[1979Ste] Chemical vapor transport reaction, XRD, 1100˚C, Nb~2Fe~1Si~2
EMPA
[1980Ste] EMPA, XRD 1200˚C, Nb32.7±1Fe26±1Si41.3±1
(αNb4Fe3Si5, βNb4Fe3Si5)
[1982Mal] Chemical vapor transport reaction, XRD 1200˚C, 40Nb-20Fe-40Si (at.%),
(single crystal), EMPA isothermal section for the temperature
range 1000-1200˚C, 30-50 at.% Si,
βNb4Fe3Si5
[1983Mal] Chemical vapor transport reaction, XRD Nb4Fe~3Si~5
(single crystal)
[1985Gle1] Induction melting, XRD, SEM, Fe-11Si-1(2; 3)Nb (at.%)
photoelectron spectroscopy, mechanical,
magnetic, electrical properties
[1985Gle2] Transmission electron microscopy (TEM), Fe-11(12)Si-(0 to 12)Nb (at.%), 500-800˚C
XRD, high temperature XRD, mechanical
properties
[1985Tro] Arc melting, XRD, microhardness 900-1200˚C, Nb0.8Si0.2Fe2
measurements, OM (66.6Fe-26.7Nb-6.7Si (at.%))
[1986Bla] Arc melting, XRD, OM, microhardness 800-1200˚C, NbFe2- Nb0.2Si0.8Fe2
measurements
[1989Kum] Calculation 950, 1050, 1150, 1250˚C, isothermal
sections of the Fe corner
[1989Sud] Calorimetry 1614˚C, FeSi-Nb (0 ≤ xNb ≤ 0.4), enthalpy
of dissolution and mixing
[1993Gao] Mechanical alloying, XRD, Mössbauer 450˚C, nanocrystalline powder
spectroscopy, TEM, energy dispersive (Fe3Si)0.95Nb0.05
X-ray spectrometry (EDS)
[1994Gao] Mechanical alloying, Mössbauer 450˚C, (Fe3Si)0.95Nb0.05
spectroscopy, XRD, TEM, EDX
[2001Rix] Mechanical alloying and inductive up to 1050˚C, Fe16Nb6Si7 (D8a)
melting; XRD, Mössbauer spectroscopy,
DTA
[2001Ito] XRD, SEM, EDX, electrical resistivity, from room temperature to 900˚C,
thermoelectric power, thermal Fe1–xNbxSi2 (0 ≤ x ≤ 0.04)
conductivity
[2005Bar] Melt spinning, NMR, magnetic properties Rapidly quenched ribbons,
Fe100–x–ySixNby (9.5 ≤ x ≤ 20, 0.5 ≤ y ≤ 12)

Fe–Nb–Si 7 7

[2005Pen] Melt spinning, high-resolution XRD as cast and annealed at 850˚C,

Fe80–xSi20Nbx (0 ≤ x ≤ 12)
[2005Tur] Melt spinning, high-resolution XRD, SEM, as cast and annealed at 850˚C,
NMR, magnetic properties Fe80–xSi20Nbx (x = 0.5, 1.5, 2.0, 3.0, 10)
ribbons
[2006Tur1] Melt spinning, magnetic properties (2- Fe77.9Nb10Si12.1, Fe70Nb10Si20
1123 K), Mössbauer spectroscopy, XRD
[2006Tur2] Melt spinning, XRD, magnetic properties 2-413 K, Fe80–xSi20Nbx (x = 12, 20)
. Table 2
Pearson
Symbol /
Phase / Space Lattice
Temperature Group / Parameters
α, (αFe,δFe) cI2
(δFe) Im3m a = 293.15 pure Fe at 1390˚C [Mas2, V-C2]
1538 - 1190 W Fe-Nb system, dissolves up to 3.2 at.% Nb
[1993Bej]
Fe-Si system, dissolves up to 19.5 at.% Si
[1982Kub]
< 912 [1993Bej], dissolves 0.73 at.% Nb
< 960 δα (Fe-Si) solid solutions [1982Kub]
γ, (γFe) cF4 a = 364.67 pure Fe at 915˚C [Mas2, V-C2]
1394 - 912 Fm3m dissolves 1 at.% Nb [1993Bej],
3.19 at.% Si [1982Kub]
Cu
(Nb) cI2 a = 330.04 [Mas2]
< 2469 Im3m dissolves 7 at.% Fe [1993Bej], 3.5 at.% Si
[Mas2]
W
a = 330.4 ~1.9 at.% Fe, 1000˚C [1960Gol]
a = 329.1 ~3.4 at.% Fe, 1200˚C [1960Gol]
(Si) cF8 a = 543.06 [Mas2]
< 1414 Fd3m
C (diamond)

8 7 Fe–Nb–Si
Pearson
Symbol /
λ, hP12 [1960Gol, 1963Bar, 1967Den, 1972Sin,

Nb1±y(Fe1–xSix)2 P63/mmc 1985Tro, 1986Bla]
MgZn2 0 ≤ x ≤ 0.375, ~ 0.79 ≤ 1 ± y ≲; 1.06
1100˚C [1972Sin]
1300˚C [1967Den]
(25 at.% Si);
at 1000˚C 0 to ~34 at.% Si [1960Gol]
a = 483.7 [1993Bej, V-C2]
c = 788.4 32 to 37 at.% Nb [1993Bej]
NbFe2 a = 481.1 to 483.2 from 20 to 40 at.% Nb, annealed at 1000˚C
< 1630 c = 785.7 to 787.1 [1960Gol]
a = 483.5 to 483.9
c = 788.5 to 786.8 Nb(Fe1–xSix)2, 0 ≤ x ≤ 0.33, homogenized at
a = 484.14 to 483.6 1100˚C [1963Bar]
c = 789.33 to 785.9 at ~33 at.% Nb, 0 to 25 at.% Si (annealed at
1300˚C) [1967Den]
a = 482.1 70Fe-30Nb (at.%), annealed at 1100˚C
c = 786.4 [1972Sin]
a = 482.2 65Fe-30Nb-5Si (at.%) (annealed at 1100˚C
c = 786.1 [1972Sin]
a = 482.2 55Fe-30Nb-15Si (at.%) (annealed at
c = 785.7 1100˚C) [1972Sin]
a = 481.0 55Fe-25Nb-20Si (at.%) (1100˚C, three-
c = 780.0 phase alloy) [1972Sin]
a = 481.4 Nb0.8Si0.2Fe2 (annealed at 900-1200˚C)
c = 785.5 [1985Tro]
μ, Nb19Fe21 hR39 a = 492.6 [1993Bej, V-C2]
< 1520 R3m c = 268.0 48 to 52 at.% Nb, < 1400˚C, ~50 to 54 at.%
W6Fe7 Nb at 1520 to 1500˚C [1993Bej]
dissolves up to 15 at.% Si at 1000˚C
[1960Gol], 10 at.% Si at 1100˚C [1972Sin]
Nb3Fe2 metastable [1993Bej]
1490 - 1460 cF96 [Mas2]
Fd3m a = 1126.1 [1960Gol]
Ti2Ni

Fe–Nb–Si 7 9
Pearson
Symbol /
α2, Fe-Si cP2 ordered B2 modification of Fe with 10 to 22

≲ 1280 Pm3m at.% Si [1982Kub, Mas2]
CsCl a = 281 [V-C2]
α1, Fe3Si cF16 ordered D03 modification of Fe with 11 to
≲ 1235 Fm3m 30 at.% Si [1982Kub, Mas2]
BiF3 a = 565.0 [V-C2]
β, Fe2Si hP6 ~33.0 to ~34.3 at.% Si [1982Kub]
1212 - 1040 P3m1 a = 405.2 ± 0.2 [V-C2]
Fe2Si c = 508.55 ± 0.03
η, Fe5Si3 hP16 37.5 at.% Si [1982Kub]
1060 - 825 P63/mcm a = 675.9 ± 0.5 [V-C2]
Mn5Si3 c = 472.0 ± 0.5
ε, FeSi cP8 49.6 to 50.8 at.% Si [1982Kub]
< 1410 P213 a = 451.7 ± 0.5 [V-C2]
FeSi
ζl, αFeSi2(r) oC48 66.7 at.% Si [1982Kub]
< 982 Cmca a = 986.3 ± 0.7 [V-C2]
αFeSi2 b = 779.1 ± 0.6
c = 783.3 ± 0.6
ζh, βFeSi2(h) tP3 69.5 to 73.5 at.% Si [1982Kub]
1220 - 937 P4/mmm a = 269.01 [V-C2]
βFeSi2 c = 513.4
Nb3Si tP32 a = 1022.4 ± 0.3 [Mas2, V-C2]
1980 - 1770 P42/n c = 518.9 ± 0.1
Ti3P
βNb5Si3 tI32 a = 1002.6 37.5 to 40.5 at.% Si [Mas2, V-C2]
2520 - 1650 I4/mcm c = 507.17
W5Si3
αNb5Si3 tI32 a = 657.1 37.5 to 38.5 at.% Si [Mas2, V-C2]
< 1940 I4/mcm c = 1188.9
Cr5B3
NbSi2 hP9 a = 481.9 ± 0.2 [Mas2, V-C2]
< 1940 P6422 c = 659.2 ± 0.2
CrSi2
* V, Nb4Fe4Si7 tI60 a = 1265.2 ± 0.2 [1969Jei]
I4/mmm c = 498.1 ± 0.1
Zr4Co4Ge7

10 7 Fe–Nb–Si
Pearson
Symbol /
* E, NbFeSi oP12 a = 623.1 ± 0.2 [1969Jei]

Pnma b = 367.7 ± 0.2
TiNiSi c = 719.0 ± 0.4
or a = 711 [1963Spi]
Co2Si b = 529
c = 1125
a = 624 [1969Yar]
b = 722
c = 369
* τ1, NbFeSi2 tI56 a = 1258 ~NbFeSi2 [1967Mar]
I4/mmm, c = 497
I4m2, I
42m,
I4mm or I422
TiNiSi2
or
Co3Nb4Si7 [V-C2]
orthorhombic a = 868.9 ± 0.5 [1975Ste]
Pmmm, b = 973.3 ± 0.5
Pmm2 or c = 757.6 ± 0.5
P222
or
oP48 [V-C2]
Pbam
TiMnSi2
* τ2, Nb2FeSi2 tP198 [1979Ste, V-C2]
P42/mcm
Nb2FeSi2
a = 2372 ± 3 for Nb76Fe42Si80 [1979Ste]
c = 495.5 ± 0.7
a = 2376 ± 1 for Nb78Fe40Si80 [1979Ste]
c = 495.9 ± 0.1
a = 2378 ± 3 for Nb80Fe38Si80 [1979Ste]
c = 496.0 ± 0.7
* τ3, βNb4Fe3Si5 oP72 a = 1282.1 ± 0.6 [1980Ste, 1982Mal, 1983Mal] (1200˚C)
> 1130 ± 10 Pmn21 b = 491.2 ± 0.1 exact formula Nb24Fe19Si29 [1983Mal]
Nb4Fe3Si5 c = 1552.1 ± 0.2
* τ3´, αNb4Fe3Si5 hP12 a = 486.8 ± 0.1 annealed at 1100˚C [1980Ste]
< 1130 ± 10 P63/mmc c = 775.8 ± 0.1
MgZn2

Fe–Nb–Si 7 11
Pearson
Symbol /
* τ4, Nb4FeSi tP12 a = 619.3 ± 0.2 annealed at 1100˚C [1965Gla, V-C2]

P4/mmc c = 505.6 ± 0.1
Nb4CoSi
* Nb6Fe16Si7 cF116 a = 1133.5 ± 0.1 [1992Rix, 2001Rix], in mechanically alloyed
Fm3m alloy annealed at 900˚C; presumably
Th6Mn23 or metastable
Mg6Cu16Si7
. Table 3
Enthalpies of Dissolution and Mixing of the FeSi-Nb Alloys at 1164˚C [1989Sud]
xNb, at. fraction –ΔHd [kJ·mol–1] –ΔHmix [kJ·mol–1] [kJ·mol–1]

–ΔH
–ΔH –1
Nb FeSi [kJ·mol ]
0 0 0 125 ± 15 0
0.1 8.2 ± 0.1 11.1 ± 0.1 80 ± 10 3.3 ±0.5
0.2 10.9 ±0.1 16.5 ± 0.2 43 ±10 10.5 ± 0.8
0.3 10.4 ± 0.2 18.7 ± 0.3 23 ± 3 17.2 ± 1.0
0.4 10.2 ± 0.2 18.5 ± 0.3 15 ± 2 21.6 ± 1.5

12 7 Fe–Nb–Si
. Fig. 1
Fe-Nb-Si. Isothermal section at ~1150˚C

Fe–Nb–Si 7 13
. Fig. 2
Fe-Nb-Si. Partial calculated isothermal section at 950˚C

14 7 Fe–Nb–Si
. Fig. 3

Fe–Nb–Si 7 15
. Fig. 4

16 7 Fe–Nb–Si
. Fig. 5

Fe–Nb–Si 7 17
References
[1956Gol] Goldschmidt, H.J., “The Metallurgy of Niobium”, J. Inst. Met., 85, 547-558 (1956) (Phase Diagram,
Phase Relations, Review, 2)
[1960Gol] Goldschmidt, H.J., “The Constitution of the Fe-Nb-Si System”, J. Iron Steel Inst., 169-180 (1960) (Crys.
Structure, Experimental, Magn. Prop., Phase Diagram, Phase Relations, Phys. Prop., 51)
[1961Eng] English, J.J., “Binary and Ternary Phase Diagrams of Columbium, Molybdenum, Tantalum and Tungsten”,
Defense Metals Information Center, Batelle Memorial Institute, Columbus, Ohio, 152, 101-102 (1961)
(Phase Diagram, Phase Relations, Review, 1)
[1963Bar] Bardos, A.M., Bardos, D.I., Beck, P.A., “The Effective Atomic Radius of Si in Ternary Laves Phase
Alloys”, Trans. Metall. Soc. AIME, 227, 991-993 (1963) (Crys. Structure, Experimental, 12)
[1963Spi] Spiegel, F.X., Bardos, D., Beck, P.A., “Ternary G and E Silicides and Germanides of Transition
Elements”, Trans. Metall. Soc. AIME, 227, 575-579 (1963) (Crys. Structure, Experimental, 13)
[1965Gla] Gladyshevsky, E.I., Kuzma, Yu.B., “The Nb4FeSi, Nb4CoSi, and Nb4NiSi Compounds and Their Crystal
Structures”, J. Struct. Chem., 6, 60-63 (1965), translated from Zh. Strukt. Khim., 6, 70-74 (1965) (Crys.
Structure, Experimental, 5)
[1967Den] Denham, A.W., “Extent and Lattice Parameters of the Laves Phase Field in the Fe-Nb-Si System”, J. Iron
Steel Inst., 205, 435-436 (1967) (Crys. Structure, Experimental, Phase Diagram, Phase Relations, 5)
[1967Mar] Markiv, V.Ya., Gladyshevsky, E.I., Skolozdra, R.V., Kripyakevich, P.I., “Ternary Compounds of the
RX´X´´2 Type in the Ti-V(Fe, Co, Ni)-Si and Similar Systems” (in Ukrainian), Dopov. Akad. Nauk
Ukrain. RSR (A), (3), 266-269 (1967) (Crys. Structure, Experimental, 12)
[1969Yar] Yarmolyuk, Y.P., Markiv, V.Y., Gladyshevsky, E.I., “Compounds with the TiNiSi Structure in the
Systems of Two Transition Metals and Either Si or Ge” (in Ukrainian), Vestn. L’vov. Univ. Khim., 11, 14-
17 (1969) (Crys. Structure, Experimental, 5)
[1969Jei] Jeitschko, W., Jordan, A,G., Beck, P.A., “V and E Phases in Ternary Systems with Transition Metals and
Si or Ge”, Trans. Met. Soc. AIME, 245, 335-339 (1969) (Crys. Structure, Experimental, 27)
[1972Sin] Singh, B.N., Gupta, K.P., “Laves and μ Phases in the Nb-Fe-Si and Nb-Co-Si Systems”, Metall. Trans., 3,
1427-1431 (1972) (Crys. Structure, Experimental, Phase Diagram, Phase Relations, 17)
[1975Ste] Steinmetz, J., Albrecht, J.-M., Zanne, M., Roques, B., “A New Ternary Silicide of Nb and Fe, NbFeSi2”
(in French), Compt. Rend. Acad. Sci. Paris, 281(C), 831-833 (1975) (Experimental, Crys. Structure, 6)
[1978Hao] Haour, G., Mollard, F., Lux, B., Wright, G., “New Eutectics Based on Fe, Co or Ni”, Z. Metallkd., 69, 26-
32 (1978) (Experimental, Morphology, Phase Diagram, Phase Relations, Phys. Prop., 24)
[1979Ste] Steinmetz, P.J., Roques, B., Courtois, A., Protas, J., “Crystal Structure of Nb78Fe40Si80” (in French), Acta
Crystallogr., Sect. B: Struct. Crystallogr. Crys. Chem., 35, 2509-2514 (1979) (Crys. Structure, Experimen-
tal, 9)
[1980Ste] Steinmetz, J., Steinmetz, P., “Structure of NbFe2–xSix Alloys” (in French), J. Less-Common Met., 69, 379-
[1982Kub] Kubaschewski, O., “Iron - Silicon” in “Iron Binary Phase Diagrams”, Springer Verlag, Berlin, 136-139
(1982) (Phase Diagram, Phase Relations, Review, #, 23)
[1982Mal] Malaman, B., Steinmetz, J., Venturini, G., Roques, B., “Crystal Structure of the Phase Nb4Fe~3Si~5-β
and a Diagram of the Nb-Fe-Si System” (in French), J. Less-Common Met., 87, 31-43 (1982) (Crys.
Structure, Experimental, Phase Diagram, Phase Relations, 11)
[1983Mal] Malaman, B., Steinmetz, J., Venturini, G., Roques, B., “β-Nb4Fe3Si5 with New Orthorhombic Structure
Type; Its Relationships to Other Ternary Silicides of Niobium-Iron” in “VII International Conference on
Solid Compounds of Transition Elements”, Proc. CNRS, 11A8 (1983) (Crys. Structure, Experimental,
Phase Relations, 4)
[1984Rag] Raghavan, V., Ghosh, G., “The Fe-Nb-Si System”, Trans. Ind. Inst. Met., 37, 421-425 (1984) (Experi-
mental, Phase Diagram, Phase Relations, 18)
[1985Gle1] Glezer, A.M., Maleeva, I.V., Zakharov, A.I., “Atomic Ordering and Mechanical Properties of Alloyed
High-Silicon Iron” (in Russian), Izv. Acad. Nauk SSSR, Ser. Fiz., 49, 1633-1644 (1985) (Crys. Structure,
Experimental, Mechan. Prop., Phase Relations, 12)
[1985Gle2] Glezer, A.M., Maleeva, I.V., Zakharov, A.I., “Influence of Alloy Elements on the Plasticity of High-
Silicon Iron”, Met. Sci. Heat Treat., 27, 908-912 (1985), translated from Metallov. Term. Obrab. Met., 27,
27-30 (1985) (Crys. Structure, Experimental, Morphology, Thermodyn., 7)

18 7 Fe–Nb–Si
[1985Tro] Trojko, R., Blazina, Z., “Metal-Metalloid Exchange in Some Friauf-Laves Phases Containing Two
Transition Metals”, J. Less-Common Met., 106, 293-300 (1985) (Crys. Structure, Experimental, 13)
[1986Bla] Blazina, Z., Trojko, R., “Structural Investigations of the Nb1–xSixT2 and Nb1–xAlxT2 (T = Cr, Mn, Fe, Co,
Ni) Systems”, J. Less-Common Met., 119, 297-305 (1986) (Crys. Structure, Experimental, 6)
[1987Rag] Raghavan, V., “The Fe-Nb-Si (Iron-Niobium-Silicon) System” in “Phase Diagrams of Ternary Iron
Alloys”, Ind. Inst. Techn. Delhi, 1, 55-59 (1987) (Crys. Structure, Phase Diagram, Phase Relations,
Review, 20)
[1989Kum] Kumar, K.C.H., Raghavan, V., “BCC – FCC Equilibrium in Ternary Iron Alloys. – II”, J. Alloy Phase
Diagr., 5, 77-96 (1989) (Calculation, Phase Diagram, Phase Relations, Thermodyn., #, 24)
[1989Sud] Sudavtsova, V.S., Zelenina, L.N., Sharkina, N.O., “Reaction in the System FeSi-Nb(Zr)”, Inorg. Mater.
(Engl. Trans.), 1330-1331 (1989), translated from Izv. Akad. Nauk SSSR, Neorg. Mater., 25, 1569-1570
(1989) (Experimental, Thermodyn., 2)
[1992Rix] Rixecker, G., Schaaf, P., Gonser, U., “Crystallization Behaviour of Amorphous Fe73.5Cu1Nb3Si13.5B9”,
J. Phys.: Condens. Matter, 4, 10295-10310 (1992) (Crys. Structure, Experimental, Morphology, Phase
Relations, 43)
[1993Bej] Bejarano, J.M.Z., Gama, S., Ribeiro, C.A., Effenberg, G., “The Iron-Niobium Phase Diagram”,
Z. Metallkd., 84, 160-164 (1993) (Experimental, Phase Diagram, Phase Relations, #, 6)
[1993Gao] Gao, Z., Fultz, B., “The Thermal Stability of Nanocrystalline Fe-Si-Nb Prepared by Mechanical
Alloying”, Nanostruct. Mater., 2, 231-240 (1993) (Electronic Structure, Experimental, Kinetics, Magn.
Prop., Morphology, Nano, 35)
[1994Gao] Gao, Z.Q., Fultz, B., “Inter-Dependence of Grain Growth, Nb Segregation, and Chemical Ordering in
Fe-Si-Nb Nanocrystals”, Nanostruct. Mater., 4, 939-947 (1994) (Experimental, Kinetics, Magn. Prop.,
19)
[2001Ito] Ito, M., Nagai, H., Katsuyama, S., Majima, K., “Effects of Ti, Nb and Zr Doping on Thermoelectric
Performance of β-FeSi2”, J. Alloys Compd., 315, 251-258 (2001) (Crys. Structure, Experimental, Phase
Relations, 18)
[2001Rix] Rixecker, G., Haberkorn, R., “Fe16Nb6Si7 and Fe16Ta6Si7: New D8a Phases Synthesized by the Crystalli-
zation of Mechanically Alloyed Amorphous Powders”, J. Alloys Compd., 316, 203-208 (2001) (Crys.
Structure, Experimental, Phase Relations, 18)
[2001Tur] Turtelli, R.S., Schonhart, M., Sassik, H., Grossinger, R., Kolbeck, C., Duong, V.H., Ferrara, E.,
“Enhancement of the Coercive Force with Addition of Nb in α-FeSi as-Quenched Ribbons”, J. Magn.
Magn. Mater., 226(2), 1498-1500 (2001) (Experimental, Magn. Prop., 5)
[2005Bar] Barbatti, C.F., Turtelli, R.S., Schoenhart, M., Sassik, H., Sinnecker, J.P., Sinnecker, E.H.C.P., Sarthour, R.
S., Guimaraes, A.P., Groessinger, R., “NMR, Magnetic and Structural Study of Fe-Si-X (X = Nb, Ta)
Alloys”, J. Magn. Magn. Mater., 290-291, 612-614 (2005) (Crys. Structure, Experimental, Magn. Prop.,
Phase Relations, 8)
[2005Pen] Penton-Madrigal, A., Turtelli, R.S., Estevez-Rams, E., Grossinger, R., “Structural Evolution with Nb
Content in Melt-Spun Fe80–xSi20Nbx Ribbons”, J. Alloys Compd., 395, 63-67 (2005) (Crys. Structure,
Experimental, 12)
[2005Tur] Turtelli, R.S., Penton-Madrigal, A., Barbatti, C.F., Groessinger, R., Sassik, H., Estevez-Rams, E.,
Sarthour, R.S., Sinnecker, E.H.C.P., Guimaraes, A.P., “Effect of the Addition of Cr, Ta and Nb on
Structural and Magnetic Properties of Fe-Si Alloys”, J. Magn. Magn. Mater., 294, e151-e154 (2005)
(Crys. Structure, Experimental, Magn. Prop., Phase Relations, 6)
[2006Tur1] Turtelli, R.S., Sinnecker, J.P., Grossinger, R., Wiesinger, G., de Morais, E., Penton-Madrigal, A., Estevez-
Rams, E., “Magnetic Transitions in Melt-Spun Nanocrystalline Fe-Si-Nb Alloys”, Phys. B: Condens.
Mater., 384, 303-305 (2006) (Experimental, Magn. Prop., Phase Relations, 7)
[2006Tur2] Turtelli, R.S., Sinnecker, J.P., Penton-Madrigal, A., Groessinger, R., Skorvanek, I., Krenicky, T., Estevez-
Rams, E., “An Unusual Temperature Dependence of the Coercive Field in the Melt-Spun Fe80–xSi20Nbx
(x = 12, 20)”, J. Magn. Magn. Mater., 304, e690-e692 (2006) (Experimental, Magn. Prop., Phase
Relations, 4)
(1990)

Fe–Nb–Zr 8 1
Iron – Niobium – Zirconium

Jean-Claude Tedenac, Pierre Perrot
Introduction
The Fe-Nb-Zr system is a base for nuclear materials. Due to their corrosion resistance some of
zirconium alloys are used as cladding and structural materials. One other field of nuclear
applications concerns their use in active zone of nuclear reactors [2002Gra, 2002Ram,
2002Tof]. Two problems were evidenced in this ternary system. The first one is related to
the existence of intermetallic compounds in the phase diagram, greatly influencing the
mechanical properties, of the alloys. The situation was clarified recently in [2002Ram,
2002Tof], where the phase relationship have been redetermined. The second problem concerns
the oxygen acting as an impurity but taking part to phase equilibria [2004Bar].
Investigations of the system related to phase relations, structures and thermodynamic are
presented in Table 1. Crystal structures of phases are summarized in Table 2.
Reviews of early works on phase equilibria in the Fe-Nb-Zr system have been presented by
[1973Sve, 1992Rag] and some isothermal sections were presented, but contradictory informa-
tion on phase relationships in this system exists [1968Gru, 1973Sve, 1979Ale, 1989Ale,
1989Kor1, 1997Per, 2002Gra]. Finally, the last review of Fe-Nb-Zr presented by [2003Rag] is
mainly based on the work of [2002Gra], but it does not reproduce the stability domain of the
ternary compound τ2.
Binary Systems
The Nb-Zr binary system is accepted from the thermodynamic assessment of [1991Fer]. The
miscibility gap of the solid solution (βZr,Nb) is at 977˚C and 59.2 mass% Nb; the minimum of
the liquidus is at 1742˚C and 22 mass% Nb. The Fe-Nb binary system is accepted from the
thermodynamic assessment carried out by [2000Tof]. The μ phase presents an incongruent
melting at 1520˚C, which is 70˚C lower than that given in [Mas2]. The eutectic invariant
reaction L Ð μ + (Nb) is at 1500˚C, which is 100˚C higher than given in [Mas2]. The Fe-Zr
binary system is accepted from experimental study of [2002Ste]. In this study it was pointed
out that the phase of Zr6Fe23 shown by [Mas2] is oxygen stabilized and is not an equilibrium
phase. According to [2002Ste] the Zr2Fe phase is stable in quite narrow temperature range of
780-951˚C, while according to [Mas2] it is stable below 974˚C. Beside cubic ZrFe2 (C15
structure, stable below 1673˚C, λ2) exists a hexagonal ZrFe2 (C36 structure, stable between
1240 and 1345˚C, λ3).
Solid Phases
Since the first published experimental work in this system, three Laves phases and one μ phase
have been evidenced. The existence of ternary intermetallic compounds is more or less
2 8 Fe–Nb–Zr
controversial. For example the ternary compound Zr54Nb9Fe37 cited by [1989Ale, 1989Kor1,
1989Kor2] was not shown in the recent experimental work [2002Gra, 2003Ram, 2007Ram2]
and its crystal structure is unknown. On the other hand, its composition lies very near by that
of the τ1 compound. It is the reason why this new compound was not introduced in Table 2.
Depending on the niobium content, the intermetallic phase Zr1–xNbxFe2 presents three
different Laves-type structures (see Table 2) [1968Kan, 1969Kan, 1972Fuj]. The crystal struc-
ture changes from C15 (MgCu2 up to x = 0.3) to C14 (MgZn2 from x = 0.5). In the middle
composition range (0.35 < x < 0.5) this phase adopts a superstructure C36 (MgNi2 type) with
six atom layers leading to a c axis value approximately equal to 2c (C14) [1969Kan]. The crystal
parameters of the C15 and C14 solid solutions from [1968Kan] are shown in Fig. 1.
The phase transformation from C15 to C14 in the solid solutions was studied as a function
of temperature of heat treatment and the Nb content by X-ray and magnetization experiments
[1972Fuj]. It shows that the Nb content where the phase transformation appears depends on
the temperature of heat treatment.
[2002Gra] in an experimental investigation on the zirconium rich corner found two new
intermetallic phases in this system: τ1, a Ti2Ni type phase (labeled λ1 in the original work)
ranging from 2.4 to 13 at.% Nb and 31 to 33 at.% Zr, and τ2, a C14 Laves phase (labeled λ2
in the original work) with a homogeneity range of 32-53 at.% Fe, 12-31 at.% Nb and
35-37 at.% Zr. As this work does not concern the niobium rich part, he did not report on
the μ phase which was evidenced in the former researches.
Quasibinary Systems
[1972Pet] presents a quasibinary diagram of the ZrFe2-NbFe2 section showing, towards
1200˚C, a solubility of 30 mol% NbFe2 in λ2 (ZrFe2, C15), a solubility of 50 mol% ZrFe2 in
λ1 (NbFe2, C14), and between 30 and 50 mol% NbFe2, a two-phase domain. Now, it is
recognized that this two-phase domain is actually a solid solution of the C36 structure.
It is not clear if the transitions C15-C36 and C36-C14 are of the first or second order. From
the shape of the solidus and liquidus lines proposed by [1972Pet], it is probable that the
liquidus of the ZrFe2-NbFe2 system presents a minimum towards 1600˚C and 40 mol% NbFe2.
A partial reaction scheme in the Fe-ZrFe2-NbFe2 region is presented in Fig. 2 [1989Kor1]. The
τ1 phase is formed by a peritectic reaction P at the temperature of 950˚C. Two solid state
transformations appear at 864˚C for the eutectoid reaction of formation of the mixture
{ZrFe2+NbFe2+(γFe)} and at 928˚C for the last reaction {ZrFe2+NbFe2+(αFe)}.
Liquidus Surface
The liquidus projection has been investigated in the whole composition range by [1989Ale]
and in the iron-rich corner by [1989Kor1] and mainly reproduced by [1992Rag]. Figure 3
represents the liquidus projection and the primary crystallization field, mainly from [1989Ale,
1992Rag], and slightly modified to take into account the phase equilibria in the accepted
Fe–Nb–Zr 8 3
binary systems. The primary crystallization field labeled τ by [1989Kor1] has been labeled τ1 in
Fig. 3 because we have identified above the ternary compound τ with the Laves phase τ1. It
must be pointed out that the ternary compound τ2 does not seems to have a primary
crystallization domain. Actually, it is probable that the domain labelled NbFe2 (C14) must
be split in two: one domain “NbFe2” and one domain “τ2”, both phases NbFe2 and τ2 having
the same C14 structure.
Isothermal Sections
The sub-ternary system Fe-ZrFe2-NbFe2 was first investigated by [1989Kor1] at the tempera-
tures 1337˚C and 1315˚C. The samples were prepared by melting in arc furnace, remelted four
times, annealed at 900˚C. The alloys were treated at the temperatures of the sections and then
quenched. [1989Ale] and [1989Kor2] studied seven isothermal sections at the temperatures
500, 650, 700, 800, 900, 945 and 1200˚C. This study was taken into account by [1992Rag] in its
evaluation. But new experimental determinations, [2002Gra], are in disagreement because
[1989Kor2] does not take into account the τ1 and τ2 phases whose existence and crystal
structure are well established [2003Ram, 2007Ram2] and according to those results a tentative
isothermal section at the temperature of 800˚C is given by [2003Rag]. It is presented in Fig. 4
and differs from the section presented by [2003Rag] mainly by the shape of the τ2 domain,
which presents, in [2003Rag], an extension which has never been reported by [2002Gra,
2002Tof]. Due to the lack of more experimental informations the solubilities in the (Nb)
solid solution and the triangulation for the compositions are presented only as an indication.
[2007Ram2] made some complementary X-ray determinations and presented, also as an
indication, phase equilibria at 900˚C which are very similar to the diagram given in Fig. 4.
In [2004Bar] the zirconium rich part of the ternary system has been studied at the
temperature of 580˚C. The authors precise this part of the isothermal section and the solubility
of Nb in (αZr). They used for that study specially elaborated alloys with 600-1200 ppm of
oxygen. The phase repartition in the Zr rich corner is presented in Fig. 5. The influence of Fe
and Nb ((Fe+Nb) < 3 mass %) on the αZr/βZr transition and the reversibility of the
precipitation/dissolution of the secondary phase has been investigated by [2008Tof].
The main experimental works are reported in Table 3. Several investigations have been made
on magnetic properties of intermetallic phases. [1994Cro] studied magnetic order resulting
from 10 at.% substitution of Zr for Nb in the weak itinerant antiferromagnet NbFe2. The Curie
temperature for Zr1–xNbxFe2 as a function of the niobium content has been studied by
[1968Kan, 1969Kan]. It was shown that the magnetic moment is strongly dependent on the
crystal structure, decreasing dramatically during the transition from C15 to C14.
In [1978Zak] the decomposition of the (βZr,Nb) solid solution in Nb-Zr alloys with added
Fe was studied by electron microscopy and X-ray diffraction on single crystals.
The Mössbauer effect, X-ray diffraction, and electron microscopy were used to study
structural-phase transformations in an alloy rolled at room temperature of the Zr-0.5Nb-
0.31Fe composition after annealing in the range 300-700˚C [1985Kir]. The main effect
observed is the strengthening of Zr by precipitation of (Zr,Nb)2Fe (C16) and (Zr,Nb)Fe2
4 8 Fe–Nb–Zr
(C15) compounds. The segregation of Fe and Nb near the Zr surface with precipitation of the
C15 and C16 phases was also observed by [1988Igr, 1999Ram] in Zr rich alloys. Samples with
the following compositions: Zr62Nb14Fe24, Zr65Nb10Fe25 and Zr52Nb10Fe38 were analyzed by
[2002Ram]. All of them showed the precipitation of τ1, a ternary cubic Ti2Ni type phase and
traces of C16 (tetragonal Zr2Fe) phase. [2007Ram1] prepared Zr-Nb-Fe alloys with Nb
contents between 5 and 50 at.% and Fe contents between 10 and 60 at.%. After a heat
treatment at 900˚C for 4 month, analysis of the phases showed the presence of C15 and C16
phases. The kinetics of the phase precipitation during annealing of (αZr) alloyed with Fe and
Nb was carried out by [1985Kir, 1988Igr]. The presence of Fe as impurities in a Zr+2.5 at.%
Nb induces the precipitation of the C16-Zr2Fe phase [1990Woo]. The partition coefficient of
Fe between (αZr) and (βZr) has been evaluated at {Fe}β / {Fe}α = 1.5 to 2, which agrees with the
β stabilizer characteristics of Fe. The presence of Fe in a (βZr,Nb) alloy lowers the solvus line
(α+β)/β [1993Per].
Miscellaneous
Amorphous state and glassy materials were evidenced by [1987Tre, 2004Yao]. The ternary Fe-
Nb-Zr takes part in glass forming quaternary systems. The composition Fe91–x Nb4Zr5Bx was
studied as glassy material by [2004Yao] as a function of the boron content as well as the
magnetic properties. In [1993Per], an analytical transmission electron microscopy study of
two-phase (α-β) structures in a Zr-2.5 mass% Nb pressure tube alloy was used to follow the
distribution of Nb and Fe as a function of alloy heat treatment and tube processing. The
presence of Fe (~0.1 mass%) modifies the (α-β) phase equilibria as Fe is a beta-stabilizing
element, [1993Per]. Significant segregation of Fe to βZr and Nb structures was measured.
The effects of different Nb and Fe addition ratios on the microstructure, corrosion and
oxide characteristics of Zr based alloys were investigated by [1995Per, 2005Kim]. The Nb/Fe
ratio was controlled to with the same amount of Nb + Fe in each alloy. The microstructural
analysis and precipitate characterization were performed to obtain the correlation between the
corrosion and the microstructures.
. Table 1
Investigations of the Co-Fe-Si Phase Relations, Structures and Thermodynamics
Temperature / Composition / Phase Range

Reference Method / Experimental Technique Studied
[1968Gru] Thermal analysis, metallography, 700-1000˚C, > 84 mass% Zr, Fe/Nb = 1/3, 1/1
hardness and 3/1
[1972Pet] XRD ZrFe2-NbFe2 join
[1989Ale] Thermal analysis, XRD, 850-1600˚C, Zr-Nb-NbFe2-ZrFe2, isothermal
metallography sections, reaction scheme
[1989Kor1] Thermal analysis, XRD, 850-1600˚C, Fe-ZrFe2-NbFe2, isothermal
metallography section, reaction scheme
[1989Kor2] Thermal analysis, XRD, 500-800˚C, the whole diagram, isothermal
metallography section

Fe–Nb–Zr 8 5
Temperature / Composition / Phase Range

Reference Method / Experimental Technique Studied
[1997Per] SEM, EDX, XRD 600-800˚C, < 20 at.% Nb, < 0.1 at.% Fe,
equilibrium (α+β)/β
[2002Gra] XRD, SEM, metallography, EMPA 800-900˚C, > 40 at.% Zr, < 40 at.% Nb, < 40 at.%
Fe
[2002Tof] XRD, TEM, EDX, analysis of 700-1100˚C, < 2 mass% Nb, < 0.75 mass% Fe
secondary phase particles
[2003Ram] XRD, SEM, EPMA, Mössbauer 800˚C, 35 at.% Fe, < 15 at.% Nb
[2007Ram2] XRD, SEM, metallography 900˚C, phase equilibrium in the whole diagram
[2008Tof] DTA, TEM, calorimetry 750-1050˚C, < 2 mass% Nb, < 1 mass% Fe, αZr/
βZr transition
. Table 2
Pearson
Symbol/

P63/mmc c = 396.0
Mg
(δFe) cI2 a = 293.15 [Mas2]
1538 - 1394
Im3m Dissolves up to 3.2 at.% Nb at 1373˚C and 4.5
at.% Zr at 1357˚C
W
(γFe) cF4 a = 364.67 at 915˚C [Mas2]
1394 - 912 Fm3m Dissolves up to 0.9 at.% Nb at 1210˚C and 0.7
at.% Zr at 1337˚C
Cu
(αFe) cI2 a = 286.65 at 25˚C [Mas2]
< 912 Im3m Dissolves up to 0.7 at.% Nb at 961˚C
W
(ωZr) hP3 a = 503.6 at 25˚C, HP > 1 atm [Mas2]
P6/mmm c = 310.9
ωTi

6 8 Fe–Nb–Zr
Pearson
Symbol/
β, (βZr,Nb) cI2
Im3m
(βZr) W a = 360.90 pure βZr [Mas2, V-C2]
1855 - 863 Dissolves up to 6 at.% Fe at 928˚C
Zr0.5Nb0.5 a = 344.5
(Nb) a = 330.04
< 2469 pure Nb at 25˚C [Mas2]
Dissolves up to 7.6 at.% Fe at 1500˚C
(αZr) hP2 a = 323.16 at 25˚C [Mas2]
< 863 P63/mmc c = 514.75 Dissolves up to 0.03 at.% Fe at 730˚C and 0.6
at.% Nb at 620˚C
Mg
μ, Nb6Fe7 hR39 a = 492.8 ± 4 [2000Tof]
< 1520 R
3m c = 2683 ± 2 47 to 49 at.% Nb
W6Fe7
Zr3Fe oC16 a = 332 74.8 to 75.4 at.% Zr
< 851 Cmcm b = 1100 [2002Ste]
BRe3 c = 882 Dissolves up to 1.7 at.% Nb [2002Gra]
Zr2Fe tI12 a = 638 66.7 to 67.2 at.% Zr [2002Ste]
951 - 780 I4/mcm c = 560 C16 structure. Dissolves up to 0.5 at.% Nb
[2003Ram]
Al2Cu
(Zr1–xNbx)Fe2
hP12 0.5 < x < 1, C14 structure
λ1, NbFe2 P63/mmc a = 481.7 x = 1 [2000Tof], 27 to 38 at.% Nb
< 1629 MgZn2 c = 787.2
0 < x < 0.3, C15 structure
cF24 x=0
λ2, ZrFe2 Fd
3m 27.5 to 34.4 at.% Zr [2002Ste]
< 1673 MgCu2 a = 702 to 709
x = 0.25 [1983Bus]
Zr0.75Nb0.25Fe2 a = 703.8
0.35 < x < 0.5, C36 structure
hP24 x ~ 0.5 (stable)
P63/mmc a = 498.8
MgNi2 c = 1632
x = 0 [2002Ste]
λ3, ZrFe2 a = 485 26.5 to 27 at.% Zr [2002Ste]
1345 - 1240 c = 1614

Fe–Nb–Zr 8 7
Pearson
Symbol/
Zr6Fe23 cF116 a =1169 Sometimes labelled ZrFe3 [1997Oka].

1482 - 1175
Fm3m Metastable, stabilized by oxygen [2002Ste]
Th6Mn23
*τ1, (Zr1–xNbx)2Fe1–y cF96 0.035 < x < 0.25 [2003Ram]
Fd3m 0 < y < 0.06 [2002Gra]
Ti2Ni labeled as λ1 in [2002Gra]
a = 1212 (Zr0.88Nb0.12)2Fe0.96
a = 1218 (Zr0.92Nb0.08)2Fe0.97
*τ2, Zr1+y(NbxFe1–x)2 hP12 0.18 < x < 0.54
P63/mmc 0 < y < 0.12,
MgZn2 C14 structure
labeled as λ2 in [2002Gra]
a = 532.7 Zr1.12(Nb0.49Fe0.51)2 [2002Gra]
c = 863.0
a = 540.1 Zr1.00(Nb0.54Fe0.46)2 [2002Tof]
c = 866.5
. Table 3
Investigations of the Fe-Nb-Zr Materials Properties
Method / Experimental Temperature / Composition / Phase Range

Reference Technique Studied
[1968Kan, Magnetic moment, Curie Zr1–xNbxFe2 with x < 0.5 (magnetism) and x < 1
1969Kan] temperature, crystal parameters (crystal parameters)
[1972Fuj] X-ray diffraction (XRD), < 600˚C, Zr0.6Nb0.4Fe2
magnetism
[1978Zak] XRD, EMPA, electron diffraction 450-550˚C, 13 mass% Zr, 5 mass% Fe, martensitic
transformation
[1979Ale] XRD, metallography 1000˚C, < 35 at.% Nb, > 64 at.% Zr, precipitation
of metastable (ωZr)
[1983Bus] Magneto-optic, Kerr effect, Zr0.75Nb0.25Fe2 (C15)
saturation magnetization
[1985Kir] XRD, SEM, Mössbauer, kinetics 0.5 mass% Nb, 0.3 mass% Fe, cold rolled then
annealed 300-700˚C
[1988Igr] Mössbauer effect in the 57Fe, < 1000˚C, segregation of Fe and Nb near the
kinetics surface

8 8 Fe–Nb–Zr
Method / Experimental Temperature / Composition / Phase Range

Reference Technique Studied
[1990Woo] Microstructural analysis, neutron Zr-2.5 at.% Nb + Fe impurities, Fe partition

and electron diffraction, between (αZr) and (βZr)
Mössbauer
[1993Per] SEM, energy dispersive X-Ray 500-800˚C, 2.5 mass% Nb, 0.1 mass% Fe,
analysis (EDX)
[1994Cro] Magnetic moments, spontaneous C14 Nb1–xZrxFe2 (x < 0.5), magnetic diagram
magnetization
[1995Per] SEM, EDX, XRD, neutron Zr-2.5 Nb-0.1 Fe (in mass%), Fe and Nb
irradiation distribution between α and β
[1999Ram] SEM, XRD, Mössbauer, EMPA 800˚C, 0.9 to 2.4 mass% Nb, 0.6 to 10.0 mass% Fe
[2002Kim] Thermoelectric power 540-940˚C, < 0.8 at.% Nb
[2002Ram] XRD, Mössbauer, optical Zr62Nb14Fe24, Zr65Nb10Fe25, Zr52Nb10Fe38,
metallography, SEM, EPMA 1200 h at 800˚C
[2003Ram] XRD, Mössbauer, optical Zr64.5Nb0.5Fe35, Zr61Nb4Fe35, Zr55Nb10Fe35,
metallography, SEM, EPMA Zr50Nb15Fe35
[2004Bar] Microstructures by TEM, corrosion Nb < 1.2 mass%, Fe < 0.1 mass%
in autoclaves
[2004Yao] XRD, DTA, DSC, TEM magnetic Fe91–x Nb4Zr5Bx with 5 < x < 30 prepared by arc
properties by VSM. melting solidification
[2005Kim] EDS, TEM, XRD Nb/Fe = 0.6 to 7.0. Corrosion by H2O at 360˚C
under 18.9 MPa
[2006Fil] Mössbauer spectroscopy Dependence of Mössbauer absorption line area
from effective thickness of sample
[2007Ram1] Mössbauer, XRD, DTA, DSC, TEM, Zr-Nb-Fe alloys with Nb contents between 5 and
magnetic properties 50 at.% and Fe contents between 10 and 60 at.%

Fe–Nb–Zr 8 9
. Fig. 1
Fe-Nb-Zr. Crystal parameters of the C15 and C14 solid solutions in the ZrFe2-NbFe2 system

10 8 Fe–Nb–Zr
. Fig. 2
Fe-Nb-Zr. Reaction scheme

Fe–Nb–Zr 8 11
. Fig. 3
Fe-Nb-Zr. Liquidus surface projection

12 8 Fe–Nb–Zr
. Fig. 4
Fe-Nb-Zr. Isothermal section at 800˚C

Fe–Nb–Zr 8 13
. Fig. 5
Fe-Nb-Zr. The Zr-rich part of the diagram at 580˚C

14 8 Fe–Nb–Zr
References
[1968Gru] Gruzdeva, N.M., Zagorskaya, T.N., Raevsky, I.I., “The Zr corner of the Zr-Fe-Nb Phase Diagram”, Fiz.
Khim. Splavov Tsirkoniya, 117–121 (1968) (Phase Diagram, Experimental, 5)
[1968Kan] Kanematsu, K., “Magnetism and Crystal Structures of Zirconium Compounds with Laves Structure”,
J. Appl. Phys., 39, 465–466 (1968) (Calculation, Crys. Structure, Experimental, Magn. Prop., 2)
[1969Kan] Kanematsu, K., “Structural and Magnetic Properties of Pseudobinary System (Zr1–xNbx)Fe2”, J. Phys.
Soc. Jpn., 27, 849–856 (1969) (Crys. Structure, Experimental, Magn. Prop., 17)
[1972Fuj] Fujita, Y., “The Effect of Heat Treatment on Crystallographic and Magnetic Properties of
Zr0.80MO0.20Fe2 and Zr0.60Nb0.40Fe2”, J. Phys. Soc. Jpn., 33, 1720 (1972) (Crys. Structure, Experimental,
Magn. Prop., 2)
[1972Pet] Petkov, V.V., Cherkashin, E.E., “Interaction of Laves Phases in the Quasibinary Sections ZrFe2-(NbFe2,
TaFe2)” (in Ukrainian), Dop. Akad. Nauk Ukr. RSR, (A) (3), 276–279 (1972) (Crys. Structure, Phase
Diagram, Phase Relations, Experimental, 11)
[1973Sve] Svechnikov, V.N., Kocherzhinsky, Yu.A., Markiv, V.Ya., Pet’kov, V.V., “Laves Phases in Transition Metal
Systems of the IV-VII Groups of Periodic Systems” (in Russian), Akad. Nauk Ukr. SSR, Metallofizika,
46, 35–45 (1973) (Experimental, Phase Diagram, Phase Relations, Review, 74)
[1978Zak] Zakharova, M.I., Kirov, S.A., Khundzhua, A.G., “Formation of Metastable and Equilibrium Phases in
the Decomposition of the β Solid Solution in Zr Alloys”, Phys. Status Solidi A, 49A(2), 803–10 (1978)
(Crys. Structure, Phase Relations, Kinetics, Experimental, 11)
[1979Ale] Alekseenko, G.K., “Influence of U and Fe on the Distribution of the Metastable Phases in the Zr-Nb
System” (in Russian), in “Alloys for Atomic Energy”, Ivanov, O.S., Alekseeva, Z.M. (Eds.), Nauka,
Moscow, 144–148 (1979) (Experimental, Mechan. Prop., Morphology, Phase Relations, 5).
[1983Bus] Buschow, K.H.J., van Engen, P.G., Jongebreur, R., “Magneto-Optical Properties of Metallic
Ferromagnetic Materials”, J. Magn. Magn. Mater., 38, 1–22 (1983) (Magn. Prop., Optical Prop.,
Experimental, 23)
[1985Kir] Kirichenko, V.G., Snurnikova, A.I., Chekin, V.V., “Structural and Phase Transformations during
Thermomechanical Treatment of α-Zr Alloys with Nb and Fe”, Phys. Met. Metallogr., 59(5), 100–103
(1985), translated from Fiz. Met. Metallov., 59(5), 943–946 (1985) (Electronic Structure, Experimental,
Phase Relations, Kinetics, 9)
[1987Tre] Tregubov, I.A., Evseeva, L.N., Maslenkov, S.B., “Production and Examination of Zirconium Alloys in
the Amorphous State”, Phys. Chem. Mater. Treatment, 21(1), 85–87 (1987), translated from Fiz. Khim.
Obrab. Mater., USSR, 21(1), 124–127 (1987) (Experimental, Phase Relations, 9)
[1988Igr] Igrushin, V.V., Kirichenko, V.G., Petel’guzov, I.A., Chekin, V.V., “Kinetics of a Phase Transformation of
Iron Intermetallics during Annealing of α-Zr Alloyed with Nb and Fe”, Phys. Met. Metallogr., 65(1),
126–129 (1988), translated from Fiz. Met. Metallov., 65(1), 137–140 (1988) (Experimental, Electronic
Structure, Kinetics, 6)
[1989Ale] Alekseeva, Z.M., Korotkova, N.V., “Isothermal Sections of State Diagram of Zr-Nb-Fe in the
Temperature Range 1600–850˚C”, Russ. Metall., (1), 199–205 (1989), translated from Izv. Akad. Nauk
SSSR, Met., (1), 199–205 (1989) (Experimental, Phase Diagram, Phase Relations, 17)
[1989Kor1] Korotkova, N.V., “The Fe-ZrFe2-NbFe2 Phase Diagram”, Russ. Metall., (6), 185–188 (1989),
translated from Izv. Akad. Nauk SSSR, Met., (6), 194–197 (1989) (Experimental, Phase Diagram,
Phase Relations, 3)
[1989Kor2] Korotkova, N.V., Alekseeva, Z.M., “Topology of the Zr-Nb-Fe Phase Diagram in the Range 500-800˚C”,
Russ. Metall., (3), 198–204 (1989), translated from Izv. Akad. Nauk SSSR, Met., (3), 207–214 (1989)
(Experimental, Phase Diagram, Phase Relations, 19)
[1990Woo] Woo, O.T., Carpenter, G.J.C., Sawicki, J.A., MacEwen, S.R., “Zr-Fe Intermetallic Precipitates and Fe
Partitioning in Zr-2.5 at.% Nb”, J. Nucl. Mater, 172, 71–76 (1990) (Electronic Structure, Experimental,
[1991Fer] Fernandez-Guillermet, A., “Thermodynamic Analysis of the Stable Phases in the Zr-Nb System and
Calculation of the Phase Diagram”, Z. Metallkd., 82(6), 478–487 (1991) (Phase Diagram, Phase
Relations, Thermodyn., Assessment, 38)
[1992Rag] Raghavan, V., “The Fe-Nb-Zr (Iron-Niobium-Zirconium) System” in “Phase Diagrams of Ternary Iron
Alloys”, Indian Institute of Metals, Calcutta, 6B, 1031–1041 (1992) (Crys. Structure, Phase Diagram,

Fe–Nb–Zr 8 15
[1993Per] Perovic, A., Perovic, V., Weatherly, G.C., Purdy, G.R., Fleck, R.G., “A Study of the Distribution of Nb
and Fe in Two-Phase Zr-2.5 wt.% Nb Alloys”, J. Nucl. Mater, 199, 102–111 (1993), (Experimental,
Phase Diagram, Phase Relations, 21)
[1994Cro] Crook, M.R., Cywinski, R., “Spin Fluctuations and Magnetic Order in Nb1–xZrxFe2”, Hyperfine
Interact., 85, 203–208 1994 (Crys. Structure, Electronic Structure, Experimental, Magn. Prop., 8)
[1995Per] Perovic, V., Perovic, A., Weatherly, G.C., Purdy, G.R., “The Distribution of Nb and Fe in a Zr-2.5 wt%
Nb Alloy, before and after Irradiation”, J. Nuclr. Mater, 224, 93–102 (1995) (Experimental, Kinetics,
[1997Oka] Okamoto, H., “Fe-Zr (Iron-Zirconium)”, J. Phase Equilib., 18(3), 316 (1997) (Phase Diagram, Phase
Relations, Review, 5)
[1997Per] Perovic, A., Weatherly, G.C., “The Promonotectoid Region of the Nb-Zr System”, J. Phase Equilib., 18
(3), 245–248 (1997) (Experimental, Phase Relations, Review, 10)
[1999Ram] Ramos, C., Saragovi, C., Granovsky, M., Arias, D., “Mössbauer Spectroscopy of the Zr-Rich Region in
Zr-Nb-Fe Alloys with Low Nb Content”, Hyperfine Interact., 122, 201–207 (1999) (Electronic Structure,
Experimental, Phase Relations, 9)
[2000Tof] Toffolon, C., Servant, C., “Thermodynamic Assessment of the Fe-Nb System”, Calphad, 24(2), 97–112
(2000) (Phase Diagram, Phase Relations, Thermodyn., Assessment, 40)
[2002Gra] Granovsky, M.S., Canay, M., Lena, E., Arias, D., “Experimental Investigation of the Zr Corner of the
Ternary Zr-Nb-Fe Phase Diagram”, J. Nucl. Mater., 302, 1–8 (2002) (Crys. Structure, Experimental,
Morphology, Phase Diagram, Phase Relations, 25)
[2002Kim] Kim, S.J., Hong, H.S., Oh, Y.M., “Study of the Thermoelectric Power Evolution of Zr-based Alloys
with Nb Additions”, J. Nucl. Mater, 306, 194–201 (2002) (Electronic Structure, Experimental, Mor-
phology, Thermodyn., 21)
[2002Ram] Ramos, C., Saragovi, C., Granovsky, M., Arias, D., “Mössbauer Spectroscopy Studies of some
Intermetallics in the Zr-Nb-Fe System”, Hyperfine Interact., 139, 363–368, (2002) (Electronic Structure,
[2002Ste] Stein, F., Sauthoff, G., Palm, M., “Experimental Determination of Intermetallic Phases, Phase
Equilibria, and Invariant Reaction Temperatures in the Fe-Zr System”, J. Phase Equilib., 23(6), 480–494
(2002) (Phase Diagram, Phase Relations, Crys. Structure, Experimental, #, 88)
[2002Tof] Toffolon-Masclet, C., Brachet, J.-Ch., Jago, G., “Studies of Second Phase Particles in Different
Zirconium Alloys Using Extractive Carbon Replica and an Electrolytic Anodic Dissolution Procedure”,
J. Nucl. Mater., 305, 224–231 (2002) (Crys. Structure, Experimental, Morphology, Phase Relations, 19)
[2003Rag] Raghavan, V., “Fe-Nb-Zr (Iron-Niobium-Zirconium)”, J. Phase Equilib., 24(4), 354–355 (2003) (As-
sessment, Crys. Structure, Phase Diagram, Phase Relations, 6)
[2003Ram] Ramos, C., Saragov, C., Granovsky, M., Arias, D., “Effects of Nb Content on the Zr2Fe Intermetallic
Stability”, J. Nucl. Mater., 312, 266–269 (2003) (Crys. Structure, Experimental, Morphology, Phase
[2004Bar] Barberis, P., Charquet, D., Rebeyrolle, V., “Ternary Zr-Nb-Fe(O) System: Phase Diagram at 853 K and
Corrosion Behaviour in the Domain Nb < 0.8%”, J. Nucl. Mater., 326, 163–174 (2004) (Crys. Structure,
Phase Diagram, Phase Relations, Experimental, Interface Phenomena, Morphology, 30)
[2004Yao] Yao, B., Zhang, Y., Si, L., Tan, H., Li, Y., “Boron Content Dependence of Crystallization, Glass Forming
Ability and Magnetic Properties in Amorphous Fe-Zr-B-Nb Alloys”, J. Alloys Compd., 370, 1–7 (2004)
(Crys. Structure, Kinetics, Magn. Prop., Morphology, Phase Relations, 35)
[2005Kim] Kim, H.G., Park, J.Y., Jeong, Y.H., “Ex-reactor Corrosion and Oxide Characteristics of Zr-Nb-Fe Alloys
with the Nb/Fe Ratio”, J. Nucl. Mater., 345, 1–10 (2005) (Crys. Structure, Kinetics, Morphology,
Experimental, 21)
[2006Fil] Filippov, V.P., Petrov, V.I., Lauer, D.E., Shikanova, YuA., “Calculation of Absolute Concentrations and
Probability of Resonant Absorption for Iron-bearing Precipitates in Zirconium Alloys”, Hyperfine
Interact., 168, 965–971 (2006) (Electronic Structure, Experimental, Phase Relations, 7)
[2007Ram1] Ramos, C.P., Granovsky, M.S., Saragovi, C., “Mössbauer Spectroscopy Characterization of Zr-Nb-Fe
Phases”, Physica B: Condens. Matter., 389B, 67–72 (2007) (Electronic Structure, Experimental, Phase
Relations, 9)
[2007Ram2] Ramos, C., Saragovi, C., Granovsky, M.S, “Some New Experimental Results on the Zr-Nb-Fe
System”, J. Nucl. Mater. 366, 198–205 (2007) (Crys. Structure, Phase Diagram, Phase Relations,
Experimental, 32)

16 8 Fe–Nb–Zr
[2008Tof] Toffolon-Masclet, C., Guilbert, T., Brachet, J.C., “Study of Secondary Intermetallic Phase
Precipitation/Dissolution in Zr Alloys by High Temperature - High Sensitivity Calorimetry”, J.
Nucl. Mater., 372, 367–378 (2008) (Phase Relations, Transport Phenomena, Thermodyn., Experimen-
tal, 25)
(1990)

Fe–Nd–Si 9 1
Iron – Neodymium – Silicon

Peter Rogl
Introduction
Various research groups have contributed to the phase relations in the ternary system. Phase
equilibria along the section Fe - NdSi2–x and for the section at 33.3 at.% Nd have been
investigated by [1969May, 1970Bod, 1972May, 1973Bau, 1973May, 1973Pin, 1974Nar,
1975Fel, 1978Kot, 1978Ros, 1983Noa, 1983Uma, 1990Mal, 1998Wel] with emphasis in many
cases on the physical properties of solution phases and compounds and revealed five different
structure types: AlB2 [1969May, 1972May, 1973May, 1974Nar], ThSi2, TiNiSi [1973May] or
PbFCl [1970Bod, 1998Wel], and NdFeSi2 [1990Mal]. Further ternary compounds were dis-
covered: with ThCr2Si2 structure [1972May, 1973Bau, 1973Fel, 1973Pin, 1975Fel, 1978Ros,
1983Noa, 1983Uma, 1987Lec]; Nd6Fe13Si [1990All, 1994Yan, 1996Lei, 1998Gro, 2002Taj,
2002Isn], NdFe10Si2 [1991Bus, 2003Sor] and NdFeSi3 [1996Sal]. Two independent investiga-
tions have supplied information on the phase equilibria within a partial isothermal section at
500˚C [1995Zhu] and a full isothermal section at 600˚C [1996Sal]. Unfortunately information
gathered is not without controversies on the phase regions and stabilities as a function of
temperature and therefore only a tentative version of the phase equilibria can be provided
throughout this assessment. New studies are encouraged to solve the puzzling situation.
An early assessment of the formation of compounds in the Fe-Nd-Si system is due to
[1984Rog]. Table 1 includes all experimental data on phase equilibria, crystal structure and
thermodynamics.
Binary Systems
The Fe-Si phase diagram adopted for this assessment is based on [1982Kub] complimented by
recent experimental data of [2005Mec] for the liquidus and solidus curves in the Fe rich part.
A thermodynamic assessment is due to [1998Mie]. The Fe-Nd system is taken from a
thermodynamic calculation by [1993Hen]. The Nd-Si system as presented by [2000Oka]
needs to be revised in many aspects (i) with respect to the existence of two modifications
for the Nd5Si4 compound [2006Rog], (ii) with respect to the correct position of the phase
labelled as “Nd3Si4” at NdSi1.4 [1992Sch, 2001Bou, 2006Rog], and (iii) with respect to the
exact location of the phases with AlB2 type, GdSi2–x type and ThSi2 type (see Table 1). It is
unclear if Nd5Si3 with the Mn5Si3 structure type is part of the Nd-Si binary [2001Bou,
2006Rog] or is impurity stabilized.
Solid Phases
Although at least nine ternary compounds have so far been reported in literature, ternary phase
equilibria after [1996Sal] show only four ternary compounds NdFeSi~3 (τ1), NdFe2Si2 (τ2),
2 9 Fe–Nd–Si
NdFe1+xSi1–x (τ3) and Nd6Fe13Si (τ4), which except for τ3 were reported to exist at fixed
compositions without significant homogeneity regions. The crystal structures of these phases
(except τ1) have all been elucidated (see Table 2).
Particularly the section at constant 33.3 at.% Nd {Nd(Fe1–x Six)2} shows the formation of a
series of compounds: Nd(Fe0.125Si0.875)2 (τ6), Nd(Fe0.20Si0.80)2 (τ9), and Nd(Fe0.33Si0.66)2 (τ5).
According to early data by Mayer and Tassa [1969May] Nd(Fe0.125Si0.875)2 (τ6) crystallized
with the ThSi2 structure type and Nd(Fe0.20Si0.80)2 (τ9) was single phase AlB2 type. The ThSi2
type structure was reported to be stable for compositions x < 0.4 at 700 - 800˚C [1969May,
1973May]. For a statistical distribution of Fe and Si atoms in the 2d sites of P6/mmm of Nd
(Fe0.20Si0.80)2 the calculated and observed X-ray powder intensity data were said to be in good
agreement. Nd(Fe0.33Si0.66)2 (τ5) was said to transform above 950˚C: the d values of the new
phase were reported as 2.61(90), 2.53(100), 2.06(70) and 1.62(50), with relative intensities in
brackets [1972May]. It is interesting to note that both structure types ThSi2 and AlB2 are
found with binary defect Nd-silicides NdSi2–y.
Some controversies exist along the concentration line Fe - NdSi2 which contains two
phases: NdFeSi2 (τ8) and NdFe1+xSi1–x (τ3). NdFeSi was claimed to be single-phase with an
orthorhombic “TiNiSi type” of structure [1973May]. The existence of a compound NdFeSi
was confirmed by [1970Bod, 1995Zhu, 1998Wel], but at variance with [1973May] a tetragonal
PbFCl type of structure (CeFeSi type) was obtained from arc-melted alloys heat treated at
800˚C for 3 months (low-temperature phase?). Due to the high temperature of preparation
and homogenization the “TiNiSi type” phase as reported by Mayer and Felner [1973May] is
likely to represent a high-temperature modification. At variance to [1996Sal], the findings of
[1995Zhu] revealed a significant homogeneity region NdFe1+xSi1–x extending at 500˚C from
28 to 36 at.% Si.
NdFeSi2 (τ8) with TbFeSi2 structure type was prepared at 1000˚C (1273 K) and quenched.
The material was consecutively investigated at temperatures below 300 K (27˚C) without any
signs of decomposition [1990Mal]. Presently it is unclear if NdFeSi2 is stable at high tem-
peratures only.
Many contributions are concerned with the physical and predominantly the magnetic
properties of NdFe2Si2 (τ2) (see section Notes on Materials Properties and Applications).
Although the compound ties to most neighboring phases (see phase relations in Fig. 1),
heating of NdFe2Si2 above 700˚C was reported to result in a decomposition into a mixture of
Nd5Si4 and Fe3Si [1972May].
The crystal structure of Nd6Fe13Si (τ4) (space group I4/mcm) was derived from single
crystal X-ray data and was found to be an ordered version of the Nd6Fe11Ga3 type [1990All].
At subsolidus temperatures solubility of Si in Nd2Fe17 was found to extend at least to
NdFe12.91Si4.09 from a neutron diffraction experiment on samples Nd2Fe17–xSix (x up to 4)
reducing anisotropically the unit cell volume: silicon atoms avoid the 6c site but prefer the 18h
site (the site with the highest Nd-coordination number) [1993Lon, 1995Yel, 1996Yel,
1996Gir]. Samples at x = 5 annealed at 1000˚C for one month showed in the X-ray spectrum
besides majority of Nd2Fe17–xSix phase also NdFe2Si2, Fe-Si and small amounts of a bct Nd(Fe,
Si)11 phase [1997Hua].
The crystal structures of the ternary compounds are all summarized in Table 2.

Fe–Nd–Si 9 3
Isothermal Sections
A partial isothermal section at 500˚C for the region < 40 at.% Nd and < 40 at.% Si [1995Zhu]
and a full isothermal section at 600˚C [1996Sal] have been derived. Although the two
investigations were only apart in temperature by 100˚C, there are severe differences in (i)
the extent of the homogeneity region of the NdFeSi phase (point compound in [1996Sal], but
NdFe1+xSi1–x with –0.8 < x < 0.16 reported by [1995Zhu]); (ii) the phase equilibria NdFeSi +
Nd6Fe13Si + Nd5Si3 [1996Sal] in contrast to NdFe1+xSi1–x + Nd2(Fe1–xSix)17 + Nd by
[1995Zhu], and (iii) maximal solubility of Si in Nd2Fe17 given at about 4 at.% Si by
[1996Sal] but 12 at.% Si by [1995Zhu]. Figure 1 shows the isothermal section at 600˚C,
which was slightly modified to comply with the accepted binary systems. Furthermore,
equilibria as given by [1996Sal] were used for the Fe-Nd rich side but a homogeneity region
was inferred from [1995Zhu] for the NdFeSi phase and a higher solubility of 12 at.% Si was
adopted for the Nd2Fe17 phase. It needs to be noted, however, that at 600˚C only few of the
compounds discovered were reported and neither phases such as τ9 (AlB2 type) and τ6 (ThSi2
type) nor solid solutions of Fe in these phases have been observed [1996Sal], although both
structure types exist in the binary Nd-Si system. Furthermore phases τ5, τ7, τ8 were not
observed [1996Sal, 1995Zhu]. This may be either due to slow reaction kinetics and diffusion
at low temperature or on the fact that these phases are all high temperature phases which are
only stable at temperatures above 600˚C.

In view of the various magnetic and electric properties of binary Nd-silicides basic interest in
Nd-Fe-silicides essentially covered Si rich compounds τ2, τ6, τ9, τ8 among which the most
studied phase is τ2 (NdFe2Si2, tetragonal with the ordered ThCr2Si2 type of structure: I4/mmm,
a = 399.2, c = 1007.0 pm, px = 6.46 kg·dm–3 [1978Ros]; X-ray powder diffraction). After the
discovery of the permanent magnet Nd2Fe14B with high magnetic anisotropy and high
magnetic energy product due to the interaction of magnetic Nd and Fe sublattices, scientific
interest in permanent magnet materials was concerned with Fe-Nd rich phases stabilized by
silicon: Nd6Fe13Si (τ4), NdFe10Si2 (τ7) and the solid solution Nd2Fe17–xSix.
τ2-NdFe2Si2: In a neutron powder diffraction study of NdFe2Si2 by Pinto and Shaked
[1973Pin] five superlattice reflections were observed at 4.2 K. These lines were found to be
consistent with a doubling of the c-axis according to a new unit cell a’ = 398.0 and c’ = 1990 pm
with the magnetic space group P2c4/nm’m’. The Nd sublattice with Nd atoms in the “2a sites”
{3.01(3) μB per Nd atom} orders antiferromagnetically. A collinear magnetic structure with
tetragonal symmetry of the Fe sublattice could be excluded. The Néel temperature at TN = 15.6
K was determined from the intensity-temperature curve of the strongest superlattice reflec-
tions. The magnetic structure consists of ferromagnetic sheets perpendicular to the c-axis
(magnetic axis along c) and with a stacking sequence ++ –. The neutron powder diffraction
pattern at room temperature (I4/mmm, a = 398.3, c = 1003 pm) was refined to R = 0.083 and
yielded a small statistical distribution of Fe/Si atoms according to: Nd in 2a sites, 0.902 Fe +
0.098 Si in 4d, and 0.098 Fe + 0.902 Si in the 4e sites with zSi= 0.372. The structure type at
room temperature was confirmed (a = 3.995 ± 0.05, c = 1007 ± 5 pm) by [1973Bau, 1975Fel],
who also reported magnetic susceptibility data with a weak ferromagnetic ordering at
713 ±⊊5 K; the rare earth sublattice orders antiferromagnetically at TN = 11 K, and from
4 9 Fe–Nd–Si
magnetization measurements a spin-flop transition is observed for a field of 11 kOe below the
Néel temperature. Mössbauer effect and magnetization measurements reveal most of the iron
to be diamagnetic (94 %). More recent magnetization and Mössbauer data by [1983Noa,
1983Uma] (57Fe, 297 K, 4.2 K) prove the absence of a magnetic moment at the Fe site and the
spectra at 4.2 K were interpreted by the presence of an internal magnetic field at the Fe nucleus,
due to the antiferromagnetic ordering of the R atom (conduction electron polarization caused
by Nd ion). Thus two magnetic sites were concluded for the Fe atoms without and with an
internal field of 22 ± 1 kG [1983Uma]. The thermal expansion coefficients of NdFe2Si2 have
been determined by Mayer and Felner [1972May] by means of high temperature diffractome-
try (see also NdFe0.4Si1.6): αa = 5.5 · 10–6 deg–1; αc = 11.1 · 10–6 deg–1;
a = 7.4 · 10–6 deg–1. The
volume expansion coefficient was γ = 22.6 · 10 deg . The electrical resistivity of NdFe2Si2
–6 –1
was 9.7 mΩ·cm at 300 K [1973Fel]. For a calculation of the electronic state of the Fe atoms in
NdFe2Si2, see Koterlin and Lutsiv [1978Kot]. Magnetic data on NdFe2Si2 were discussed by
[1987Lec] as part of a summary on isotypic rare earth and actinide compounds. Crystal
growth and analysis of basic thermodynamic properties of NdFe2Si2 was reported by
[2003Svo, 2003Vej].
Nd(Fe0.20Si0.80)2 (τ9):
Mayer and Felner [1972May] determined the thermal expansion coefficient of NdFe0.4Si1.6 by
means of high-temperature X-ray diffraction. Samples were held in Ta crucibles and the
temperature was accurate within ± 10˚C: αa = 10.5 · 10–6 deg–1, αc = 15.00 · 10–6 deg–1 and

a = 12.0 · 10–6 deg–1; the volume expansion coefficient was γ = 35.0 · 10–6 deg–1. NdFe0.4Si1.6
was said to exhibit a complex magnetic spin structure [1974Nar].
NdFeSi2 (τ8):
A detailed study of the magnetic structure of NdFeSi2 revealed a sine-modulated antiferro-

magnetic structure (Nd-moments = 2.52μB at 4.2 K) q = (0,0.591,0) below TN = 6.5 K
[1990Mal]. 57Fe Mössbauer data prove the absence of a magnetic moment at the Fe site but
indicated a progressive squaring of the sine modulation of the Nd-moments with a pure
square wave at 3 K suggesting orbital polarization of conduction electrons [1990Mal].
Nd6Fe13Si (τ4):
Nd6Fe13Si was found to be an antiferromagnet below TN = 725 K (452˚C) [1990All]

whereas [1998Gro] reported TN = 421 K (148˚C). Magnetization and Mössbauer measure-
ments on Nd6Fe13Si show antiferromagnetism with a net moment of 0 - 1μB/formula unit
but on hydrogenation to Nd6Fe13SiH14.6 there is ferromagnetic behavior with a moment of
23 - 27 μB/formula unit at room temperature [1996Lei]. The hydrogenation properties show a
marked reduction of the maximum hydrogen uptake related directly to the Si substitution rate
[1999Art].
[2002Taj] investigated magnetoelastic interactions in Nd6Fe13Si by magnetostriction and
thermal expansion measurements (77 - 300 K). A reversal in sign of magnetostriction versus
Fe–Nd–Si 9 5
temperature occurred at 115 K, accompanied by a spin re-orientation of iron ions from basal
plane to c axis at higher temperatures. At the spin re-orientation temperature (Tsr) of 115 K,
magnetostriction remains around zero due to the compensation of the negative magnetostric-
tion of the low-temperature phase by positive magnetostriction of the high temperature spin
phase. The magnetostriction compensation effect appears as a peak in the thermal expansion
coefficient curve.
A reinvestigation of the magnetic structure Nd6Fe13Si by means of powder neutron
diffraction and Mössbauer spectral studies between 2 - 295 K [2002Isn] confirmed earlier
findings: a collinear antiferromagnetic structure with the wave vector q = (0, 0, 1) below the
TN = 421 K. A spin reorientation is observed at T < 100 K in both the neutron diffraction
patterns and the Mössbauer spectra. Above and below 100 K, the magnetic moments of the
four iron and the two neodymium crystallographic sites are ferromagnetically coupled within
one block along the c axis and the resulting magnetic moment of this block is antiferromag-
netically coupled with that of the adjacent block along the c axis through a layer of silicon
atoms. Above and below 100 K, the magnetic moments are found to be parallel or very close to
the c axis and within or close to the (a, b) basal plane of the tetragonal unit cell, respectively.
NdFe10Si2 (τ7):
The substitutional effect on magnetic properties has been studied by X-ray powder diffraction
and Mössbauer spectroscopy on Nd2Fe15Si2, NdFe10Si2 [2003Sor]. A review on crystal struc-
ture, formation and magnetic properties of the hard magnetic phase NdFe10Si2 (TC = 574˚C) is
presented in [1991Bus].
Solution Nd2Fe17–xSix:
Substitution of Si for Fe in Nd2Fe17–xSix was investigated by [1993Lon, 1995Yel, 1995Zha,

1996Yel] by magnetization [1993Lon, 1997She, 1997Hua] and Mössbauer spectroscopy
[1993Lon], by neutron diffraction [1995Yel, 1996Yel] and high temperature X-ray diffraction
[1995Zha]. Fe/Si substitution was observed to raise the Curie temperature from TC = 325 K
(52˚C) for x = 0 to TC = 492 K (219˚C) for x = 3 [1993Lon, 1996Gir, 1997She]; reaching a
maximum at x = 4 [1995Yel]. The easy direction of magnetization was found to change from
basal at low Si content (x < 3) to axial at high Si content [1996Yel, 1995Zha] consistent with
Mössbauer spectra, magnetization and hyperfine field parallel to the c axis [1993Lon]. The
iron moment decreases on Si substitution [1997She]. Due to the various substitution effects
an Invar type of anomalies were reported for the temperature dependence of a, c parameters
below TC [1995Zha]. The observed spontaneous magnetostriction is due to isotropic exchange
contribution - no spin reorientation was observed for x < 3 [1995Zha]. The complicated mode
of substitution was interpreted in terms of a model which includes contributions from the
enthalpy of solution of the Si atom at each Fe site, the elastic energy due to the differences in
the volume of the site and the volume of the Si atom, and a structure dependent contribution
reflecting the difference in the average number of valence electrons at each Fe site [1998Gir].
The model was used to predict site occupation by the different sorts of atoms in various
intermetallics [2000Gir].

6 9 Fe–Nd–Si
. Table 1
Investigations of the Fe-Nd-Si Phase Relations, Structures and Thermodynamics
[1969May] HF melting under Ar from RE-ingots and Synthesis of Nd(Fe0.2Si0.8)2 with AlB2 type.
Fe,Si powders on MgO or Al2O3 crucibles.
Annealing in quartz at 700 to 800˚C for 24
to 96 h. Microstructure analysis, XPD
[1970Bod] Ar-arc melting from 50 g RE-ingots and Fe, Determination of the crystal structure of
Si powders. Annealing in quartz at 800˚C NdFeSi (PbFCl type); RF = 0.135.
for 3 months. Single crystals isolated from
center of alloy; X-ray single crystal study
[1972May] HF melting under He from RE-ingots and Synthesis of Nd(Fe0.2Si0.8)2 with AlB2 type.
Fe,Si powders on MgO or Al2O3 crucibles. Synthesis of NdFe2Si2 with ThCr2Si2 type.
Annealing in quartz at 700˚C for 48 h. Determination of thermal expansion
In situ high temperature XPD 20 to 1200˚C coefficients.
in Ta-sample holder.
[1973Bau] HF melting under Ar from RE-ingots and Synthesis of Nd(Fe0.125Si0.875)2 with ThSi2
Fe,Si powders on MgO or Al2O3 crucibles. type.
Annealing in HF at 1600˚C (reaction Synthesis of Nd(Fe0.2Si0.8)2 with AlB2 type.
temperature) for 20 min. XPD, 57Fe Synthesis of NdFeS with TiNiSi type.
Mössbauer analysis (4.2 and 300 K),
magnetic susceptibility (1.5 to 300 K)
[1973Fel] HF melting under Ar from RE-ingots and Synthesis of NdFe2Si2 with ThCr2Si2 type.
Fe,Si powders on MgO or Al2O3 crucibles. Electrical resistivity (100 to 280 K)
Annealing in HF at 1600˚C (reaction
temperature) for 30-60 min. XPD, electrical
resistivity (100 to 280 K)
[1973May] HF melting under Ar from ingots on Al2O3 Synthesis of NdFe2Si2 with ThCr2Si2 type.
crucibles. Annealing in HF at 1600˚C Electrical resistivity (100 to 280 K)
(reaction temperature) for 30 min. XPD
[1973Pin] See [1973May]; XPD, NPD at 4.2, 300, 650 K Synthesis of NdFe2Si2 with ThCr2Si2 type.
Determination of crystal and magnetic
structure by neutron diffraction.
[1974Nar] HF melting under Ar from ingots in Al2O3 Synthesis of Nd(Fe0.2Si0.8)2 with AlB2 type.
crucibles. Annealing in Vycor tubes at Elucidation of magnetic structure.
850˚C for 1 week. Microstructure analysis,
XPD. Magnetic susceptibility and
magnetization measurements (4.2 to
630 K)
[1975Fel] See [1973May]; magnetic susceptibility Synthesis of NdFe2Si2 with ThCr2Si2 type.
and magnetization measurements (1.5 to Determination of magnetic behavior.
300 K)

Fe–Nd–Si 9 7
[1978Ros] HF melting under Ar from ingots. Synthesis of NdFe2Si2 with ThCr2Si2 type.
Annealing in Vycor tubes at 500˚C for
1 week. Microstructure analysis, XPD.
[1990All] Single crystals of Nd6Fe13Si were isolated Synthesis of Nd6Fe13Si. Determination of
from an alloy 90Nd10Fe + 2 mass% Si crystal structure from X-ray single crystal
melted under vacuum and slowly cooled data.
from 700 to 500˚C (3˚C/h).
[1990Mal] Sintering of pellets from powders of Fe,Si Synthesis of NdFeSi2. Determination of
and filings of Nd at 1000˚C in silica tubes crystal and magnetic structure from X-ray
with repeated crushing. and neutron powder data.
X-ray (RT) and neutron (1.5 to 40 K)
powder diffraction ; 57Fe Mössbauer
analysis (1.6 and 295 K)
[1993Lon] HF melting (or arc casting) under Ar from Samples Nd2Fe17–xSix (x up to 4).
ingots. X-ray and neutron powder Determination of crystal and magnetic
diffraction; 57Fe Mössbauer spectrometry structure from X-ray and neutron powder
at 295K. Susceptibility and magnetization data.
(1.8 to 300 K)
[1995Zhu] 88 alloys prepared by HF melting under Ar Constitution of a partial isothermal
from ingots in alumina crucibles. section at 500˚C for the region < 40 at.%
Annealing for alloys < 20 at.% Nd: 800˚C Nd and < 40 at.% Si.
30 d - cooled to 500˚C at 10 K/h. Other
alloys were annealed at 650˚C for 40 d,
cooled at 10 K/h to 500˚C kept for 7 d
prior to quenching in ice water. XPD
[1996Sal] Ar-arc melting of ingots annealed in Determination of isothermal section at
quartz at 600˚C for 3 weeks. XPD 600˚C.
[1995Yel] Ar-arc or HF melting of ingots annealed in Samples Nd2Fe17–xSix (x up to 4.2). X-ray
[1996Yel] vacuum at 980˚C for 1 to 3 weeks and neutron powder diffraction to
[1996Gir] [1995Yel, 1996Yel] or at 1070˚C under Ar determine detailed atom site distribution
for several days [1996Gir]. X-ray and as a function of x.
neutron powder diffraction
[1998Wel] HF melting of ingots under Ar, annealed in X-ray single crystal structure
quartz at 1000˚C for 10 d. Crystals for determination of NdFeSi.
X-ray analyses isolated from ingot.
[2003Sor] Ar arc-melting of ingots, annealed in Preparation of Nd2Fe15Si2, NdFe10Si2
quartz at 950 to 1050˚C for 10 d. XPD, 57Fe
Mössbauer spectrometry at 295 K.

8 9 Fe–Nd–Si
. Table 2
Pearson
Phase/ Symbol/ Lattice
(βNd) cI2 a = 413 [Mas2]

1021 - 863 Im3m
W
(αNd) hP4 a = 365.82 [Mas2]
< 863 P63/mmc c = 1179.66
αLa
1538 - 1394 Im3m
W
(γFe) cF4 a = 364.67 pure Fe at 915˚C [Mas2]
1394 - 912 Fm3m
Cu
< 912 Im3m
W
(αSi) cF8 a = 543.06 at 25˚C [Mas2]
< 1414 Fd
3m
C (diamond)
Nd5Si3 tI32 a = 776.8 at 25˚C [V-C2]
< 1477 I4/mcm c = 1369
Cr5B3
a = 778.7 at 280˚C [V-C2]
c = 1373
Nd5Si3 hP16 a = 867.1 ± 2 [2006Rog]
? P63/mmc c = 657.7 ± 2
Mn5Si3
a = 778.7 may be impurity stabilized
c = 1373
Nd5Si4 tP36 a = 787.30 ± 0.01 [2006Rog]
< 1567 P41212 c = 1483.89 ± 0.01
Zr5Si4
Nd5Si4 oP36 a = 786.7 [V-C2]
Pnma b = 1474
Sm5Ge4 c = 790.7
a = 786.70 ± 0.03 [2006Rog]
b = 1508.35 ± 0.05
c = 789.20 ± 0.03

Fe–Nd–Si 9 9
Pearson
NdSi oP8 a = 818.74 ± 0.09 [2001Bou]

< 1677 Pnma b = 392.35 ± 0.04
FeB c = 588.40 ± 0.06
Nd2Si3–x (NdSi1.33) oC20 Listed as “Nd3Si4” [2000Oka]
< 1397 Cmcm
Ho3Si4 a = 435.89 ± 0.01 at NdSi1.40 [2001Bou]
or better V2B3 b = 2457.74 ± 0.04 [1992Sch] attributed V2B3 type
c = 391.61 ± 0.01
a = 436.2 x = 0.5 at 293 K [1992Sch]
b = 2458.4 Ferromagnetic TC = 80 K
c = 391.6
a = 434.75 x = 0.5 at 20 K [1992Sch]
b = 2456.42
c = 391.11
NdSi2–x hP3 x close to 0.4 [V-C2]
(h1) P6/mmm a = 395.03 ± 0.03 x close to 0.34 [2001Bou]
< 1507 AlB2 c = 425.73 ± 0.04
a = 394.8 [1990Pie]
c = 426.9 TN1 = 3.5 K, antiferromagnetic
Tm = 1.5 K, metamagnetism
NdSi2–x oI12 a = 417.6 NdSi1.8 [V-C2]
(h2) Imma b = 414.5
< 527 ? GdSi2–x c = 1359.9
a = 413.5 NdSi1.73
b = 410.1 TC = 10 K, ferromagnetic [1990Pie]
c = 1374
NdSi2–x(h3) tI12 a = 414.2 ± 0.6 x close to 0.2 [V-C2]
< 1757 I41/amd c = 1365 ± 2 [1990Pie]:
ThSi2 TN1 = 10 K, antiferromagnetic
TN2 = 6 K, collinear antiferromagnet
α1, Fe3Si cF16 D03, 11.0 to 30.0 at.% Si [1982Kub]
≤ 1235 Fm3m a = 565 [V-C2]
BiF3
α2, Fe-Si cP2 B2, 10.0 to 22.0 at.% Si [1982Kub]
≤ 1280 Pm3m a = 281 [V-C2]
CsCl
Fe2Si hP6 ~33.0 to ~34.3 at.% Si [1982Kub]
1212 - 1040 P
3m1 a = 405.2 ± 0.2
Fe2Si c = 508.55 ± 0.03 [V-C2]

10 9 Fe–Nd–Si
Pearson
Fe5Si3 hP16 37.5 at.% Si [1982Kub]

1060 - 825 P63/mmc a = 675.9 ± 0.5 [V-C2]
Mn5Si3 c = 472.0 ± 0.5
FeSi cP8 49.6 to 50.8 at.% Si [1982Kub]
< 1410 P213 a = 451.7 ± 0.5 [V-C2]
FeSi
FeSi2(h) tP3 69.5 to 73.5 at.% Si [1982Kub]
1220 - 937 P4/mmm a = 269.01 [V-C2]
FeSi2 c = 513.4
FeSi2(r) oC48 66.7 at.% Si [1982Kub]
< 982 Cmca a = 986.3 ± 0.7 [V-C2]
FeSi2 b = 779.1 ± 0.6
c = 783.3 ± 0.6
Nd2Fe17(r) hR57 a = 857 to 859 [V-C2]
< 1208 R
3m c = 1244 to 1248
Th2Zn17
Nd2(Fe1–xSix)17
0 < x < 0.16 [V-C2] linear
dependence
0 < x < 0.13 at 500˚C [1995Zhu]
x is at least 0.235 at subsolidus
[1993Lon]
a = 859.0 nonlinear dependence
c = 1247.6
at x = 0 [V-C2]
a = 852.1
c = 1249.7
at x = 0.16 [V-C2]
a = 856.1
c = 1247.5
x = 0.059 [1995Zha]
a = 853.3 TC = 149˚C
c = 1249.0
x = 0.118 [1995Zha]
a = 853.25 TC = 219˚C
c = 1245.54
x = 0.235 (subsolidus) [1993Lon]
TC = 227˚C
Nd5Fe17 hP228 a = 2021.4 ± 0.8 [1991Lan]
< 780 P63/mcm c = 1232.9 ± 0.8
Nd5Fe17

Fe–Nd–Si 9 11
Pearson
NdFe5 hP6 a = 494.6 [1986Sta]

metastable? P6/mmm c = 417.0 from splat-cooled alloy
CaCu5
* τ1, NdFeSi3 - [1996Sal]
* τ2, NdFe2Si2 tI10 a = 398.1 ± 0.1 at 25˚C [1972May]
< 700 I4/mmm c = 1002 ± 0.2 at 400˚C [1972May]
ThCr2Si2
a = 399.2 ρexp = 6.46 Mg·m–3 [1978Ros]
c = 1011 a supercell was found at 4.2 K
a = 398.0, c = 1990 pm = 2c0
[1973Pin]
TN = 15.6 K
a = 400.7 at 1150˚C [1972May]
c = 1026 linear dependency 25 to 1150˚C
* τ3, NdFeSi (h) oP12 a = 689 [1973May]
Pnma b = 532
TiNiSi or Co2Si c = 1118
* τ3, NdFe1+xSi1–x (r) tI12 –0.8 < x < 0.16 at 500˚C [1995Zhu]
P4/nmm a = 405.7 x = 0, quenched from 800˚C;
PbClF c = 689.3 ρexp= 6.54 Mg·m–3[1970Bod]
(CeFeSi type) [V-C2] lists Cu2Sb type
a = 392.1 [1995Zhu] no x given
c = 694.2
a = 405.7 ± 0,3 x = 0, SC data from alloy at 1000˚C
c = 691.9 ± 0,5 [1998Wel]; R = 0.076
* τ4, Nd6Fe13Si tI80 a = 803.4 [1990All]
I4/mcm c = 2278 RF = 0.07
Nd6Fe13Si derivative of Nd6Fe11Ga3 type
* τ5, Nd(Fe0.33Si0.67)2 - - [1972May]
< 950
* τ6, Nd(Fe0.125, Si0.875)2 tI12 a = 411.5 [1973May]
I41/amd c = 1390
ThSi2
*τ7, NdFe10Si2 cF296 - [1991Bus, 2003Sor]
Fm3m no lattice parameters given
ThMn12
* τ8, NdFeSi2 oC16 a = 408.2 ± 0,3 [1990Mal]
Cmcm b = 1698 ± 3 TbFeSi2 type
variant of c = 400.4 ± 0,3 TN = 6.5 K sine modulated AF
CeNiSi2

12 9 Fe–Nd–Si
Pearson
* τ9, Nd(Fe0.2Si0.8)2 tP3 a = 403.1 quenched from 700 to 800˚C

< 950 P6/mmm c = 419.2 [1969May]
AlB2
a = 404.6 at 25˚C [1972May]
c = 421.7
a = 405.9 at 500˚C [1972May]
c = 423.7
a = 406.5 at 600˚C [1972May]
c = 425.3
a = 407.2 at 820˚C [1972May]
c = 426.1

Fe–Nd–Si 9 13
. Fig. 1
Fe-Nd-Si. Isothermal section at 600˚C. Location of ternary compounds, τ5 to τ9, not detected by
[1996Sal], are shown as filled circles

14 9 Fe–Nd–Si
References
[1969May] Mayer, I., Tassa, M., “Rare-Earth-Iron (Cobalt, Nickel)-Silicon Compounds”, J. Less-Common Met.,
19, 173–177 (1969) (Crys. Structure, Experimental, 9)
[1970Bod] Bodak, O.I., Gladyshevsky, E.I., Kripyakevich, P.I., “Crystal Structure of Ce-Fe Silicide and Similar
Compounds.”, Zh. Strukt. Kim., 11, 305–310 (1970) (Experimental, Crys. Structure, 20)
[1972May] Mayer, I., Felner, I., “High-Temperature X-Ray Study of Rare-Earth Silicides”, J. Less-Common Met.,
[1973Bau] Bauminger, E.R., Felner, I., Froindlich, D., Grill, A., Lebenbaum, D., Mayer, I., Nowik, I., Ofer, S.,
Schieber, M., “Magnetic Properties of RFe2Si2 and RFe2Ge2 Compounds” in “Proc. Intl. Conf. Magne-
tism”, Moscow, 5, 56–59 (1973) (Experimental, Crys. Structure, Magn. Prop., 5)
[1973Fel] Felner, I., Mayer, I., “The Electrical Resistivity of RFe2Si2 Type Rare-Earth Silicides”, Mater. Res. Bull.,
8, 1317–1319 (1973) (Crys. Structure, Electr. Prop., Experimental, 5)
[1973May] Mayer, I., Felner, I., “Structure Types of Ternary Rare Earth - Transition Metal Silicides of the LnMxSi2–x
Type”, J. Solid State Chem., 7, 292–296 (1973) (Crys. Structure, Experimental, 12)
[1973Pin] Pinto, H., Shaked, H., “Neutron-Diffraction Study of NdFe2Si2”, Phys. Rev. B (Solid State), 7(7),
[1974Nar] Narasimhan, K.S.V.L., Steinfink, H., “Magnetic Investigations on AlB2 Type Structures”, J. Solid State
Chem., 10, 137–141 (1974) (Crys. Structure, Experimental, Magn. Prop., 10)
[1975Fel] Felner, I., Mayer, I., Grill, A., Schieber, M., “Magnetic Ordering in Rare-Earth Fe Silicides and
Germanides of the RFe2X2 Type”, Solid State Commun., 16, 1005–1009 (1975) (Crys. Structure, Experi-
mental, Magn. Prop., 17)
[1978Kot] Koterlin, M.D., Lutsiv, R.V. “Electron State of Iron Atoms in the Neodymium Iron Silicide (NdFe2Si2)
Compound” (in Russian), Fiz. Elektronika, 17, 18–21 (1978) cited from Ref. Zh., Fiz., E, Abstr. No. 2E58
(1979) (Experimental, Phys. Properties, 4)
[1978Ros] Rossi, D., Marazza, R., Ferro, R., “Lattice Parameters of Some ThCr2Si2 Type Phases in Ternary Alloys of
Rare Earths with Cobalt (or Iron) and Silicon (or Germanium)”, J. Less-Common Met., 58(2), 203–207
(1978) (Crys. Structure, Experimental, 10)
[1982Kub] Kubaschewski, O., “Iron-Silicon” in “Iron - Binary Phase Diagrams”, Springer Verlag, Berlin, 136–139
(1982) (Phase Diagram, Review, #, *, 23)
[1983Noa] Noakes, D.R., Umarji, A.M., Shenoy, G.K., “Mössbauer Studies of REFe2Si2 (RE = Gd-Lu) Com-
pounds”, J. Magn. Magn. Mater., 39, 309–316 (1983) (Experimental, Crys. Structure, Magn. Prop., 22)
[1983Uma] Umarji, A.M., Noakes, D.R., Vccaro, P.J., Shenoy, G.K., Aldred, A.T., “Magnetic Properties of REFe2Si2
Compounds”, J. Magn. Magn. Mater., 36(1–2), 61–65 (1983) (Experimental, Crys. Structure, Magn.
Prop., 19)
[1984Rog] Rogl, P., “Phase Equilibria in Ternary and Higher Order Systems with Rare Earth Elements and Silicon”
in “Handb. Phys. Chem. Rare Earths”, North-Holland Publ. Co, Amsterdam, vol. 7, 1–264 (1984)
(Review, Crys. Structure, Phys. Properties, 10)
[1986Sta] Stadelmaier, H.H., Schneider, G., Ellner, M., “A CaCu5-type Iron-Neodymium Phase Stabilized by
Rapid Solidification”, J. Less-Common Met., 115, L11–L14 (1986) (Crys. Structure, Experimental, 5)
[1987Lec] Leciejewicz, J., Szytula, A., “The Systematics of Magnetic Structure Observed in MT2X2 Compounds”,
Acta Phys. Pol., A72(1), 65–68 (1987) (Assessment, Electronic Structure, Magn. Prop., 8)
[1990All] Allemand, J., Letant, A., Moreau, J.M., Nozieres, J.P., Perrier de la Bathie, R., “A New Phase in Nd2Fe14B
Magnets. Crystal Structure and Magnetic Properties of Nd6Fe13Si”, J. Alloys Compd., 166, 73–79 (1990)
(Experimental, Crys. Structure, Magn. Prop., 9)
[1990Mal] Malaman, B., Venturini, G., Le Caer, G., Potonnier, L., Fruchart, D., Tomala, K., Sanchez, J.P.,
“Magnetic Structures of PrFeSi2 and NdFeSi2 from Neutron and Mössbauer Studies”, Phys. Rev. B, 41(7),
4700–4712 (1990) (Experimental, Crys. Structure, Magn. Prop., 33)
[1990Pie] Pierre, J., Auffret, S., Siaud, E., Madar, R., Houssay, E., Rouault, A., Senateur, J.P., “Magnetic Properties
of Rare Earth Silicide Single Crystals RSi2–x (R = Pr, Nd, Gd)”, J. Mag. Magn. Mater, 89(1-2), 86–96
(1990) (Experimental, Crys. Structure, Magn. Prop., 10)
[1991Bus] Buschow, K.H.J., “New Developments in Hard Magnetic Materials”, Rep. Prog. Physics, 54, 1123–1213
(1991) (Review, Magn. Prop., 223)

Fe–Nd–Si 9 15
[1991Lan] Landgraf, F.J.G., Missell, F.P., Rechenberg, H.R., Schneider, G., Villas-Boas, V., Moreau, J.M., Paccard,
L., Nozieres, J.P., “Magnetic and Structural Characterization of Nd5Fe17”, J. Appl. Phys., 70(10),
6125–6127 (1991) (Crys. Structure, Magn. Prop., Experimental, 16)
[1992Sch] Schobinger-Papamantellos, P., DeMooij, D.B., Buschow, K.H.J., Fischer, P., “Magnetic Ordering in
Silicon Defect Nd-Si Compounds Studied by Neutron Diffraction and Magnetic Measurements”,
J. Alloys Compd., 178, 151–159 (1992) (Crys. Structure, Experimental, Magn. Prop., 13)
[1993Hen] Hennemann, K., Lukas, H.L., Schaller, H.J., “Constitution and Thermodynamics of Fe-Nd Alloys”, Z.
Metallkd., 84, 668–674 (1993) (Experimental, Calculation, Thermodyn., Phase Diagram, 34)
[1993Lon] Long, G.J., Marasinghe, G.K., Mishra, S., Pringle, O.A., Grandjean, F., Buschow, K.H.J., Middleton, D.P.,
Yelon, W.B., Pourarian, F., Isnard, O., “A Neutron Diffraction and Mössbauer Study of the Nd2Fe(17–x)Si(x)
Solid Solution”, Solid State Commun., 88(10), 761–764 (1993) (Crys. Structure, Experimental, 10)
[1994Yan] Yan, Q.W., Zhang, P.L., Sun, X.D., Hu, B.P., Wang, Y.Z., Rao, X.L., Liu, G.C., Gou, C., Chen, D.F.,
Cheng, Y.F., “The Magnetic Structure of Nd6Fe13Si”, J. Phys., Condens. Matter, 6(16), 3101–3107, (1994)
(Experimental, Crys. Structure, Magn. Prop., 10)
[1995Yel] Yelon, W.B, “Neutron Investigations of Novel Magnetic Phases”, IEEE Trans. Magn., 31(6), 3689–3694
[1995Zha] Zhang, X.D., Shumsky, M.G., James, W.J., “Anomalous Thermal Expansion in Substituted Nd2Fe17–xSix
and Nd2Fe17–xAlx Compounds”, IEEE Trans. Magn., 31(6), 3662–3664 (1995) (Crys. Structure, Experi-
mental, 10)
[1995Zhu] Zhuang, Y., Pan, C., Li, J., “Phase Equilibria in the Fe-Rich Alloys of the Ternary System Nd-Fe-Si at
500˚C”, J. Alloys Compd., 217, 161–163 (1995) (Experimental, Phase Relations, 10)
[1996Gir] Girt, Er., Altounian, Z., Ming Mao, Swainson, I.P., Donaberger, R.L., “Neutron Diffraction Study of Fe
Substitutions in Nd2Fe17–δXδ (X = Al, Si, Ga, Mo, W)”, J. Magn. Magn. Mater., 163, L251–L256 (1996)
(Crys. Structure, Experimental, Magn. Prop., 15)
[1996Lei] Leithe-Jasper, A., Skomski, R., Qi, Q., Coey, J.M.D., Weitzer, F., Rogl, P., “Hydrogen in RE6Fe13XHy
Intermetallic Compounds (RE = Pr, Nd; X = Ag, Au, Si, Ge, Sn, Pb)”, J. Phys.: Condens. Matter, 8(19),
[1996Sal] Salamakha, P.S., Stepen-Damm, J., Bodak, O., “Isothermal Section of the Nd-Fe-Si System at 870 K”, J.
Alloys Compd., 242, L1–L2 (1996) (Crys. Structure, Experimental, Phase Diagram, Phase Relations, 12)
[1996Yel] Yelon, W.B., Hu, Z., Chen, M., Luo, H., Ezekwenna, P.C., Marasinghe, G.K., James, W.J., Buschow, K.H.J.,
Middleton, D.P., Pourarian, F., “Neutron Diffraction and Magnetic Studies of Nd2Fe17–xTx (T = Si, Mn)
Alloys”, IEEE Trans. Magn., 32(5), 4431–4433 (1996) (Crys. Structure, Experimental, 10)
[1997Hua] Huang, M.Q., Wallace, W.E., “Structure and Magnetic Properties of RFe13-xSix (R = Pr, Nd or Gd,
x = 2.5 - 5)”, J. Magn. Magn. Mater., 173, L225–L229 (1997) (Crys. Structure, Experimental, 10)
[1997She] Shen, B.-G., Liang, B., Cheng, Z.-H., Gong, H.-Y., Zhan, W.-S., Tang, H., de Boer, F.R., Buschow, K.H.J.,
“Magnetic Properties of R2Fe14M3 Compounds with M = Ga and Si; R = Y, Nd, Sm, Gd, Tb, Dy, Ho, Er
and Tm)”, Solid State Commun., 103, 71–75 (1997) (Crys. Structure, Experimental, 10)
[1998Gir] Girt, E., Altounian, Z., “Origin of Fe Substitution in Nd2Fe17–δXδ”, Phys. Rev. B, Cond. Matter, 57(10),
5711–5714 (1998) (Calculation, Crys. Structure, Experimental, Thermodyn., 20)
[1998Gro] Groot de, C.H., Buschow, K.H.J., Boer de, R.F., “Magnetic Properties of R6Fe13–xM1+x Compounds and
Their Hydrides”, Phys. Rev. B, Condens. Matter, 57(18), 11472–11482 (1998) (Crys. Structure, Experi-
[1998Mie] Miettinen, J., “Reassessed Thermodynamic Solution Phase Data for Ternary Fe-Si-C System”, Calphad,
22(2), 231–256 (1998) (Calculation, Assessment, Thermodyn., 36)
[1998Wel] Welter, R., Ijjaali, I., Venturini, G., Malaman, B., “X-Ray Single Crystal Refinement on Some CeFeSi
type RTX Compounds (R = RE Elements; T = Mn, Fe, Co, Ru; X = Si, Ge). Evolution of the Chemical
Bonds”, J. Alloys Compd., 265, 196–200 (1998) (Crys. Structure, Experimental, 16)
[1999Art] Artigas, M., Fruchart, D., Gasdeblay, C., Isnard, O., Miraglia, S., “Structural, Magnetic and
Hydrogenation Properties of R2Fe17–xSix Compounds (R = Rare Earth Element). II. Effects of Hydrogen
Insertion on the Magnetic Properties (R = Ce, Nd; 0 < x < 0.5”, J. Alloys Compd., 291, 282–288 (1999)
(Crys. Structure, Experimental, Magn. Prop. 19)
[2000Gir] Girt, E., Altounian, Z., “Model for Predicting Atomic Substitutions in Intermetallic Compounds”, J.
Appl. Phys., 87(9), 4747–4749 (2000) (Calculation, Crys. Structure, 19)
[2000Oka] Okamoto, H., Desk Handbook Binary Phase Diagrams, ASM International, Materials Park, Ohio, 611
(2000) (Review, Phase Diagram, 1).

16 9 Fe–Nd–Si
[2001Bou] Boulet, P., Weitzer, F., Hiebl, K., NoNl, H., “Structural Chemistry, Magnetism and Electrical Properties
of Binary Nd Silicides”, J. Alloys Compd., 315(1-2), 75–81 (2001) (Experimental, Crys. Structure, Magn.
Prop., 15)
[2002Isn] Isnard, O., Ling, G.J., Hautot, D., Buschow, K.H.J., Grandjean, F., “A Neutron Diffraction and
Mössbauer Spectral Study of the Magnetic Spin Reorientation in Nd6Fe13Si”, J. Phys.: Condens. Matter,
14(47), 12391–12409 (2002) (Crys. Structure, Experimental, Magn. Prop., 33)
[2002Taj] Tajabor, N., Alinejad, M.R., Pourarian, F., “Anomalies of Magnetostriction and Thermal Expansion
in Nd6Fe13Si Solid Solution”, Physica B, 321(1-4), 60–62 (2002) (Experimental, Magn. Prop., Phys.
Prop., 7)
[2003Sor] Sorescu, M., Valeanu, M., Diamandescu, L., “Effect of Substitution on the Hyperfine Magnetic Field in
Nd-based Intermetallics”, Intermetallics, 11(8), 749–754 (2003) (Crys. Structure, Experimental, Magn.
Prop., Morphology, 8)
[2003Svo] Svoboda, P., Vejpravova, J., Honda, F., Santava, E., Schneeweiss, O., Komatsubara, T., “The Analisis of
the Specific Heat of RFe2Si2 Compounds”, Physica B, 328(1-2), 139–141 (2003) (Crys. Structure,
Experimental, Thermodyn., 6)
[2003Vej] Vejpravova, J., Svoboda, P., Sechovsky, V., Janecem, M., Komatsubara, T., “Crystal Growth and Basic
Thermodynamic Properties of NdFe2Si2”, Physica B, 328(3-4), 173–178 (2003) (Experimental, Magn.
Prop., Phase Relations, Thermodyn., 8)
[2005Mec] Meco, H., Napolitano, R.E., “Liquidus and Solidus Boundaries in the vinicity of Order-Disorder
Transitions in the Fe-Si System”, Scr. Mater., 52, 221–226 (2005) (Experimental, Calculation, Phase
[2006Rog] Roger, J., Babizhetskyy, V., Jardin, R., Halet, J.-F., GuJrin, R., “Solid State Phase Equilibria in the
Ternary Nd-Si-B System at 1270 K”, J. Alloys Compd., 415(1-2), 73–84 (2006) (Experimental, Crys.
Structure, 41)
(1990)

Fe–Ni–P 10 1
Iron – Nickel – Phosphorus

Kostyantyn Korniyenko
Introduction
Phase relations in the Fe-Ni-P system are of great interest, in particular, for the basic study of
meteoritic minerals, for applications in electronics etc. However, the amount of information
available about the constitution of this system is insufficient at the present time. The available
experimental data regarding phase equilibria were published quite long ago [1931Vog,
1966Buc, 1970Doa, 1975Nor, 1980Rom, 1984Nar2]. The reaction scheme and liquidus surface
projection of the Fe-Fe2P-Ni5P2-Ni partial system as well as series of partial isothermal and
vertical sections have been reported. However, data on the liquid-solid equilibria and the
liquidus surface projection presented in [1931Vog] are in contradiction with later versions of
the boundary binary Fe-Ni system and therefore, reinvestigation of this aspect of the phase
diagram using physico-chemical analysis techniques is necessary. Moreover, expansion of the
known concentration range involving the binary Fe-P and Ni-P phases with higher P contents
is an important issue.
Publications relating to experimental studies of phase relations, crystal structures and
thermodynamics as well as the techniques applied are listed in Table 1. Information on
thermodynamic properties, in the first instance concerning the activity of phosphorus in
liquid iron with nickel additions, was obtained experimentally by [1969Sch, 1979Yam,
1983Yam, 1984Ban]. Reviews of literature data relating to the phase equilibria of the
Fe-Ni-P system are presented in [1949Jae, 1988Rag], crystal structures - in [1988Rag],
thermodynamics - in [1979Yam, 1984Ban]. A thermodynamic description of the Fe-Ni-P
system was derived by [1990Gus].
Binary Systems
The Fe-P and Fe-Ni binary boundary systems are accepted from [2002Per] and [2008Kuz],
respectively. The Ni-P boundary system is accepted from [Mas2].
Solid Phases
Crystallographic data relating to the known unary and binary Fe-Ni-P phases and their
concentration as well as temperature ranges of stability are presented in Table 2. The (γFe)
and (Ni) phases form a continuous series of solid solutions in the binary Fe-Ni system, with
little solubility of phosphorus in the Fe-Ni alloys [1965Kan2]. The P solubility in the (Fe,Ni)
alloys increases with the Ni content of the alloy, which agrees with the quite high solubility of P
in pure Ni.

2 10 Fe–Ni–P
Two continuous series of solid solutions are reported to form between isostructural binary
phases existing over the whole composition range and wide temperature ranges; namely the
M3P phase (Ni3P type structure) and the M2P phase (Fe2P type) [1988Rag]. High solubilities
of nickel in the FeP-based phase [1986Fje] as well as of iron in the NiP3-based phase [2000Jei]
exist. The crystal structures of the M3P solid solutions, having the mineralogical names
schreibersite and rhabdite, which have been extracted from Canyon Diablo, Morasko as well
as Orange River meteorites, are reported in [2003Mor1, 2003Mor2, 2003Mor3], respectively.
No ternary phase has been found in the system.
Quasibinary Systems
It was concluded by [1931Vog] that the Fe2P-Ni5P2 section is a quasibinary, probably of the
simple eutectic type with eutectic temperature of about 990˚C. Position of the eutectic point e6
is presented in Table 3. Solubilities of third component in the Fe2P- and Ni5P2-based phases
were not established.
Temperatures, types of reactions and compositions of the phases taking part in the invariant
equilibria (that are available) for the partial Fe-Fe2P-Ni5P2-Ni system are listed in Table 3. A
partial reaction scheme (Fig. 1) is compiled on the basis of data from [1931Vog] and
[1970Doa] concerning the constitution of the liquidus surface, the character of the invariant
equilibria in the partial Fe-Fe2P-Ni5P2-Ni system and the constitution of the accepted bound-
ary binary systems. It is essentially the same as that proposed in the assessment of [1988Rag].
The compositions of the phases taking part in the transition reaction L + αδ Ð γ + M3P and
the corresponding invariant temperature are taken from [1970Doa]. The remaining invariant
equilibria are based on [1931Vog]. A maximum point (max), Table 3, corresponds to the
change in character of the univariant process involving the liquid, M3P and Ni5P2 phases.
Its composition is ~18.7Fe56.3Ni25P (at.%).
The liquidus surface projection of the partial Fe-Fe2P-Ni5P2-Ni system was constructed by
[1931Vog] on the basis of experimental data obtained by using thermal analysis and metallo-
graphic techniques. The proposed diagram was reproduced in the review of [1949Jae]. But
later, because of revision of the Fe-Ni boundary system, the necessity for a reinvestigation of
the liquidus surface projection has arisen. Figure 2 presents the liquidus surface projection of
the partial Fe-Fe2P-Ni5P2-Ni system based mainly on the critical review of [1988Rag]. The
positions of the invariant points E, e6 and max given by [1931Vog] are preserved but the U
point is placed in accordance with [1970Doa]. Univariant curves are drawn as dashed lines but
their accurate location needs to be determined. The author of [1990Gus] proposed a calculat-
ed liquidus surface projection of the Fe-Fe2P-Ni5P2-Ni partial system. This must be considered
as speculative as no attempt was made to fit the experimental data of [1931Vog].

Fe–Ni–P 10 3
The positions of the apexes of the invariant three-phase plane α-γ-M3P existing on the
solidus surface of the ternary system at 1000 ± 5˚C are listed in Table 3, taken from the work of
[1970Doa]. Below 995˚C, the three-phase fields are L + γ + M3P and L + γ + αδ; above 1005˚C,
the three-phase fields are L + αδ + γ and L + αδ + M3P.
Isothermal Sections
A series of isothermal sections of the ternary Fe-Ni-P system were proposed on the basis of
experimental data [1966Buc, 1970Doa, 1975Nor, 1980Rom, 1984Nar2] and calculated results
[1990Gus].
Isothermal sections at the temperature of 1100˚C in the range of phosphorus content of up
to about 20 at.% P were proposed independently by [1966Buc] and [1970Doa], but the latter
work is preferable because the materials used in the investigation were of higher purity and the
annealing times were longer than in the former work. This section is shown in Fig. 3 on the
basis of [1970Doa], with amendments according to the constitution of the accepted binary
systems. So, the L/(L + αδ) boundary from the side of the Fe-P binary is shifted in the direction
of nickel corner. The isothermal section at 1100˚C for the same composition range calculated
by [1990Gus] shows good agreement with the experimental data of [1966Buc, 1970Doa],
except for the liquid phase composition (apex of the L-αδ-γ triangle corresponding to the
composition of liquid is proposed to be at about Fe75.6Ni10.8P13.6 (in at.%)).
Partial isothermal sections at 1060 and 1010˚C constructed by [1970Doa] are shown in
Figs. 4 and 5, respectively; with amendments according to the accepted Fe-P binary system
(the L + αδ field in Fig. 4 is now narrower). One can see that above the Fe-P eutectic
temperature, 1048˚C, the L + αδ field is separated from the L + γ field by a three-phase region
(L + αδ + γ). Below 1048˚C, the αδ + M3P field forms while the L + αδ field is still stable.
[1970Doa] noted that these two-phase regions must be separated by a three-phase field (L + αδ
+ M3P) but, their specimens didn’t contain these phases and therefore the (L + αδ + M3P) field
is estimated in Fig. 5.
A partial isothermal section for 1000˚C was reported by [1966Buc] and later by [1970Doa].
Actually, the temperature of 1000 ± 5˚C is that of the invariant L + αδ Ð γ + M3P whose phase
compositions are given in Table 3. The partial isothermal section at this temperature calculat-
ed by [1990Gus] shows good agreement with experimental data of [1966Buc] and [1970Doa],
except for the liquid phase composition (given as about Fe74.1Ni10.7P15.2 in at.%).
In comparison with the section at 1000˚C, the partial isothermal section at 995˚C
[1970Doa] shows two three-phase fields separated by a newly formed γ + M3P region. No
alloys with composition lying inside this three-phase field (L + γ + M3P) were studied, and so
the boundaries which enclose this region were defined by tie lines obtained within the L + M3P
and L + γ fields. An isothermal section for 975˚C in the range of phosphorus content of up to
25 at.% and nickel content of up to about 15 at.% was constructed by [1975Nor] during a
study of the ternary dissolution kinetics in the Fe-Ni-P system using diffusion couples. The
section contains the three-phase field (M3P + αδ + γ). The partial isothermal section for 970˚C
proposed by [1966Buc] was presented as corresponding to the temperature of the four-phase
invariant equilibrium L + αδ Ð γ + M3P, but this was later corrected by [1970Doa]. Therefore,
the section at 950˚C constructed by [1966Buc] should also be corrected.
A partial isothermal section for 875˚C was reported by [1966Buc, 1970Doa] (the results of
the latter work are presented in Fig. 6). An isothermal section for this temperature was also
4 10 Fe–Ni–P
calculated by [1990Gus]; quite good agreement with the experimental data of [1966Buc] and
[1970Doa] is observed. All the reported isothermal sections in the Fe rich corner
corresponding to this and lower temperatures are analogous with regard to the phase regions
(three-phase field (M3P + αδ + γ) and the adjacent fields corresponding to the (αδ + γ + M3P)
phases as well as two-phase regions αδ + M3P, M3P + γ and αδ + γ). This type of section
contains the partial isothermal sections at 750, 650, 550, 450, 350˚C constructed by [1966Buc],
partial isothermal sections at 750, 650, 550˚C [1970Doa], at 600 and 400˚C [1988Rag], partial
isothermal sections at 700, 600, 500, 400 and 300˚C [1980Rom] as well as calculated
partial isothermal sections at 750 and 650˚C [1990Gus]. Also, on the basis of the investigation
of the growth of intergranular ferrite in Fe-Ni-P alloys, [1984Nar2] presented partial isother-
mal sections at phosphorus contents of up to about 2 at.% at 800, 720 and 700˚C.

A series of schematic temperature-composition sections were proposed by [1931Vog] with a
view to illustrate the conditions of crystallization in the ternary system. These sections, like the
liquidus surface projection, need further verification using modern methods of physico-
chemical analysis.
Thermodynamics
The effect of nickel on the activity coefficient of phosphorus in liquid iron alloys at different
temperatures was studied by [1969Sch, 1979Yam, 1983Yam, 1984Ban]. It was reported by
[1969Sch], that the addition of nickel up to 32 at.% to liquid Fe-P alloys at 1550˚C does not
influence the activity of phosphorus, and therefore the interaction parameter εP(Ni) = ∂ ln aNi /
∂ ln xP) ~ 0. [1979Yam, 1983Yam] used a mass spectrometer equipped with a newly developed
ion current measuring system combined with a Knudsen cell. For measurements carried out at
1600˚C, a value of 0.7 ± 0.7 was obtained for the interaction parameter εP(Ni). Later, the vapor
pressure of phosphorus in liquid Fe-Ni-P alloys containing up to 28.3 mass% Ni was measured
by [1984Ban] using the transportation method at 1400˚C. By applying the interstitial solution
model of Chipman to the results, the effect of nickel on the activity coefficient of phosphorus
in liquid iron was determined by assuming the nickel dissolves substitutionally. A value of
εP(Ni) = – 1.48 ± 0.88 at 1400˚C was reported.
A thermodynamic description of the Fe-Ni-P system was derived by [1990Gus], and a
partial liquidus surface projection and partial isothermal sections at 1100, 1000, 875, 750 and
650˚C were calculated. According to [1998Mie], the value of the ternary parameter LFeNiP in
the γ phase did not give good agreement between calculated and published experimental
results, and hence, the value of this parameter needs to be re-optimized. A non-metal
interaction model for the segregation of trace metals during solidification of the Fe-Ni-P
alloys was proposed by [1990Jon]. A method for parameterizing solid metal - liquid metal
partition coefficients for siderophile (iron-loving) elements as a function of the metallic liquid
composition based on the theory of [1990Jon] was proposed in [2003Cha]. The interaction
parameter in liquid iron at 1600˚C was evaluated by [1993Din] as εP(Ni) = 1.81. By consider-
ation of the effect of various concentrations (up to 0.9 mass%) of added phosphorus on grain
growth in Fe-50 mass% Ni for sintering temperatures ranging from 950 to 1250˚C [2002Chu],
Fe–Ni–P 10 5
three different grain growth mechanisms having different ratios of activation energy to grain
growth exponent were identified. The ratios of activation energy to grain growth exponent for
these three domains were 50, 202 and 72 kJ·mol–1, respectively. It was reported by [2006Gao]
that during the heating of an electrodeposited amorphous Fe8Ni69P23 (at.%) alloy, six exo-
thermic reactions take place continuously. Their temperatures are 248, 303, 322, 350, 376 and
442˚C; the activation energies of the exothermic reactions were proposed. The amorphous
Fe22Ni60P18 alloy crystallizes when heating beyond 250˚C.
The Fe-Ni-P and related alloys (complicated nickel-containing steels and ferronickel alloys)
are of great interest for practical applications in modern technology. In addition to studies of
Fe-Ni-P alloys as the basic component of meteoritic minerals, it was recently established by
[2000Jei] that the NiP3-based phase with the addition of iron (Fe0.5Ni0.5P3) has the skutter-
udite type structure that exhibits useful electric and magnetic behavior. Information about
phase relations in the Fe-Ni-P system is important also for clarification of the effect of the non-
metallic element phosphorus on the properties of the well-known industrial alloy, invar
(Fe64Ni36 in mass% or Fe65.1Ni34.9 in at.%), which possesses a low thermal expansion coeffi-
cient and is used as the shadow mask in cathode ray tubes for color TV and as the structural
material for liquid nitrogen gas tanks used in industry [1987Ina].
The experimental techniques applied and types of properties investigated are listed in
Table 4.
The variation of hardness during tempering was studied by [1966Buc] for different alloys
containing up to 40 mass% Ni and 0.4 mass% P. It was noted that a considerable increase in
hardness was experienced when phosphides precipitated from the austenite (γFe), but the
hardness was seen to decrease considerably when the phosphides precipitated from the α/α2
phase. After heat treating a Fe-25Ni-0.4P (mass%) alloy (Fe75.3Ni24.0P0.7) for extensive periods
at 350˚C, a hardness peak developed, which has been tentatively ascribed to the order
hardening reaction giving Fe3Ni. It was reported by [1987Ina], that additions of P influence
the thermal expansion coefficient of the invar alloy (Fe-36Ni (mass%)) in the following
way: the thermal expansion coefficient α = (1/V)(∂V/∂T)P of the as-rolled specimen decreased
slightly with an increase in phosphorus content up to 0.05 mass% P, which generates disloca-
tions and vacancies. Above 0.05 mass% P, however, α increases monotonically. Both 0.2 %
yield strength (σ0.2) and tensile strength (σB) increase rapidly with P additions of up to 0.05
mass% P in the as-rolled specimens, whereas for the sample annealed at 780˚C, both σ0.2 and
σB decrease with P contents up to 0.05 mass%. When the quantity of P added to the annealed
specimen exceeds 0.05 mass%, however, both σ0.2 and σB increase monotonically. Experiments
with high purity Fe-based alloys containing 0.21 or 0.22 mass% P and up to 0.95 mass% Ni
have been performed by [1988Sai] in order to clarify the mechanism of reduction of the
intergranular fracture (IGF) of Fe-P alloys owing to the presence of nickel. Among the factors
affecting IGF and the ductile-to-brittle transition temperature (DBTT), the degree of phos-
phorus segregation and the grain size are independent of the bulk nickel concentration. Two
other factors are the plasticity of the matrix and the interaction between nickel and phospho-
rus. It was shown that the solution-softening effect of Ni is the mechanism reducing the
susceptibility of the Fe-P alloys to IGF. [1997Gao] reported that the thermostability of
electrodeposited amorphous Fe-Ni-P alloys increased with increasing Fe content. According
6 10 Fe–Ni–P
to the data of [2001Wan], the microhardness of ternary Fe-Ni-P electroless alloy deposits
increased when the heat treatment temperature was 400˚C or below, and was shown to be
related to the precipitation of Ni3P- and Fe3P-based phases within the Fe-Ni solid solution
matrix.
Investigations of the magnetic properties of (Fe1–xNix)2P solid solutions were carried out
by [1969Fru, 1969Rog], revealing evidence that the substitution of nickel by iron produces a
similar sharp increase in Curie temperature, which reaches a maximum of 342 K at x ≈ 0.08,
decreasing rapidly with larger x up to 100 K at x = 0.5. The saturation magnetization was not
measured. Later, magnetoelastic properties and the electronic structure of (Fe1–xNix)2P solid
solutions were studied by [2004Zac]. The values of local magnetic moments as derived from
neutron diffraction refinements and the total saturation magnetization were found to be in
fair agreement with total energy coherent potential approximation (KKR-CPA) calculations. It
was suggested that strong electron polarization at the Fermi level (P ~ 90 %) as established
theoretically for the (Fe1-xNix)2P compounds having the smallest nickel content, may be
responsible for the marked magnetoelastic phase transition, as observed, for example, in
(Fe0.975Ni0.025)2P.
Miscellaneous
Ternary diffusion coefficients in the (αFe) and (γFe) phases at 1200, 1100, 1000 and 900˚C
were determined by [1973Hey]. Cooling rates for twelve group IVA iron meteorites have
been determined by [1979Mor] using a new ternary Fe-Ni-P system model that simulates the
growth of the Widmanstaetten structure. It was proposed that the group IVA irons were
accommodated at various depths in an asteroid-sized body. The diffusion of nickel in
amorphous and crystalline Fe65.5Ni17P17.5 and Fe48.5Ni34P17.5 (units were not specified) alloys
has been studied by [1983Gru] using the radioisotope absorption-kinetic method. The
structural state is found to have an appreciable effect on diffusion in the amorphous alloy.
Annealing at temperatures above the crystallization point of the amorphous alloy, results in
the Ni diffusion slowing down. On the basis of the results obtained, it was supposed that the
diffusibility of metalloid atoms is much slower and that of metal atoms is more rapid in
amorphous alloys than in ordinary alloys. The diffusivity of Ni in Fe-Ni-P martensite was
determined by [1981Rom] in the temperature range 700 to 300˚C using EMPA and STEM
techniques. The lattice and grain boundary tracer diffusion coefficients in the Fe98.87Ni1.03P0.1
(at.%) alloy were measured by [1983Mat] in the temperature range from 659 to 882˚C. It was
concluded that the effect of nickel on the lattice and grain boundary tracer diffusion coeffi-
cients, as compared to binary Fe-P alloys, is small. The equilibrium “intergranular segregation
extent (ISE)” of phosphorus in Fe-Ni-P alloys was calculated in [1983Shi] using a model
analogous to Ono’s discrete lattice approach based on a simple regular solution model
assuming only nearest neighbor interactions. The ISE of phosphorus was defined as the
monolayer thickness of a P-enriched bulk region adjacent to the grain boundary, where a
normalized concentration of P is greater than one-tenth of that of the grain boundary. The
nucleation of intergranular ferrite from austenite in Fe-Ni-P alloys containing 5 to 10 mass%
Ni and up to 1 mass% P was studied by [1984Nar1] with a view to understand the develop-
ment of the Widmanstaetten structure in iron meteorites. A series of alloy compositions were
chosen to simulate the constitution of iron meteorites. In the investigated alloys, intergranular
ferrite precipitates were found to have a rod-like morphology, intergranular ferrite and the
Fe–Ni–P 10 7
parent austenite have an orientation relationship close to that given by Kurdjumov-Sachs and
phosphides act as nucleation sites for intergranular ferrite precipitation. At the same time,
ferrite doesn’t precipitate in the absence of P. The authors of this work also used analytical
electron microscopy (AEM) techniques to study the growth of intergranular ferrite in their
specimens; the results were presented in [1984Nar2]. It was shown that the growth kinetics are
dictated by the bulk diffusion of nickel in austenite; full equilibrium takes place during
intergranular ferrite growth with full partitioning of Ni and P between austenite and ferrite,
and chemical equilibrium occurs at the (αFe)/(γFe) interface in both phases. A numerical
model to simulate ferrite growth was developed based on equilibrium growth considerations.
The Ni concentrations and precipitate sizes predicted by the model agree well with those
measured by AEM techniques in the experimental alloys. The computer model has been
extended to predict the thermal histories of iron meteorites and their parent asteroidal bodies.
In [1986Dea], the AEM technique was used to measure the interdiffusion coefficients in the
Fe-Ni-P system (0.2 mass% P, up to 30 mass% Ni) between 925 and 610˚C in austenite and
between 850 and 550˚C in ferrite. The results obtained were compared with the data obtained
using binary Fe-Ni specimens. The possibilities of using atom probe tomography characteri-
zation of solute segregation to dislocations and interfaces were reported in [2006Mil]. A
neutron irradiated Fe98.375Ni1.6P0.025 (at.%) alloy and a neutron irradiated beltline weld
from the Midland reactor were the subject of the investigation. It was concluded that this
technique is best applied to materials with high dislocation densities due to the relatively
limited volume of analysis. The level of solute segregation at the interfaces of nanometer scale
precipitates may also be estimated using this technique.
. Table 1
Investigations of the Fe-Ni-P Phase Relations, Structures and Thermodynamics

[1931Vog] Melting in Pythagor’s crucibles, thermal < 1500˚C, the Fe-Fe2P-Ni5P2-Ni region
analysis, optical microscopy, chemical
analysis
[1948Now] XRD (X-ray diffraction) The Fe3P-Ni3P and Fe2P-Ni2P sections
[1965Kan1] Electrolytical isolation, XRD, chemical 2.5 mass% P in the alloys
analysis
[1965Kan2] XRD, chemical analysis 1000, 900, 800˚C, 1 at.% Ni or 10 to 14
mass% Ni
[1966Buc] Sintering in hydrogen, XRD, Electron ≤ 1100˚C, ≤ 40 mass% Ni, ≤ 10 mass% P
Microprobe Analysis (EMPA)
[1968Doe] XRD Fe2NiP
[1969Fru] XRD (Seeman-Bohlin camera), Mössbauer The Fe2P-Ni2P section
spectroscopy
[1969Rog] XRD (Seeman-Bohlin camera), Mössbauer The Fe2P-Ni2P section
spectroscopy

8 10 Fe–Ni–P

[1969Sch] Equilibrium P (vapor) – molten Fe with Ni 1550˚C

additions
[1970Doa] EMPA, XRD, quantitative metallography 1100-550˚C, ≤ 16.5 mass% P, induction
melting, heat treatment, quenching,
[1970Doe] XRD Fe2NiP
[1970Spr] Heat treatment, XRD 25 at.% P
[1973Mae] XRD on powder, Mössbauer 900˚C, the Fe2P-Ni2P section
spectroscopy
[1975Nor] Optical microscopy, EMPA, diffusion 975-750˚C, the Fe3P-Ni3P section
couples technique
[1977Got] XRD The Fe3P-Ni3P section
[1979Yam] Melting, Knudsen cell-mass spectrometry εPNi in liquid phase, 1600˚C,
≤ 10 mass% Ni
[1980Rom] Induction melting, annealing, EMPA, STEM 700-300˚C, < 60 mass% Ni
[1981Maa] XRD, Mössbauer spectroscopy FeNiP
[1982Sas] XRD, EMPA, sealed-tube method 700˚C, phosphorus vapor at 0.1 MPa
[1983Yam] Melting, Knudsen cell-mass spectrometry 1600˚C
[1984Ban] Transportation method εPNi in liquid phase, 1400˚C, ≤ 28.3
mass% Ni
[1984Nar2] Analytical electron microscopy (AEM), ≤ 9.72 mass% Ni, ≤ 0.75 mass% P
isothermal and nonisothermal heat
treatments
[1986Fje] XRD on powder, neutron diffraction 50 at.% P, 0 to 15 at.% Ni
[1986Reu] Physico-chemical analysis techniques < 400˚C, < 58 mass% Ni
[2000Jei] XRD on single crystal, energy-dispersive X- FexNi1–xP3 (x = 0, 0.455, 0.555)
ray analysis (EDX)
[2000Wan] Electroless plating 38 at.% Fe
[2001Wan] Electroless plating, X-ray diffraction 700-200˚C
[2003Mor1] EMPA (Cameca SX 100), XRD (single crystals Fe1.7Ni1.3P (a Schreibersite extracted
technique) from Canyon Diablo meteorite)
technique) from Morasko meteorite)
technique) from Orange River meteorite)

Fe–Ni–P 10 9

[2004Zac] Heat treatment, XRD, Rietveld profile 420-80 K, (Fe1–xNix)2P (x = 0.015, 0.02,
refinement 0.025, 0.25)
[2005Gei] TEM, TEM-EDX, X-ray diffraction, The Fe3P-Ni3P section
electron backscatter diffraction (EBSD)
[2006Gao] DTA, DSC, X-ray diffraction ≲ 25 at.% P
. Table 2
Pearson
αδ, (αFe, δFe) cI2 dissolves 4.55 at.% P at 1048˚C, and 4 at.%
Im3m P at 1000˚C [2002Per], dissolves 4.5 at.% P
W at 1 at.% Ni, 1000˚C [1965Kan2]
(δFe) (h) a = 293.15 pure Fe, at 1360˚C [V-C2]
1538 - 1394 dissolves 3.8 at.% Ni at 1517˚C [2008Kuz]
(αFe) (r) (ferrite) a = 286.64 pure Fe, at 20˚C [V-C2]
< 912 dissolves 4.6 at.% Ni at 495˚C [2008Kuz]
γ, (γFe,Ni), cF4
(γFe) (austenite) Fm3m a = 364.68 pure Fe, 912˚C [Mas2]
1394 – 912 Cu dissolves 0.56 at.% P at 1150˚C [2002Per]
dissolves 1 mass% P at 10 to 14 mass% Ni,
1000˚C [1965Kan2]
dissolves 0.3 mass% P at 10 to 14 mass%
Ni, 800˚C [1965Kan2]
(Ni) a = 352.40 pure Ni, 25˚C [V-C2]
< 1455 dissolves 0.32 at.% P at 870˚C [Mas2]
FeNi3 cP4 a = 355.50 ordered γ(Fe,Ni) [1988Rag]
Pm3m
AuCu3
α2, martensite tI4 - metastable, from quenched austenite
I4/mmm [Mas2]
α2, martensite
γ´, FeNi3 cP4 a = 355.25 63 to 85 at.% Ni
< 517 Pm3m [1991Swa, 2008Kuz]
AuCu3

10 10 Fe–Ni–P
Pearson
FeP oP8 a = 519.3 [2002Per]

≲ 1370 Pna21 b = 579.3
MnP c = 309.9
Fe1–xNixP a = 519 to 510.5 x = 0 to 0.3, room temperature, slowly
b = 579.5 to 569.7 cooled samples [1986Fje]
c = 309.5 to 325.3
a = 510.5 to 517 x = 0.3, T = 25 to 800˚C [1986Fje]
b = 569.7 to 578.2
c = 325.2 to 327
FeP2 oP6 a = 497.29 66 to 67 at.% P [2002Per]
Pnnm b = 565.68
FeS2 c = 272.30
(marcasite)
FeP4 mP30 a = 461.9 80 at.% P [2002Per]
P21/c b = 1367.0
FeP4 c = 700.2
β = 101.48˚
βNi5P2 (h) - - 28.6 at.% P [Mas2]
1170 - 1000
αNi5P2 (r) hP168 a = 1322.0 ± 0.2 28.6 at.% P. Annealed at 700˚C
< 1025 P3 c = 2463.2 ± 0.2 [1988Rag]
αNi5P2
βNi12P5 (h) - - 29.4 at.% P [Mas2]
1125 - 1000
αNi12P5 (r) tI34 a = 864.6 29.4 at.% P [1988Rag]
< 1025 I4/m c = 507.0
αNi12P5
M3P, (Fe1–xNix)3P tI32 0 ≤ x ≤ 1 [1931Vog, 1948Now]
I4 a = 910.8 x = 0 [2002Per]
Ni3P c = 445.5
Fe3P a = 904.0 x = 0.33 [1968Doe, 1970Doe]
< 1166 c = 446.2
Ni3P a = 895.4 x = 1 [1988Rag]
< 970 c = 438.6

Fe–Ni–P 10 11
Pearson
M2P, (Fe1–xNix)2P hP9 0≤x≤1

Fe2P
P62m a = 586.6 ± 0.2 x = 0 [1969Fru, 1969Rog]
< 1370 Fe2P c = 345.3 ± 0.3
a = 584.07 x = 0.25, T = 10 K [2004Zac]
c = 344.4
a = 584.46 x = 0.25, T = 17˚C [2004Zac]
c = 345.75
Ni2P a = 586.4 ± 0.4 x = 1 [1969Fru, 1969Rog]
< 1100 c = 338.6 ± 0.4
Ni5P4 hP36 a = 678.9 44.4 at.% P [Mas2, V-C2]
P63mc c = 1098.6 single crystal data, annealed at 800˚C
Ni5P4
Ni1.22P - - 45 at.% P [Mas2, 1988Rag]
NiP oP16 a = 605.0 50 at.% P [Mas2, V-C2]
≲ 850 Pcba c = 488.1 single crystal data, annealed at 850˚C
NiP c = 689.0
NiP2 mC12 a = 636.6 66.7 at.% P [Mas2, V-C2]
C2/c c = 561.5 single crystal data, annealed at 900˚C and
NiP2 c = 607.2 slowly cooled
β = 126.22˚
NiP3 cI32 a = 780.8 75 at.% P [Mas2]
Im3 single crystal data [2000Jei]
FexNi1–xP3 CoAs3 a = 775.2 ± 0.2 x = 0.495 [2000Jei]
. Table 3
Composition (at.%)
Reaction T [˚C] Type Phase Fe Ni P
L + αδ Ð γ + M3P 1000 ± 5˚C U L 69.4 10.0 20.6

αδ 88.2 7.0 4.8
γ 88.2 9.3 2.5
M3 P 66.9 6.7 26.4

12 10 Fe–Ni–P
Composition (at.%)
Reaction T [˚C] Type Phase Fe Ni P
L Ð M2P + Ni5P2 ~ 990 e6 L ~ 22.7 ~ 47.0 ~ 30.3

L + M3P + Ni5P2 ~ 980 max L ~ 18.7 ~ 56.3 ~ 25.0
L Ð M2P + Ni5P2 + M3P ~ 970 E L ~ 23.5 ~ 49.0 ~ 27.5
. Table 4
Investigations of the Fe-Ni-P Materials Properties
[1966Buc] Vickers hardness tests Hardness

[1969Fru] Thermomagnetic balance technique Magnetic moments, Curie
temperatures, magnetic-transition
temperatures
[1969Rog] Thermomagnetic balance technique Magnetic moments, Curie
temperatures, magnetic-transition
temperatures
[1977Got] Thermomagnetic balance, sample vibrating Magnetic transition point, saturation
magnetometer techniques magnetic moment
[1983Mat] Residual activity method Curie temperature
[1986Fje] Differential scanning calorimetry (Mettler TA Magnetic susceptibility
3000 system), conventional Faraday balance
[1987Ina] Normal method (for thermal expansion), Tensile stress, yield strength, thermal
tensile tests expansion coefficient
[1988Sai] Charpy-type impact tests, tensile tests, optical Toughness, yield stress, grain size,
microscopy, TEM dislocation configuration
57
[1990Res] Fe Mössbauer spectroscopy, magnetic Hyperfine field distributions,
measurements magnetic phase diagram
[1997Gao] Differential scanning calorimetry, positron Magnetic properties, structure
annihilation, electronic integrating instrument defects, thermostability
techniques
[2000Wan] Corrosion resistance tests Corrosion resistance
[2001Wan] Mechanical tests Microhardness
[2004Zac] Neutron diffraction, magnetic susceptibility χac susceptibility, ferromagnetic-
measurements at high pressure (up to 1.5 paramagnetic phase transition
GPa)
[2006Gao] Improved four-ball wear tester Wear resistance

Fe-Ni-P. Partial Reaction scheme
Fe–Ni–P 10 13
. Fig. 1

14 10 Fe–Ni–P
. Fig. 2
Fe-Ni-P. Partial liquidus surface projection

Fe–Ni–P 10 15
. Fig. 3
Fe-Ni-P. Partial isothermal section at 1100˚C

16 10 Fe–Ni–P
. Fig. 4

Fe–Ni–P 10 17
. Fig. 5

18 10 Fe–Ni–P
. Fig. 6

Fe–Ni–P 10 19
References
[1931Vog] Vogel, R., Baur, H., “About the Iron-Nickel-Phosphorus Ternary System” (in German), Arch.
Eisenhuettenwes., 5(5), 269–278 (1931/1932) (Morphology, Phase Diagram, Phase Relations, Experi-
mental, 10)
[1948Now] Nowotny, H., Henglein, E., “Study of Ternary Alloys with Phosphorus” (in German), Monatsh. Chem.,
79, 385–393 (1948) (Crys. Structure, Experimental, Review, 18)
[1949Jae] Jaenecke, E., “Ni-Fe-P” (in German) in “Kurzgefasstes Handbuch aller Legierungen”, Winter Verlag,
Heidelberg, 648–649 (1949) (Phase Diagram, Phase Relations, Review, 1)
[1965Kan1] Kaneko, H., Nishizawa, T., Tamaki, K., “Phosphide-Phases in Ternary Alloys of Iron, Phosphorous and
Other Elements” (in Japanese), Nippon Kinzoku Gakkai-shi, 29(2), 159–165 (1965) (Morphology, Phase
Diagram, Phase Relations, Experimental, Review, 24)
[1965Kan2] Kaneko, H., Nishizawa, T., Tamaki, K., Tanifuji, A., “Solubility of Phosphorus in α- and γ-Iron”
(in Japanese), Nippon Kinzoku Gakkai-shi, 29(2), 166–170 (1965) (Phase Relations, Experimental,
Review, 20)
[1966Buc] Buchwald, V.F., “The Fe-Ni-P System and the Structure of Iron Meteorites”, Acta Polytech. Scand., (51),
1–46 (1966) (Crys. Structure, Morphology, Phase Diagram, Experimental, Mechan. Prop., 34)
[1968Doe] Doenitz, F.D., “Crystal Structure of the Meteorite Mineral Rhabdite” (in German), Naturwissenschaf-
ten, 55(8), 387–387 (1968) (Crys. Structure, Experimental, 4)
[1969Fru] Fruchart, R., Roger, A., Senateur, J.P., “Crystallographic and Magnetic Properties of Solid Solutions of
the Phosphides M2P, M = Cr, Mn, Fe, Co, and Ni”, J. Appl. Phys., 40(3), 1250–1257 (1969) (Crys.
Structure, Experimental, Magn. Prop., 45)
[1969Rog] Roger, A., Senateur, J.-P., Fruchart, R., “Crystallographic and Magnetic Properties of Solid Solutions
Among the Phosphides Ni2P - Co2P - Fe2P - Mn2P and Cr2P” (in French), Ann. Chim. (Paris), 4(2),
79–91 (1969) (Crys. Structure, Experimental, Phase Relations, Magn. Prop., 44)
[1969Sch] Schenck, H., Steinmetz, E., Gitizad, H., “Activity of Phosphorus in the Molten Iron and its Control by
Nickel, Manganese and Chromium” (in German), Arch. Eisenhuettenwes., 40(8), 597–602 (1969)
(Thermodyn., Experimental, 24)
[1970Doa] Doan, A.S., Jr., Goldstein, J.I., “The Ternary Phase Diagram Fe-Ni-P”, Metall. Trans., 1(6), 1759–1767
(1970) (Morphology, Phase Diagram, Phase Relations, Experimental, #, 19)
[1970Doe] Doenitz, F.-D., “The Crystal Structure of Meteoritic Rhabdite (Fe, Ni)3P” (in German), Z. Kristallogr.,
131(3), 222–236 (1970) (Crys. Structure, Experimental, 17)
[1970Spr] Spriggs, P.H., “An Investigation of the Variation of Lattice Parameters with Composition along the Tie-
line Ni3P-Fe3P”, Phil. Mag., 21, 897–901 (1970) (Crys. Structure, Experimental, 8)
[1973Hey] Heyward, T.R., Goldstein, J.I., “Ternary Diffusion in the α and γ Phases of the Fe-Ni-P System”, Metall.
Trans., 4(10), 2335–2342 (1973) (Morphology, Experimental, Interface Phenomena, Kinetics, 17)
[1973Mae] Maeda, Y., Takashima, Y., “Mössbauer Studies of FeNiP and Related Compounds”, J. Inorg. Nucl.
Chem., 35(6), 1963–1969 (1973) (Crys. Structure, Experimental, Electronic Structure, 12)
[1975Nor] Norkiewicz, A.S., Goldstein, J.I., “Ternary Dissolution Kinetics in the Fe-Ni-P System”, Metall. Trans.
A, 6A, 891–900 (1975) (Morphology, Phase Diagram, Phase Relations, Experimental, Interface Phe-
nomena, Kinetics, 17)
[1977Got] Goto, M., Tange, H., Tokunaga, T., Fujii, H., Okamoto, T., “Magnetic Properties of the (Fe1–xMx)3P
Compounds”, Jpn. J. Appl. Phys., 16(12), 2175–2179 (1977) (Crys. Structure, Experimental, Magn.
Prop., 16)
[1979Mor] Moren, A.E., Goldstein, J.I., “Cooling Rates of Group IVA Iron Meteorites Determined from a Ternary
Fe-Ni-P Model”, Earth Planet. Sci. Letters, 43(2), 182–196 (1979) (Morphology, Calculation, Theory)
cited from abstract
[1979Yam] Yamada, K., Kato, E., “Mass Spectrometric Determination of Activities of Phosphorus in Liquid Fe-P-
Si, Al, Ti, V, Cr, Co, Ni, Nb and Mo Alloys” (in Japanese), Tetsu to Hagane (J. Iron Steel Inst. Jap.), 65
(2), 273–280 (1979) (Thermodyn., Calculation, Experimental, Review, 40)
[1980Rom] Romig, A.D., Jr., Goldstein, J.I., “Determination of the Fe-Ni and Fe-Ni-P Phase Diagrams at Low
Temperatures (700 to 1300˚C)”, Metall. Trans. A., 11A, 1151–1159 (1980) (Crys. Structure, Morpholo-
gy, Phase Diagram, Phase Relations, Experimental, 20)
[1981Maa] Maaref, S., Madar, R., “Crystal Chemistry of M12P7 Phases in Relation with the M2P Phosphides”, J.
Solid State Chem., 40, 131–135 (1981) (Crys. Structure, Experimental, 11)

20 10 Fe–Ni–P
[1981Rom] Romig, A.D., Jr., Goldstein, J.I., “Low Temperature Phase Equilibria in the Fe-Ni and Fe-Ni-P Systems:
Application to the Thermal History of Metallic Phases in Meteorites”, Geochim. Cosmochim. Acta, 45
(7), 1187–1197 (1981) (Morphology, Experimental, Interface Phenomena, Kinetics, 22)
[1982Sas] Sasaki, Y., Iida, Y., Yokoo, A., Ueda, S., “High-temperature Phosphidation of Iron-Nickel Alloys by
Phosphorus Vapor” (in German), Z. Anorg. Allg. Chem., 487, 232–240 (1982) (Crys. Structure,
Morphology, Experimental, Interface Phenomena, Kinetics, 11)
[1983Gru] Gruzin, P.L., Urytu, S.G., “Diffusion of Nickel in the Amorphous Alloy Iron-Nickel-Phosphorus” (in
Russian), Ukr. Fiz. Zhurnal, (2), 255–258 (1983) (Morphology, Experimental, Interface Phenomena,
Kinetics, 3)
[1983Mat] Matsuyama, T., Hosokawa, H., Suto, H., “Tracer Diffusion of P in Iron and Iron Alloys”, Trans. Jpn.
Inst. Met., 24(8), 589–594 (1983) (Morphology, Experimental, Interface Phenomena, Kinetics, Magn.
Prop., 14)
[1983Shi] Shinoda, T., “Theoretical Estimates of Phosphorus Concentration Profiles Across Grain Boundaries in
Fe-P and Fe-Ni-P Systems”, Acta Metall., 31(12), 2051–2062 (1983) (Morphology, Calculation, Theory,
Interface Phenomena, 15)
Activity Coefficient of P in Liquid Iron”, Trans. Iron Steel Inst. Jpn., 23(1), 51–55 (1983) (Thermodyn.,
Calculation, Experimental, 16)
[1984Ban] Ban-Ya, S., Maruyama, N., Kawase, Y., “Effects of Ti, V, Cr, Mn, Co, Ni, Cu, Nb, Mo and W on the
Activity of Phosphorus in Liquid Iron” (in Japanese), Tetsu to Hagane, 70(1), 65–72 (1984) (Thermo-
dyn., Calculation, Experimenta1, Review, 21)
[1984Nar1] Narayan, S., Goldstein, J.I., “Nucleation of Intergranular Ferrite in Fe-Ni-P Alloys”, Metall. Trans. A.,
15A, 861–865 (1984) (Morphology, Experimental, 16)
[1984Nar2] Narayan, S., Goldstein, J.I., “Growth of Intergranular Ferrite in Fe-Ni-P Alloys”, Metall. Trans. A., 15A,
867–874 (1984) (Morphology, Phase Relations, Experimental, Interface Phenomena, Kinetics, 16)
[1986Dea] Dean, D.C., Goldstein, J.I., “Determination of the Interdiffusion Coefficients in the Fe-Ni and Fe-Ni-P
Systems below 900˚C”, Metall. Trans. A, 17A(7), 1131–1138 (1986) (Morphology, Experimental,
Interface Phenomena, Kinetics, 22)
[1986Fje] Fjellvag, H., Kjekshus, A., “Solid Solution Phases with MnP Type Structure: T1–tNitP (T = Ti-Co)”,
Acta Chem. Scand., Ser. A, A40, 8–16 (1986) (Crys. Structure, Phase Relations, Experimental, Magn.
Prop., 43)
[1986Reu] Reuter, K.B., “Determination of the Iron-Nickel and Iron-Nickel-Phosphorus (Sat.) Phase Diagrams
below 400˚C”, Ph. D. Thesis, Lehigh Univ., 1–309 (1986) (Phase Diagram, Experimental) as quoted by
[1988Rag]
[1987Ina] Inaba, M., Teshima, K., “Effects of Phosphorus and Sulfur on Thermal Expansion and Mechanical
Properties of Fe-36Ni”, J. Mater. Sci. Letters, 6, 727–728 (1987) (Morphology, Experimental, Mechan.
Prop., Phys. Prop., 9)
[1988Rag] Raghavan, V., “The Fe-Ni-P System” in “Phase Diagrams of Ternary Iron Alloys”, Indian Inst. Met.,
Calcutta, 3, 121–137 (1988) (Crys. Structure, Phase Diagram, Phase Relations, Assessment, Re-
view, #, 16)
[1988Sai] Saito, N., Abiko, K., Kimura, H., “Reduction of Intergranular Fracture in Fe-P Alloys by the Addition
of Nickel”, Mater. Sci. Eng. A., 102, 169–174 (1988) (Morphology, Experimental, Interface Phenomena,
Mechan. Prop., 10)
[1990Gus] Gustafson, P., “Study of the Thermodynamic Properties of the C-Cu-Fe-P, Fe-Mo-P and Fe-Ni-P
System”, Inst. Met. Res. (IM-2549), 1–50 (1990) (Phase Diagram, Thermodyn., Calculation, 52)
[1990Jon] Jones, J.H., Malvin, D.J., “A Nonmetal Interaction Model for the Segregation of Trace Metals During
Solidification of Fe-Ni-S, Fe-Ni-P, Fe-Ni-S-P Alloys”, Metall. Trans. B, 21B, 697–706 (1990) (Theory,
Thermodyn., 12)
[1990Res] Ressler, L., Rosenberg, M., “Magnetic Moments and Magnetic Transitions in the Low Iron
Concentration Range of the Amorphous FexNi80–xP20 Alloys”, J. Magn. Magn. Mater., 83(1-3),
343–344 (1990) (Morphology, Experimental, Magn. Prop., 9) cited from abstract
[1991Swa] Swartzendruber, L.J., Itkin, V.P., Alcock, C.B., “The Fe-Ni (Iron-Nickel) System”, J. Phase Equilib., 12,
288–312 (1991) (Crys. Structure, Phase Diagram, Thermodyn., Assessment, *, 255)
(China), 29(12), B527–B532 (1993) (Thermodyn., Phase Relations, Calculation, Theory, 7)

Fe–Ni–P 10 21
[1997Gao] Gao, C.H., Zhou, B.Y., “Effects of the Composition of Electrodeposited Fe-Ni-P Alloy on the
Thermostability and Magnetic Properties”, J. Mater. Sci. Technol., 13(2), 137–140 (1997) (Morphology,
Experimental, Phys. Prop.) cited from abstract
[1998Mie] Miettinen, J., “Approximate Thermodynamic Solution Phase Data for Steels”, Calphad, 22(2), 275–300
(1998) (Phase Diagram, Phase Relations, Thermodyn., Assessment, Calculation, 98)
[2000Jei] Jeitschko, W., Foecker, A.J., Paschke, D., Dewalsky, M.V., Evers, Ch.B.H., Kuennen, B., Lang, A.,
Kotzyba, G., Rodewald, U.Ch., Moeller, M.H., “Crystal Structure and Properties of some Filled and
Unfilled Skutterudites: GdFe4P12, SmFe4P12, NdFe4As12, Eu0.54Co4Sb12, Fe0.5Ni0.5P3, CoP3, and NiP3”,
Z. Anorg. Allg. Chem., 626, 1112–1120 (2000) (Crys. Structure, Morphology, Experimental, 65)
[2000Wan] Wang, L., Zhao, L., Huang, G., Yuan, X., Zhang, B., Zhang, J., “Composition, Structure and Corrosion
Characteristics of Ni-Fe-P and Ni-Fe-P-B Alloy Deposits Prepared by Electroless Plating”, Surf. Coat.
Technol., 126 (2-3), 272–278 (2000) (Crys. Structure, Morphology, Experimental, Phys. Prop.) cited
from abstract
[2001Wan] Wang, L., Zhao, L., Huang, G., Yuan, X., Zhang, B., Zhang, J., “The Structure and Microhardness of
Ni-Fe-P and Ni-Fe-P-B Alloy Deposits Prepared by Electroless Plating”, Plating & Surface Finishing,
88(6), 92–95 (2001) (Crys. Structure, Morphology, Experimental, Mechan. Prop.) cited from abstract
[2002Chu] Chuang, M.-S., Lin, S.-T., “Effect of Phosphorous Addition on the Grain Growth of Fe-50 wt.% Ni
Alloys”, Scr. Mater., 47(5), 321–326 (2002) (Morphology, Thermodyn., Experimental, Interface Phe-
nomena, Kinetics, 12)
[2002Per] Perrot, P., Batista, S., Xing, X., “Fe-P (Iron-Phosphorus)”, MSIT Binary Evaluation Program, in MSIT
Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services GmbH, Stuttgart; Docu-
ment ID: 20.16107.1.20, (2002) (Crys. Structure, Phase Diagram, Phase Relations, Thermodyn.,
Assessment, Phys. Prop., #, 23)
[2003Cha] Chabot, N.L., Jones, J.H., “The Parameterization of Solid Metal-Liquid Metal Partitioning of
Siderophile Elements”, Meteor. Planet. Sci., 38(10), 1425–1436 (2003) (Thermodyn., Experimental,
[2003Mor1] Moretzki, O., Doering, Th., Geist, V., Morgenroth, W., Wendschuh, M., “Crystal Structure of Iron
Nickel Phosphide, Fe1.7Ni1.3P, a Schreibersite Extracted from Canyon Diablo Meteorite”, Z. Kristallogr.
NCS, 218(4), 391–392 (2003) (Crys. Structure, Experimental, 5)
Nickel Phosphide, Fe1.65Ni1.35P, a Rhabdite Extracted from Morasko Meteorite”, Z. Kristallogr. NCS, 218
(4), 393–394 (2003) (Crys. Structure, Experimental, 5)
Nickel Phosphide, Fe1.8Ni1.2P, a Schreibersite Extracted from Orange River Meteorite”, Z. Kristallogr.
NCS, 218(4), 395–396 (2003) (Crys. Structure, Experimental, 5)
[2004Zac] Zach, R., Tobola, J., Sredniawa, B., Kaprzyk, S., Casado, C., Bacmanm, M., Fruchart, D., “Magneto-
elastic Properties and Electronic Structure Analysis of the (Fe1–xNix)2P System”, J. Alloys Compd., 383,
322–327 (2004) (Crys. Structure, Calculation, Experimental, Electronic Structure, Magn. Prop., 17)
[2005Gei] Geist, V., Wagner, G., Nolze, G., Moretzki, O., “Investigations of the Meteoritic Mineral (Fe,Ni)3P”,
Cryst. Res. Technol., 40(1-2), 52–64 (2005) (Crys. Structure, Morphology, Experimental, Review,
Electronic Structure, 41)
[2006Gao] Gao, C.H., “Stability of Electrodeposited Amorphous Ni-Fe-P Alloys”, Trans. Nonferrous Met. Soc. of
China, 16(6), 1325–1330 (2006) (Morphology, Phase Relations, Thermodyn., Experimental, Mechan.
Prop.) cited from abstract
[2006Mil] Miller, M.K., “Atom Probe Tomography Characterization of Solute Segregation to Dislocations and
Interfaces”, J. Mater. Sci., 41, 7808–7813 (2006) (Morphology, Experimental, 21)
Structure, Phase Diagram, Phase Relations, Assessment, #, 41)
(1990)

Fe–Ni–S 11 1
Iron – Nickel – Sulphur

Olga Fabrichnaya, Vasyl Tomashyk, Artem Kozlov
Introduction
Phase relations in the Fe-Ni-S ternary system are very important for geology as well as for
metallurgy because phases found in this system are constituents of many ores [1991Tay]. The
mineral phases (pyrrhotite, pyrite, pentlandite) in this system are both geologically wide-
spread and economically important [1974Vau, 2004Dis]. This system is very complicated and,
therefore, complex reactions occur in sulfide ores as they cool [1971Gra]. According to
geophysical data, the core of the Earth consists of Fe-Ni alloy containing a light element
(most probably sulphur). Therefore properties of Fe-Ni-S solid and liquid alloys are important
for geophysical interpretations of seismic data [1997Nas]. The Fe-Ni-S alloys are the consti-
tuents of condrites and other meteorites [1998Ma]. The distribution of elements between solid
and liquid metal helps to explain conditions of the formation of meteorites and terrestrial
planet and therefore to explain some features of evolution of the solar system [1990Jon,
2003Cha].
The considerable literature on this ternary system has been reviewed in the publications of
[1943Haw, 1949Jae, 1963Kul1, 1964Kul, 1969Kul, 1970Sug, 1981Fit, 1982Hsi, 1988Rag,
1989Bar, 1989Bat, 2004Rag, 2004Wal2, 2006Rag].
Many phases in the Fe-Ni-S system were found in nature as minerals. The ternary phases
(FexNi1–x)S2, in which the Fe/Ni ratio is ≈1 (bravoite), FeNi2S4 (violarite) and (Fe9–xNix)9S8
(pentlandite) are formed in the Fe-Ni-S ternary system [1964Kul]. However, later it was found
that violarite is an end-member of the solid solution FeNi2S4-Ni3S4 with the spinel structure
[1971Cra]. It was proved by [1963Cla] that bravoite is stable at temperatures below 137˚C, at
higher temperatures it decomposes to pyrite and vaesite. Many experimental investigations
were performed to study crystal structure and compositions of minerals from natural deposits
[1955Eli, 1963Kul2, 1971Gra, 1972Har, 1972Nic, 1973Hal, 1973Raj].
According to the data of [1955Van] and [1957Van] FeNi4S5 is formed in the Fe-Ni-S
ternary system but Fe2Ni3S4 which was obtained by [1930Vog, 1938Ura] was not found. None
of these compounds was confirmed in the later studies. The phase (Fe0.66Ni0.34)2S, was
detected to form at very reducing conditions by [1961Stu].
A liquidus surface of this system was constructed by [1930Vog, 1938Ura, 1955Van,
1964Kul, 1983Van]. It was found that Fe1–xS and Ni1–xS form a continuos series of solid
solutions at temperatures above 300˚C [1961Nis, 1974Vau, 1976Kas, 1981Oht, 1983Van].
Isothermal sections of the Fe-Ni-S ternary system were constructed at 1100, 1000, 900, 800,
700, 600, 500, 460, 400, 300, 250 and < 135˚C [1947Lun, 1956Kul, 1960Cla, 1963Cla,
1963Kul1, 1964Kul, 1967Nal, 1968Cra, 1970She, 1971Gra, 1973Cra, 1973Mis2, 1984Bee,
1978Len, 1998Kar, 1998Ma, 2000Uen, 2001Sin1, 2006Sin]. Some temperature - composition
sections were constructed by [1930Vog, 1938Ura, 1955Van, 1956Kul, 1957Van, 1964Kul,
1966Nal, 1970She, 1971Cra, 1976Chi].

2 11 Fe–Ni–S
The mutual solubility of FeS2 and NiS2 was investigated by [1962Kle]. The reaction
Ni3S2+2Fe Ð 2FeS+3Ni takes place at 1200˚C [1976Gul]. FeS and Ni3S2 form the pentlandite
solid solution (τ1) and Ni dissolves in Fe. According to the data of [1979Sha] iron interacts
with Ni3S2 on heating forming Fe1–xS and (Fe1–xNix)3+yS2 solid solutions and Fe-Ni solid
solution at 600˚C. [1976Chi] studied reaction of Fe and Ni3S2 at 1100˚C and observed
formation of Fe1–xS and Fe-Ni solid solution.
The solubility and diffusion of S in the Fe-Ni alloys was studied by [1982Net, 1983Net1,
1983Net2] by radiotrace method. In several works [1981Mar, 1984Mar1, 1984Mar2] the role
of sulfur in the dissolution and passivation of Fe-Ni alloy was investigated using radiotrace,
electrochemical method and X-ray photoelectron spectroscopy.
Thermodynamic properties of the solid and liquid alloys in the Fe-Ni-S ternary system
were investigated by [1955Cor, 1960Alc, 1968Chm, 1969Ban, 1969Vai, 1970Khe, 1970Vay,
1972Bye, 1972Vay, 1973Buz, 1973Ven, 1974Khe, 1974Sig, 1981Fit, 1984Khe, 1989Bar,
1998Kon, 1999Kon, 2003Kos].
Thermodynamic modelling in the Fe-Ni-S system was performed by [1983Chu1,
1983Chu2, 1987Hsi1, 1987Hsi2, 1987Hsi3] using associate model for liquid and by
[1999Kon, 2004Wal2, 2006Wal2] using modified quasichemical model for liquid. [1991Tay]
presented a thermodynamic description for the Fe-Ni-S system with the liquid phase described
by a two-sublattice model. Calculated isothermal section at 400˚C was presented by [1991Tay].
Magnetic properties of the phases in the Fe-Ni-S ternary system were investigated by
[1930Vog, 1961Nis, 1970Kno, 1974Vau, 1976Kas, 1976Kno, 1977Nis, 1981Oht].
Table 1 lists the numerous experimental works on phase equilibria, crystal structure and
thermodynamics of the Fe-Ni-S system.
Binary Systems
The phase diagrams of the Fe-S and Fe-Ni systems are accepted from the MSIT evaluations of
[2008Fer] and [2008Kuz], respectively. At temperatures below 315˚C several superstructures of
the NiAs type was reported [2008Fer]. The Ni-S system is accepted from the thermodynamic
assessment of [2004Wal1] and [2006Wal1]. The phase diagram presented in [2006Wal1] is in
agreement with [Mas2] except for the low temperature part, where the Ni9S8 phase was
considered by [2004Wal1, 2006Wal1] based on data of [1987Fle] and [1994Sto]. The separa-
tion of the β phase to β1 and β2 was not taken into account in [2004Wal1], but in the later work
of [2006Wal1, 2006Wal2] two different β phases are considered.
Solid Phases
The crystallographic data for solid phases are listed in Table 2.
The ternary system Fe-Ni-S is dominated by ternary solid solutions. At high sulfur
content, two solid solutions are formed based on pyrite (βFeS2) and vaesite (ηNiS2) with a
limited mutual solubility. These solid solutions have the same structure, but they never join in
one continuous solution. [1962Kle] found a quite large mutual solubility of ηNi2S and βFe2S.
However later it was indicated by [1963Cla] that these values are too high being influenced by
the metastable conditions. Also in this section, a low temperature Fe0.5Ni0.5S2 (bravoite) phase

Fe–Ni–S 11 3
exists which was found to decompose into a mixture of NiS2 and FeS2 at a temperature of
137˚C according to [1963Cla, 1977Nis].
The monosulfides γFe1–xS (pyrrhotite) and δNi1–xS (millerite) form a continuous solid
solution (mineral pyrrhotite) [1961Nis, 1981Oht, 1983Van]. However, continuous solid solu-
tion Fe1–xNixS1+y exists at the temperatures above 300˚C and at a lower temperature a
miscibility gap appears [1973Mis2, 1973Cra]. Below 283˚C Ni-rich monosulfide decomposes
to form FexNi3–xS4 (polydymite) and the low temperature millerite phases [1973Cra]. The
c-axis lattice parameter of the Fe1–xNixS solid solution decreases as x increases [1976Kas]. This
variation is divided into two regions, one where the c-axis lattice parameter decreases steeply
with increasing x (0 ≤ x ≤ 0.50) and the other where the lattice decreases gently with a further
increase in x (0.50 ≤ x ≤ 1.0). No lattice modification was found in the Fe1–xS-Ni1–xS system
[1981Oht]. [1976Fra] studied pyrrhotite by TEM and found that ordering of metal vacancies
distinguished various superstructures of monosulfide.
In the binary Ni-S system separation of the high temperature modification of haezlewoo-
dite (β) into β1 and β2 was confirmed by experimental data [2006Wal1]. Based on these data in
the binary system, the existence of two phases β1 and β2 in the ternary system was assumed by
[2006Wal2]. However, in the ternary system, there are no experimental data about the
separation of the high temperature heazlewoodite into two phases. Therefore, in many
works only one β phase is shown in the diagrams. A considerable solubility of iron in the β
phase is supported by the experimental data [2006Wal2]. Therefore solubility of Fe in both β
phases was assumed by [2006Wal2].
The violarite solid solution extends toward Ni rich compositions with decrease of temper-
ature and becomes a continuous solid solution FexNi3–xS4 at 356˚C [1971Cra]. At a tempera-
ture of 461 ± 3˚C FeNi2S4 decomposes to form Fe1–xNixS2, NixFe1–xS2 and pyrrhotite
containing Fe and Ni in the atomic ratio 1 : 2.4.
The Ni3S2 phase dissolves 1.0-1.5 mass% Fe according to [1976Chi, 1976Gul].
The solubility of S in the Fe-Ni alloys at 950-1250˚C and at p(H2S)/p(H2) ratios from
4·10–4 to 8·10–4 corresponds to the Siverts’ law [1983Net1, 1983Net2, 1989Bar]. The solubility
of S as a function of temperature and p(H2S)/p(H2) ratio was presented in [1983Net1,
1983Net2] and [1989Bar]. The maximal solubility of S in (αFe), (γFe) and (δFe) is 0.033,
0.09 and 0.24 at.%, respectively [2008Fer], while solubility of S in solid Ni is negligible [Mas2].
A τ1 (Fe9–xNixS8+y) ternary compound (pentlandite) with a wide homogeneity range
[1947Lun] starts to appear below 610˚C [1964Kul]. Pentlandite is stable below 610˚C, where
it decomposes to (FexNi1–x)1–yS, containing less than 1.0 mass% Ni, and (FexNi1–x)3±xS2 solid
solution containing several mass% Fe [1964Kul].
According to calculations of [2004Wal2, 2006Wal2] maximal temperature of stability of
the τ1 phase is ~640˚C.
Some other ternary compounds are found in nature as minerals. Probably they are
metastable at room temperatures being formed in the conditions of the Earth interior.
Many of them decompose with the temperature increase. FeNi2S4 corresponds to the mineral
violarite. [1971Cra] noted that FeNi2S4 has a maximum thermal stability at 461 ± 3˚C and a
composition of Fe0.92Ni2.08S4. It was pointed out by [1971Cra] that violarite is an end-member
of the solid solution extended towards Ni3S4 and forming continuous solution of FeNi2S4-
Ni3S4 at 356˚C. A FeNi4S5 phase was found by [1955Van, 1957Van], however this phase was
not confirmed in any later study. [1961Stu] indicated the existence of the (Fe0.66Ni0.34)2S
compound at very reducing conditions. However, such conditions were not studied later and
the formation of this compound was never mentioned. The crystal structure of the mineral
4 11 Fe–Ni–S
FeNi29S27 is described in [1987Fle]. The structure of this orthorhombic phase contains

elements of godlevskite Ni7S6, millerite NiS and pentlandite Fe9–xNixS8+y. However, this
compound was not confirmed in further experiments.
A reaction scheme from [1982Hsi] taking into account data from [2004Kos] and corrected
according to the accepted binary systems is presented in Fig. 1. The available data for the
invariant reactions from [1982Hsi] and [2004Kos] are presented in Table 3. It should be
mentioned that the reaction scheme and the data for the invariant reactions in [1982Hsi] are
provisional and in case there are new experimental measurements we recommend to use these
new data. In the work of [1982Hsi] the high-temperature heazlewoodite is considered as one
single phase β. A three-phase monovariant reaction of the peritectic type between the β phase,
pyrrhotite and liquid was studied by directional crystallization of melt in combination with
DTA by [2004Kos]. It was found that this monovariant curve has a temperature maximum at
875˚C, what is slightly higher than assumed by [1982Hsi]. The data for this maximum are
taken from [2004Kos]. It should be mentioned that DTA measurements of [1999Sin] for the
U2 reaction are not taken into account since they disagree with most of experimental data and
calculations of [2004Wal2]; the difference in temperature for the reaction U2 reported by
[1982Hsi] and [1999Sin] is more than 200˚C. In this work we accepted temperature of
reaction U2 from [2004Wal2] equal to 800˚C.

Liquidus surface was experimentally studied by [1930Vog, 1938Ura, 1955Van, 1978Len,
1999Sin]. A wide region of liquid immiscibility extends across the S rich portion of the
Fe-Ni-S ternary system at high temperatures [1964Kul, 1983Van].
The liquidus surface was calculated by [1987Hsi2] based on experimental data on liquidus
[1978Len] and measurements of partial pressure of sulphur over the liquid phase and
pyrrhotite [1987Con, 1987Hsi2, 1987Hsi3]. The liquidus surface from the work of
[1987Hsi2] is presented in Fig. 2.
Isothermal Sections
Isothermal sections were experimentally studied in several works [1963Kul1, 1973Cra,

1987Con, 1987Hsi4, 2000Uen, 2001Sin1].
The phase relations in the S rich part of the Fe-Ni-S ternary system in the 700-750˚C
temperature range were given by [1964Kul]. The isothermal sections at 500 and 460˚C between
0 and 50 at.% S were determined by the analysis of equilibrated ternary alloys and diffusion
couples in [1984Bee]. At 500˚C the iron stabilized high-temperature modification βNi3S2 was
found. A low temperature isothermal section (< 135˚C) was studied [1971Gra].
The phase relations involving the appearance of FeNi2S4 and development of the FeNi2S4-
Ni3S4 solid solution at 500, 450, 400 and 300˚C were determined by [1971Cra]. Binary sulfides
except Fe1–xS are not in equilibrium with the iron phase in the Fe-Ni-S system at 950˚C
[1963Kan].
Fe–Ni–S 11 5
The calculated isothermal sections based on the Calphad-type assessments using quasi-
chemical model [2004Wal2, 2006Wal2] reproduce experimental data at 600-1350˚C within
uncertainty limits. The assessments based on the associate model [1987Hsi1, 1987Hsi2,
1987Hsi4] also reproduce experimental isothermal sections at 700-1350˚C, but calculations
[2004Wal2] seems to be in better agreement with experimental data. The isothermal section at
400˚C was calculated by [1991Tay]. However, none of the available assessment works present
isothermal sections at all the temperatures studied experimentally. Therefore, in the present
study isothermal sections are presented based on the available calculations and experiments.
Figures 3a to 3c present isothermal sections at 1350, 1300 and 1200˚C calculated in
[2004Wal2], respectively. Figures 4a to 4c present isothermal sections calculated by
[1987Hsi2] at 1100, 1050 and 1000˚C. Figures 5a to 5c present isothermal sections at 900,
700˚C calculated by [2004Wal2] and at 600˚C [2006Wal2], respectively. As it was mentioned
above, in [2006Wal2] two haezlewoodite phases β1 and β2 were considered. Because only
one isothermal section was calculated based on the new thermodynamic description, the other
isothermal sections are presented according to [2004Wal2]. Isothermal sections at 550, 500
and 400˚C were constructed by [1963Kul1] based on experimental results. They are in a good
agreement with later studies [1968Cra, 1970She] except for a wider homogeneity range of the
pentlandite solid solution indicated by [1968Cra, 1970She]. Figures 6a and 6b present
isothermal sections at 500 and 400˚C from [1970She] and [1968Cra], respectively. The low-
temperature phase relations at 200-300˚C were studied by [1973Cra] and [1973Mis2]. Mis-
cibility gaps were found to appear in the monosulfide solid solutions: one below 263˚C and
another at 225˚C [1973Cra]. Partial isothermal sections at 300 and 200˚C are presented in
Figs. 7a and 7b from [1973Cra] and at the temperatures below 135˚C from [1971Gra]
(Fig. 7c). Phase relations involving superstructures of NiAs [1992Gro] are not very well
defined for the Fe-S system, therefore phase relations involving solid solution at 40 mass% S
and Ni up to 7 mass% Ni being superstructure of NiAs are shown tentatively in Figs. 7a and 7b.
At the temperatures below 135˚C the bravoite phase Fe0.5Ni0.5S2 was found stable.
It should be mentioned that isothermal sections at 400, 300, 200˚C and at the temperatures
below 135˚C were slightly corrected to be consistent with accepted binary system Ni-S.
According to [1994Sto] and [2004Wal1] Ni9S8 phase was accepted to be stable, while phase
γ’Ni7S6 accepted in earlier studies (see evaluation of [Mas2]) was not considered as stable one.
Therefore γ’Ni7S6 was changed to Ni9S8 phase at low temperature sections.
The phase diagram of the FeS2-NiS2 system was experimentally studied [1963Cla, 1998Kar].
Thirteen temperature - composition sections were constructed by [1930Vog, 1938Ura,
1955Van, 1957Van]. Eleven of these sections cross the ternary system from the S corner to the
Fe-Ni binary and two others (FeS-Ni6S5, FeS-Ni3S2) travers the system from FeS to the Ni-NiS
subsystem [1955Van, 1957Van]. A section along the FeNi2S4-Ni3S4 join was determined by
[1971Cra].
[2004Wal2] calculated isopleths in the Fe-Ni-S system at the constant Fe/Ni ratios of
0.6722 and 1.0, vertical sections FeS-Ni3S2, FeS2-NiS2 and at a fixed concentration of sulfur
equal to 0.471. The section FeS-Ni3S2 was recalculated by [2006Wal2] taking into account
separation of β phase into β1 and β2. The calculated vertical sections from [2004Wal,
2006Wal2] are presented in Figs. 8a to 8c.
6 11 Fe–Ni–S
Vertical sections for Fe/Ni ratio equal to 0.6722 and 1 are not shown in present evaluation,
because [2004Wal2] took into account only fcc and bcc phases in the Fe-Ni system. Therefore
calculations of [2004Wal2] at temperatures below 600˚C are not consistent with accepted
binary Fe-Ni system. At higher temperatures fine details of phase diagram are not possible to
distinguish, because the diagrams are overloaded by experimental points.
Potential Diagrams
[1987Hsi1, 1987Hsi2, 1987Hsi4] calculated potential diagrams presenting log p(S2) vs x(Fe)/
(x(Fe)+x(Ni)) ratio at temperatures 700-1100˚C. The calculations of [1987Hsi1] at 700, 800,
900 and 1100˚C from [1987Hsi1] are presented in Figs. 9a to 9d.
Thermodynamics
The activity of S in the liquid phase (matte) was measured by [1972Bye, 1987Con] using
method of equilibration with H2 and H2S gas mixtures. However, the data of [1972Bye] and
[1987Con] do not agree very well with each other. The data of [1972Bye] give higher activity
values and they are quite scattered. In the work of [1987Con] the results obtained by
equilibration technique were confirmed by vapor pressure measurements using Knudsen
mass-spectrometer. The activities of Fe in the matte were reported in [1962Vay, 1969Vai,
1972Vay], who used the emf method. Though the discrepancy between [1962Vay] and
[1969Vai] was not explained by the authors, the data of [1969Vai] are in agreement with
[1987Con]. The calculated S activities predicted by the model of [1999Kon] are consistent
with the data of [1987Con]. The agreement between the predicted Fe activities [1999Kon] and
those reported in [1969Vai] is very good. The calculated Fe and S activity in the liquid phase in
the works of [1987Hsi2, 2004Wal2] are in good agreement with experimental results of
[1969Vai] and [1987Con]. The results of calculation [2004Wal2] for the Fe and S activity in
the liquid phase are presented in Figs. 10 and 11 and Figs. 12a to 12c.
The activity of sulfur in the pyrrhotite solid solutions at different Fe/Ni ratios and S
contents were measured by [1987Hsi4] using gas equilibration technique at 700-900˚C. The
calculated results from [1987Hsi3, 2004Wal2] are in a good agreement with experimental data.
The calculated S activity in the pyrrhotite solid solutions from [2004Wal2] are presented in
Figs. 13a to 13e.
The Gibbs energy (integral and partial) in the FeS-Ni3S2 system at 1150˚C were calculated
in [1983Chu1], activity of both components at 1200˚C were calculated in [1983Chu1,
1983Chu2] and at 1300˚C in [1987Hsi1]. Calculations of [1987Hsi1] for activity in the
FeS-Ni3S2 join are presented in Fig. 14. Activities of Fe in the Ni3S2-Fe and FeS-Ni joins at
1300˚C were calculated by [1969Vai, 1987Con, 1987Hsi1].
Isoactivities of Ni and Fe in the Fe-Ni-S system at 1300˚C were presented in the works of
[1970Vay, 1972Vay, 1974Khe] based on experimental results obtained by emf measurements.
[1987Hsi1] calculated isoactivity lines for (αFe), (αNi) and log10p(S2)1/2 in liquid and liquid+γ
regions at 1200-1400˚C.
The sulfur activity in dilute Fe-Ni liquid solutions were measured by equilibration with H2
and H2S gas mixtures at 1600˚C [1955Cor] and at 1540˚C [1960Alc]. The activity coefficient of

Fe–Ni–S 11 7
sulfur in dilute liquid Fe-Ni alloys at 1540˚C were evaluated in terms of Wagner model and
compared with experimental data of [1960Alc] in the work of [1981Fit]. Addition of Ni to Fe
has a little influence on the dissolution energy of S in Fe-Ni alloys [1989Bar]. The excess Gibbs
energy of S mixing in liquid Fe-Ni alloys at 1540˚C should be negative at the Ni rich end of the
Fe-Ni system, reaching a maximum about –2.1 kJ·(g-at)–1, but positive at the Fe rich end of
this system [1960Alc]. Ni decreases slightly the activity coefficient of S in liquid Fe [1968Chm,
1969Ban], while Fe increases activity coefficient of S in liquid Ni [1973Ven]. The first
order interaction parameter up to 20 mass% Ni is equal eNiS = – 0.003 and between 20 and
32 mass% Ni its values are eNiS = – 0.006 [1968Chm] (eNiS = 0.0 and eSNi = – 0.0037 [1974Sig];
eNiS = – 0.00006 at 1550˚C and up to 50 at.% Ni [1969Ban], eNiS = – 0.005 [1973Buz]). The
value of eNiS obtained from the theoretical model is –0.49 [1981Fit]. The first order interaction
parameters up to 35 at.% Fe at 1575˚C are equal eFeS = + 0.005 [1968Chm]. The second order
interaction coefficient rNiS is equal zero [1974Sig].
The thermodynamic modelling was performed by [1983Chu1, 1987Hsi1, 1987Hsi2,
1987Hsi3] using associated solution model for the liquid phase, statistical model for mono-
sulfide solid solution and subregular model for other solutions. The liquidus projection,
isothermal sections in the range 1350-700˚C, sulfur activity over liquid and monosulfide
were calculated and compared with respective experimental data. Stability diagrams (poten-
tial diagrams) presenting partial pressure of sulfur versus composition were calculated at
1100-700˚C. Two other assessments of thermodynamic parameters [2004Wal2, 2006Wal2]
were published recently. Quasichemical model for short-range ordering was applied for
ternary liquid and sublattice model was applied for description of solid solutions: mono-
sulfide, pentlandite, pyrite, vaesite and high-temperature haezlewoodite. Based on those
thermodynamic descriptions isothermal sections in the range 1350-600˚C, vertical sections,
sulfur activity over liquid and monosulfide phase were calculated. As was mentioned before, in
the description of [2006Wal2] two phases of haezlewoodite were considered, while the
parameters for other phases were the same as in [2004Wal2].
The solubility curve of FeS2 in NiS2 was applied in geological thermometry by [1963Cla]. An
increase in S or FeS activity by addition of FeS may be effective in lowering the Ni content of
the separating Fe-Ni alloys [1972Bye].
The magnetic order Ð disorder transition occurs in regions of the monosulfide solid
solution (pyrrhotite) where it breaks on cooling [1974Vau]. Beyond this transition in the
monosulfide compositions may exhibits weak temperature independent Pauli paramagnetism
and metallic conductivity. [1976Kas] indicated that the magnetization of FexNi1–xS ceramics
reduces with increasing Ni content up to 50 at.%, increases between 50 and 60 at.% Ni and
decreases again between 60 and 100 at.% Ni. The TC reduces with increasing Ni content up to
50 at.% but was not measured for higher Ni contents at room temperature to 300˚C. The
electrical resistivity reduces uniformly with decreasing Fe content of this ceramics. [1997Dre]
noted that monosulfide within the range of composition (Fe1–xNix)0.96S at x = 0-0.6
are capable of forming magnetic structures like Fe0.96S. Ni atoms create defects in the
magnetic structure. The temperature of the magnetic - paramagnetic transition decreases
with decreasing Fe:Ni ratio and the changes in the initial monosulfide are directed towards

8 11 Fe–Ni–S
moving Ni from the magnetic monosulfide into the nonmagnetic pentlandite. Magnetic
measurement and DTA have been performed at 4.2-300 K for Ni1–xFexS by [1976Bar]. Metal
- non-metal transition temperature decreased for 1% Fe and then increased for 2-3% Fe.
Magnetic susceptibility was measured for Ni0.99Fe0.01S.
According to the data of [1961Nis] the magnetic region in the Fe-Ni-S ternary system lies
within the composition region enclosed by the line Fe-FeS-Fe9–xNixS8-Ni3S2-Ni. Specimens
outside of this area were non-magnetic. The intensity of magnetization of the specimens
decreases when the composition changes towards the line FeS-Fe9–xNixS8-Ni3S2. The speci-
mens whose S content is higher than this line were paramagnetic.
The metal-semiconductor transition in the Fe1–xS-Ni1–xS system is accompanied by the
drastic changes of electrical and magnetic properties, this being similar to that of pure NiS
[1981Oht]. Transition temperature (Tt) increases with increase in Fe content, but in the
forward direction it shows a significant increase as high as 50˚C, when specimens were aged
at a temperature below Tt. The reverse transformation is not affected by thermal history at all.
This could be explained by the relaxation process in which the strain energy stored in the low
temperature phase is relieved by aging [1981Oht].
Ni-doped FeS2 is n type semiconductor [2006Leh]. Resistivity range from 2 to 17 Ω·cm,
carrier concentration is similar for undoped and Ni doped FrS2 ranging from 1015 to
1016.6 cm–3 and Hall mobility is ranging from 60 to 270 cm2·V–1·s–1.
[1977Nis] noted that the Ni atom in the Fe0.5Ni0.5S2 solid solution has a magnetic moment
of about 1 μB at low temperatures.
Pentlandite (τ1) Fe9–xNixS8 remains Pauli-paramagnetic down to 4.2 K with no resultant
magnetic moments of the Me atoms [1970Kno, 1976Kno]. Fe1.22Ni1.81S3.97 is also Pauli-
paramagnetic with 0.13 μB per FeNi2S4 molecule [1977Tow]. Thermal expansion of pentland-
ite Fe4.5Ni4.5S8 was studied in the temperature range between 25 and 608˚C by XRD in
[1964Mor].
The compressional wave velocity in molten Fe containing 5 mass% Ni and 10 mass% S
increases with increasing temperature [1997Nas]. 10 mass% S enhances also sound attenua-
tion by one or two orders of magnitude compared with liquid Fe. Such behavior at outer core
pressures and temperatures would constrain the velocity gradient in the outer core and would
enable the discrimination of potential light alloying elements.
The temperature dependence of surface tension for the Fe-Ni melts containing the surface
active element S was measured at 1600˚C by [1993Lee]. It was found to be positive and iso-
surface tension diagram for Fe-Ni-S melts at 1600˚C were presented by [1993Lee]. Sulfur
decreases slightly the thermal expansion coefficient (α) of the as-rolled Fe-Ni alloy containing
36 mass% Ni, whereas annealed specimens with addition of S below 0.05 mass% exhibit a
value of α lower than that for zero addition [1987Ina]. S addition above 0.05 mass% make
rolling of the sheet impracticable. Yield strength and tensile strength of such alloys rapidly
increase for addition below 0.03 mass% S, which indicates that the work hardening, due to
addition of S, is significant.
Experimental studies of material properties are presented in Table 4.
Miscellaneous
Fe-Ni-S alloys are believed to be a possible component of the cores of planetary bodies such as
Earth, Mars and Io [1997Nas].
Fe–Ni–S 11 9
The S diffusion coefficients in bulk Fe-Ni alloys, containing 25, 50 and 75 at.% Ni, have
been determined in the 950 to 1200˚C temperature range by [1982Net]. The values of the
activation energy have been experimentally found between 142 and 209 kJ·mol–1.
FexNi1–xS solid solutions could be prepared by the metal oxide - carbon disulfide reaction
sintering method [1976Kas].
Pentlandite (τ1) is one of the main ores minerals and the biggest part of world Ni
production is obtained from this mineral [1955Eli, 1974Vau]. It is likely that much hypogene
violarite (FeNi2S4) is formed by exsolution from initially deposited monosulfide solid solution
[1971Cra]. FeNi2S4 is also an important mineral quite common in natural Fe-Ni sulfide
assemblages containing pentlandite [1977Tow].
FeS2 crystals doped with Ni were synthesized using a chemical vapor transport with FeBr3
as a transport agent [2006Leh]. Ni concentration was ~200-1500 ppm.
Physicochemical behavior of Ni, Fe and Pt group elements impurities at an early stage of
crystallization of Fe-Ni melts with a small surplus of S relative to the total of metals indicates
that under certain conditions Pt group element-bearing phases can form: (Pt, Fe, Ir)-alloy (at
initial Fe >> Ni), RuS2 (at initial Ni > Fe), (Pt, Ni)S - in a specimen of pure Ni initial
composition [2001Sin2].
As S is added to the Fe-Ni alloys, segregation coefficients (k) of trace constituents
change dramatically [1990Jon]. If the composition of the metallic liquid is known, k may be
predicted - even if the temperature, exact Fe/Ni ratio and information about the activity
coefficient in the solid phase are unknown.
Mössbauer study of iron sulfides doped with 3d-transition metals were performed by
[2000Kim, 2005Nam] at temperatures ranging from liquid nitrogen to 600 K.
Kinetic of exsolution of pentlandite (τ1) from monosulfide solid solution was studied by
[2004Ets] by anneal/quench and in-situ cooling experiments. The extent of exsolution was
monitored using powder neutron diffraction data. Mechanism of pentlandite formation was
discussed by [2001Kos] based on results obtained by combination of directional crystallization
with thermal analysis. According to the obtained results it form due to solid state reactions on
cooling. Solidification behavior of Fe-41 Ni (mass%) alloys at 520-665˚C with flowing H2/
H2S/N2 gas mixtures was investigated by [1989Orc1, 1989Orc2]. Reaction kinetics were
irregular at 520˚C and parabolic at higher temperatures consistent with ratio of self-diffusion
coefficient DFe/DNi=0.4. [1989Bat] calculated partition coefficient for nickel and sulfur in
solid/liquid interaction based on parameters from binary systems. The poor agreement
between calculations and experiments could be due to significant second-order S-S and
Ni-S effect at higher sulfur concentrations. The electromagnetic levitation of sulfur in liquid
iron, nickel and iron-nickel alloys was studied by [1986Jac]. By applying principle of local
equilibrium at metal drop/gas interface, the activities of sulfur in liquid alloys were evaluated.
Influence of sulfur to dissolution/passivation of Ni-25%Fe alloy was investigated by
[1981Mar, 1984Mar1, 1984Mar2] using electrochemical and radiotrace technique.
First-principle calculations of electronic structure and stability of pentlandite solid solu-
tion were performed by [2002Cha]. Lattice parameters, bulk modulus and heat of formations
were predicted.

10 11 Fe–Ni–S
. Table 1
Investigations of the Fe-Ni-S Phase Relations, Structures and Thermodynamics
[1930Vog] DTA, metallography Up to 1500˚C / Fe-FeS-Ni3S2-Ni

[1938Ura] DTA, metallography Up to 1300˚C / Fe-Ni-S
[1947Lun] Phase equilibria, XRD 200, 400, 680˚C / Fe-Ni-S
[1955Cor] Equilibration with gas mixtures 1600˚C / sulfur partial pressure over
Fe-Ni liquid
[1955Eli] XRD Room temperature / Fe9–xNixS8
[1956Kul] XRD 500˚C / Fe-Ni-S, 500-1000˚C / Fe/
Ni = 1 (Fe+Ni)/S from 7.5/8 to 9/8
[1955Van] DTA, metallography Up to 1300˚C / Fe-FeS-Ni6S5-Ni
[1957Van] DTA, metallography, microhardness Up to 1400˚C / Fe-FeS-NiS-Ni
measurement
[1960Alc] Equilibration with H2/H2S gas mixture 1540˚C / (Fe-Ni) + S, S activity
[1960Cla] XRD 500-800˚C up to 40 mass% S, up to
40 mass% Ni
[1961Kno] XRD, neutron diffraction, pyknometry Pentlandite solid solutions
[1961Nis] XRD, magnetization intensity Up to 1100˚C / Fe1–xS-Ni1–xS
measurements, thermomagnetic analysis
[1961Stu] XRD, EPMA, chemical analysis, Room temperature / (FexNi1–x)2S
metallography
[1962Vay] EMF measurements 1300˚C / up to 50 at.% S
[1963Cla] Hydrothermal experiments, optical 100-1000˚C / FeS2-NiS2, 50-100
microscopy, XRD at.% S
[1963Kan] XRD, chemical analysis 950˚C / Fe1–xS-Ni1–xS
[1963Kul1] XRD 400-1100˚C / Fe-Ni-S isothermal
sections
[1963Kul2] DTA, high-temperature XRD 500-800˚C / pentlandite
[1966Nal] XRD 250-600˚C / 35-40 mass% S
[1967Nal]
[1968Jos] Metallography, chemical analysis 1000˚C / (Fe + 10 mass% Ni) + S
[1968Chm] Equilibrating with H2/H2S gas mixtures, Fe-Ni-S up to 32 mol% Ni
chemical analysis
[1968Cra] XRD, electron microprobe, optical 400˚C / Fe-Ni-S
microscopy
[1969Ban] Equilibrating with H2/H2S gas mixtures, 1550˚C / Ni-Fe-S
chemical analysis
[1969Vai] EMF measurement 1300˚C / Fe-Ni-S

Fe–Ni–S 11 11
[1970Khe] EMF measurement 1300˚C / Fe-Ni-S at 40 at.% S

[1970Kno] Mössbauer spectroscopy 4.2 K / Fe9–xNixS8
[1970She] XRD, optical microscopy 400-600˚C, 20-60 mass% S
[1970Vay] EMF measurement 1300˚C / Ni-Fe-S
[1971Cra] XRD, metallography 300-500˚C / FeS-FeS2-NiS2-NiS
[1971Gra] EPMA < 135-500˚C / Fe-FeS2-NiS2-Ni
[1972Bye] Gravimetry 1250˚C / (Fe-Ni-S) + H2S/H2
[1972Har] Electron microprobe Compositions of pentladites
[1972Nic] Optical microscopy, electron microprobe Smithite (Fe,Ni)3.3S4 associated with
pentlandite and pyrrotite
[1972Tay] XRD, EPMA Room temperature / Fe9–xNixS11
[1973Buz] XRD, EPMA 1600˚C / Fe-Ni-S
[1973Cra] XRD, electron microprobe, optical 200-300˚C/ 25-60 mass% S
microscopy
[1973Hal] XRD Pentlandite (Ni,Fe)9S8
[1973Mis1] XRD, electron microprobe, optical 230-600˚C / up to 55 at.% S
microscopy
[1973Mis2] XRD Fe1–xS-Ni1–xS, pentlandite, Fe-Ni
alloy (taenite)
[1973Raj] XRD Pentlandite solid solutions
[1973Ven] Chemical analysis, vapor pressure 1575˚C / Fe-Ni-S up to 35 at.% Fe
measurements
[1974Khe] EMF measuring 1300˚C / Fe-Ni-S
[1974Mis] Electron microprobe, single crystal XRD Composition and stability of
(Fe,Ni)3S4 violarites
[1974Vau] XRD, EPMA, Mössbauer spectroscopy 600˚C / Fe1–xS-Ni1–xS
[1976Chi] DTA, metallography, dilatometry, X-ray 138-1100˚C / Fe-Ni3S2
spectrometry analysis
[1976Fra] TEM, EPMA 600˚C / (Fe,Ni)1–xS up to 37 mass%
Ni
[1976Gul] DTA, X-ray spectrum analysis, Up to 1200˚C / Cu2S + Fe
microhardness measurements
[1976Kas] XRD, TGA, magnetic properties and 20˚C / Fe1–xS-Ni1–xS
electrical resistivity measurements
[1976Kno] XRD, neutron powder diffraction, Up to 600˚C / Fe9–xNixS8
Mössbauer spectroscopy, magnetic
susceptibility measurements

12 11 Fe–Ni–S
[1977Nis] Mössbauer spectroscopy 10-295 K / Fe0.5Ni0.5S2

[1977Tow] XRD, Mössbauer spectroscopy, magnetic 5-300 K / FeNi2S4
susceptibility and thermoelectric power
measurements
[1978Len] Equilibrium study, microprobe and chemical 1200-1400˚C / up to 25 mass% S,
analysis liquidus surface
[1979Sha] SEM, metallography 600-813˚C / Fe-Ni3S2
[1980Vol] XRD Synthesis 600-1000˚C / pressures 4
GPa, Fe1–xS-Ni1–xS
[1981Fit] Wagner model Sulfur activity in dilute Fe-Ni liquid
solution at 1540˚C
[1981Oht] XRD, DSC, magnetic susceptibility and 110-373 K / Fe1–xS-Ni1–xS
electric resistivity measurements,
Mössbauer spectroscopy
[1982Net, Radioisotope analysis 950-1200˚C / (Fe-Ni) + H2S/H2
1983Net1,
1983Net2]
[1983Chu1] Calphad 1200˚C / FeS-Ni3S2, thermodynamic
[1983Chu2] properties, liquidus 1200-1350˚C
[1983Van] Dew point method 1000-1250˚C / Fe-Ni-S
[1984Bee] XRD, EPMA, metallography 400-600˚C / Fe-Ni-S
[1984Khe] Dew point method 800-1250˚C / Fe-Ni-S
35
[1981Mar] Radiotracer S technique, electrochemical Ni-25Fe, dissolution/passivation
[1984Mar1] measurements, X-ray photoelectron
[1984Mar2] spectroscopy
[1984Sel] Electron microprobe Fe-7.2Ni-1.15S (mass%) distribution
of Ni during solidification
[1987Con] Equilibration with H2/H2S gas mixtures, 1200-1400˚C / Fe/Ni = 0.25, 1, 4
vapor pressure measurement with Knudsen Activity of Fe and Ni over liquid
effusion mass-spectrometry Fe-Ni-S
[1987Hsi1] Calphad, phase equilibration with H2/H2S 900-1400˚C / Fe-Ni-S, isoactivity
gas mixtures diagrams, isothermal sections,
stability diagrams
[1987Hsi2] Calphad 900-1350˚C / Fe-Ni-S
[1987Hsi3] Statistical thermodynamic model Monosulfide solid solution
[1987Hsi4] Equilibration with H2/H2S gas mixtures, 700-900˚C / sulfur activity over
thermodynamic calculations monosulfide solid solution

Fe–Ni–S 11 13
[1989Bar] Equilibration with H2/H2S gas mixture, 900-1250˚C / solubility and

radiotracer 35S method diffusion of S in Fe-Ni alloys
[1989Orc1] XRD, microprobe analysis, electron 520-665˚C / Fe-41mass%Ni at
microscopy PS2 = 2·10–5-6·10–1 Pa
[1989Orc2] XRD, microprobe analysis 520-665˚C / Fe-41mass%Ni at
PS2 = 2·10–5-6·10–1 Pa
[1990Jon] Thermodynamic modelling solid/liquid Fe-Ni-S
interaction
[1991Kes] XRD Room temperature / Ni3S4, FeNi2S4
[1995Ma] Electron microscopy, microprobe analysis 400, 500˚C / Fe-30Ni-10S (mass%)
[1997Dre] Differential Scanning Calorimetry (DSC) 20-305˚C / (Fe1–xNix)0.96S
[1998Ma] Electron microscopy, microprobe analysis 300-900˚C Fe-rich compositions
with 2.5-30 mass% Ni, 10 mass% S
[1998Kar] EPMA 900˚C / up to 70 at.% S
[1998Sin] XRD, DTA 950-1200˚C / Fe0.96S-Ni0.96S
liquidus, solidus
[1999Kon] Calphad 1350-1250˚C / S up to 26 at.%
[1999Nko] XRD Room temperature / Fe9–xNixS8 and
Fe1–xS
[1999Sin] XRD, optical, electron microscopy, DTA 470-1200˚C / 35-51 at.% S
[2000Kim] XRD, Mössbauer spectroscopy 77-600 K / Ni0.025Fe0.975S
[2000Uen] XRD, optical microscopy 400, 500˚C / Fe-Ni-S
[2001Far] XRD, sulfur K-edge spectra Room temperature /
Ni0.923S-Fe0.923S
[2001Kos] Directional solidification from melt, XRD, TA, 26.65 at.% Fe, 26.65 at.% Ni and
optical microscopy, microprobe analysis 46.7 at.% S
[2001Sin1] XRD, optical, electron microscopy, 600˚C / 22-55 at.% S
microprobe analysis
[2003Kos] S fugacity by equilibration technique 600˚C / Fe-FeS-NiS-Ni
[2004Kos] Directional crystallization from melt, DTA 840-875˚C / 40-55 at.% S
[2004Wal2] Calphad 600-1400˚C / Fe-Ni-S
[2005Nam] XRD, Mössbauer spectroscopy 77-600 K / Ni0.025Fe0.975S
[2006Leh] XRD, EPMA synchrotron XRD, mass Room temperature / FeS2 + Ni
spectrometry

14 11 Fe–Ni–S
[2006Sin] S fugacity by equilibration technique, XRD, 900˚C / Fe-FeS-NiS-Ni

microprobe analysis, optical microscopy,
SEM
[2006Wal2] Calphad 600˚C / Fe-Ni-S, 300-1200˚C
FeS-Ni3S2
. Table 2
Pearson
(δFe) cI2 a = 293.15 pure Fe [Mas2]

1538 - 1394 Im3m dissolves 3.8 at.% Ni at 1517˚C
W
γ, (γFe,Ni) cF4
(γFe) Fm3m a = 364.67 pure Fe at 915˚C [V-C2, Mas2]
1394 - 912 Cu
< 1455 below critical temperature:
γ1 - paramagnetic, Fe enriched
γ2 – ferromagnetic, Ni enriched
< 912 Im3m dissolves 4.6 at.% Ni at 495˚C
W
(εFe) hP2 a = 246.8 at 25˚C, 13GPa [Mas2]
P63/mmc c = 396.0
Mg
γ’FeNi3 cP4 a = 355.23 63 to 85 at.% Ni [1991Swa]
< 517 Pm3m
AuCu3
γ’’FeNi tP4 a = 357.9 [V-C2]
metastable P4/mmm metastable ordering temperature 320˚C at
AuCu 51.2 at.% Ni [1984Ros]
Fe3Ni cP4 a = 357.5 ± 0.1 metastable [V-C2, Mas2]
? Fm3m
Cu

Fe–Ni–S 11 15
Pearson
(βS) mP64 a = 1102 [Mas2]

115.22 - 95.5 P21/c b = 1096
βS c = 1090
β = 96.7˚
(αS) oF128 a = 1046.4 pure S at 25˚C [Mas2]
< 95.5 Fddd b = 1286.60
αS c = 2448.60
Pyrr, hP4 Mineral pyrrhotite,
Fe1–xNixS1±y P63/mmc 0 ≤ x ≤ 1, 0 ≤ y ≤ 0.1
< 1182 NiAs
a = 343.43 ± 0.7 x = 0.5 [V-C2]
c = 558.20 ± 0.11
a = 344.0 ± 0.2 for composition (Fe0.75Ni0.25)0.923S
c = 567.6 ± 0.3 [2001Far]
c = 559.2 ± 0.1 [2001Far]
c = 539.6 ± 0.3 [2001Far]
γFe1–xS a = 344.36 ± 0.05 pyrrhotite, 50 to 55 at.% S [V-C2, Mas2]
1188 - 315 c = 587.59 ± 0.05
a = 345.3 ± 0.1 for composition Fe0.923S [2001Far]
c = 576.5 ± 0.2
δNi1–xS a = 343.98 ± 0.03 millerite, 49.8 to 52.5 at.% S [V-C2, Mas2]
< 1001 c = 534.82 ± 0.05
a = 343.16 ± 0.07 for composition Ni0.923S [2001Far]
c = 532.5 ± 0.1
βFe1–xS hP24 a = 596.3 ± 0.1 troilite, at 21˚C [V-C2, Mas2],
315 - 138 P62c c = 1175.4 ± 0.1 0 ≤ x ≤ 0.07
Superstructure a = 586.1
of NiAs-type c = 1157.7 ± 0.1
a = 599.8 ± 1.1 at 21˚C and 3.33 GPa [V-C2, Mas2]
c = 1171 ± 1
at 120˚C [V-C2, Mas2]
β(Fe1–xNixS) a = 596.5 ± 0.2
c = 1171 ± 5
x = 0.025 [2005Nam]
αFe1–xS P31c a = 596.6± 0.1 [2008Fer] 0 ≤ x ≤ 0.07
< 138 Subgroup of c = 1176 ± 0.1
P62c
-

16 11 Fe–Ni–S
Pearson
FeS oP8 high-pressure phase

(II) Pnma a = 582.5 ± 0.2 at 190˚C [V-C2]
? MnP b = 346.8 ± 0.1
c = 693.5 ± 0.6
a = 571.6 ± 0.9 at 21˚C and 4.15 GPa [V-C2]
b = 334.7 ± 0.3
c = 669.4 ± 0.9
a = 565 ± 1 at 21˚C and 6.35 GPa [V-C2]
b = 331.6 ± 0.3
c = 663.1 ± 0.8
FeS tP4 a = 376.8 Mackinawite [V-C2]
? P4/nmm c = 503.9
PbO
Py, Fe1–xNixS2 cP12 Mineral pyrite, 0 ≤ x ≤ 0.15
Pa3
FeS2
a = 541.79 ± 0.11 x = 0 [V-C2, Mas2]
βFeS2 a = 534.8 ± 0.2 at 1.57 GPa [V-C2]
< 743 a = 529.3 ± 0.2 at 2.87 GPa [V-C2]
a = 525.5 ± 0.2 at 3.85 GPa [V-C2]
V, FexNi1–xS2 cP12 Mineral vaesite, 0 ≤ x ≤ 0.22
Pa3
FeS2
a = 566.8 x = 0.1 [V-C2]
a = 568.65 ± 0.03 x = 0 [V-C2, Mas2]
ηNiS2
< 1022 a = 561.96 ± 0.06 at 3.2 GPa [V-C2]
a = 557.45 ± 0.04 at 5.4 GPa [V-C2]
a = 558.52 ± 0.04 at 4.9 GPa [V-C2]
αFeS2 oP6 a = 444.1 Marcasite [V-C2, Mas2]
≲ 444.5 Pnnm b = 542.5
FeS2 (marcasite) c = 338.7
a = 446.4 at 327˚C [V-C2]
b = 544
c = 339
Fe2S3 tP80 a = 1053 [V-C2]
? P43212 c = 1001
-
Fe3S4 hR21 a = 347 ± 2 Smythite [V-C2]
? R3m c = 3450 ± 2
Fe3S4 a = 347 ± 0.1
c = 3440.0 ± 0.1 for composition Fe9–xNixS11 [1972Tay]

Fe–Ni–S 11 17
Pearson
Fe3S4 cF56 a = 987.6 ± 0.2 Greigite [V-C2], probably metastable

? Fd3m
MgAl2O4
Fe1–xS hP* a = 596.5 ± 0.3 [2008Fer] 0 ≤ x ≤ 0.125
< 315 Superstructure c = 1171.6 ± 0.8
of
NiAs type
o** a = 1193.0 ± 0.4 [2008Fer] x = 0.1
Superstructure b = 688.8 ± 0.3
of
NiAs type c = 2865.8 ± 0.35
m** a = 1192.0 ± 0.2 [2008Fer] x = 0.125
Superstructure b = 585.8 ± 0.4
of NiAs-type c = 2285.2 ± 0.8
β = 90.37 ± 0.6˚
β, Ni3S2 hR15 a = 573.1 ± 0.5 [V-C2] low-temperature heazlewoodite
< 533 R32 c = 711.9 ± 0.7
Ni3S2
β1(Ni1–xFex)3S2 cF10 high temperature Heazlewoodite
F43m 0 x ≤ 0.35 (36.7 to 42 at.% S)
a = 522.8 ± 0.9
β1, Ni3S2
800 - 533 36.7 to 42 at.% S [V-C2, Mas2]
β2(Ni1–xFex)4S3 cP* - high temperature Heazlewoodite
0 ≤ x ≤ 0.26 (42 to 44 at.% S) [Mas2]
β2, Ni4S3 42 to 44 at.% S [Mas2]
806 - 524
γNi7S6 oC56 a = 327.4 ± 0.1 Godlevskite [V-C2, Mas2]
573 - 400 Cmcm b = 1135.9 ± 0.4
Ni7S6 c = 1615.7 ± 0.7
γ’Ni7S6 m** a = 3238.8 ± 2.4 [V-C2, Mas2]
< 400 b = 2273.0 ± 2.0 probably metastable
c = 652.5 ± 0.7
Ni9S8 o* a = 932.5 ± 0.1 [1994Sto]
< 436 C222 b = 1123.9 ± 0.1
- c = 941.00 ± 0.1
εNiS hP4 a = 344.56 ± 0.08 50 to 50.5 at.% S,
< 379 P63mc c = 540.5 ± 0.1 low temperature phase [V-C2]
NiS

18 11 Fe–Ni–S
Pearson
FexNi3–xS4 cF56 0≤x≤1

Fd3m a = 946.4 ± 0.2 violorite, x = 1 [1991Kes]
MgAl2O4 a = 946.5 x = 1 [V-C2]
a = 945 for composition Fe1.22Ni1.81S3.97 [1977Tow]
ζNi3S4 cF56 a = 948.9 Polydymite, [V-C2, Mas2]
< 356 Fd3m
Co3S4
Ni6S5 oC48 a = 325.4 [V-C2]
Cmcm b = 1133.8
Ni6Se5 c = 1643.0
Ni17S18 hP105 a = 1029.0 ± 0.2 [V-C2]
P3121 c = 1599.3 ± 0.3
Ni17S18
*τ1, Fe9–xNixS8+y cF68 Mineral pentlandite
< 610 Fm3m 3.8 < x < 5.5 [2003Kos]
Co9S8 0<y<1
a = 1012.8 ± 0.1 x = 4, y = 0 [V-C2]
a = 1003.8 ± 0.1 x = 5, y = 0 [V-C2]
a = 1012.8 ± 0.1 x = 4, y = 0 [1976Kno]
a = 1010.9 ± 0.1 x = 4.5, y = 0 [1976Kno]
a = 1010.0 ± 0.1 x = 5, y = 0 [1976Kno]
a = 1009.4 ± 0.2 x = 5.5, y = 0 [1976Kno]
a = 1004.9 ± 0.6 x ≈ 4.5, y = 0 [1999Nko]
a = 1004.6 ± 0.4 x ≈ 4.5, y = 0 [1955Eli]
a = 1012.9 x = 3.8, y = 0 [1961Nis]
a = 1009.5 x = 5.2, y = 0 [1961Nis]
a = 1008.6 ± 0.5 x = 5.4, y = 1 [V-C2]
*τ2, Fe0.5Ni0.5S2 cP12 a = 554.7 low temperature phase, bravoite [1977Nis]
< 137 Pa3
FeS2
a = 554.5 ± 0.1 [V-C2]
FeNi29S27 oC68 a = 933.59 ± 0.07 low temperature phase, probably
C222 b = 1121.85 ± 0.1 metastable [V-C2]
FeNi29S27 c = 943.0 ± 0.6

Fe–Ni–S 11 19
. Table 3
Composition (at.%)
Reaction T [˚C] Type Phase Fe Ni S
L1 + L2 Ð Pyrr + V 1005 U1 L1 5.95 36.21 57.84

L2 0.04 0.29 99.67
Pyrr 9.75 37.10 53.15
V 1.26 33.47 65.27
L1 + Pyrr Ð β 875 pmax L1 21.3 34.5 44.2
Pyrr 34.9 13.9 51.1
β 22.5 32.5 45.0
L1 + Pyrr Ð β + γ 800 U2 L1 - - -
L2 + Pyrr Ð Py + V 729 U3 L2 - - -
Pyrr - - -
Py 30.82 2.51 66.67
V 9.46 23.83 66.67
. Table 4
Investigations of the Fe-Ni-S Materials Properties
[1961Nis] Magnetic measurements, Magnetization, Curie temperature

thermomagnetic analysis
[1964Mor] XRD Thermal expansion for pentlandite
[1974Vau] Mössbauer spectroscopy Magnetic properties
[1976Bar] Magnetic measurement, DTA Metal - non-metal transition temperature,
magnetic susceptibility at 4.2 to 300 K for
Ni1–xFexS at x = 0.01-0.06
[1976Chi] Microhardness measurements Microhardness in Fe-Ni3S2 system
[1976Kno] Faraday method Magnetic susceptibility
[1980Vol] XRD, resistivity measurements Electrical conductivity of monosulfide solid
solution at high pressure and temperature
[1987Ina] Stress-strain diagram method Thermal expansion, yield strength, tensile
strength

20 11 Fe–Ni–S
[1993Lee] Oscillating droplet method combined Surface tension

with electromagnetic levitation
technique
[1997Nas] Ultrasonic interferometry Sound velocity and attenuation
[2006Leh] Electrical measurements Resistivity, carrier concentration, Hall mobility
(Electric properties)

Fe-Ni-S. Reaction scheme
. Fig. 1
Fe–Ni–S 11 21

22 11 Fe–Ni–S
. Fig. 2
Fe-Ni-S. Liquidus surface projection

Fe–Ni–S 11 23
. Fig. 3a
Fe-Ni-S. Calculated isothermal section at 1350˚C

24 11 Fe–Ni–S
. Fig. 3b

Fe–Ni–S 11 25
. Fig. 3c

26 11 Fe–Ni–S
. Fig. 4a

Fe–Ni–S 11 27
. Fig. 4b

28 11 Fe–Ni–S
. Fig. 4c

Fe–Ni–S 11 29
. Fig. 5a

30 11 Fe–Ni–S
. Fig. 5b

Fe–Ni–S 11 31
. Fig. 5c

32 11 Fe–Ni–S
. Fig. 6a
Fe-Ni-S. Experimental isothermal section at 500˚C

Fe–Ni–S 11 33
. Fig. 6b

34 11 Fe–Ni–S
. Fig. 7a

Fe–Ni–S 11 35
. Fig. 7b

36 11 Fe–Ni–S
. Fig. 7c
Fe-Ni-S. Experimental isothermal section at < 135˚C

Fe–Ni–S 11 37
. Fig. 8a
Fe-Ni-S. Calculated temperature-composition section for the FeS-Ni3S2 join

38 11 Fe–Ni–S
. Fig. 8b
Fe-Ni-S. Calculated temperature-composition section for the FeS2-NiS2 join

Fe–Ni–S 11 39
. Fig. 8c
Fe-Ni-S. Calculated temperature-composition section for a constant S concentration of xS = 0.471

40 11 Fe–Ni–S
. Fig. 9a
Fe-Ni-S. Calculated potential diagram at 700˚C

Fe–Ni–S 11 41
. Fig. 9b

42 11 Fe–Ni–S
. Fig. 9c

Fe–Ni–S 11 43
. Fig. 9d

44 11 Fe–Ni–S
. Fig. 10
Fe-Ni-S. Calculated Fe activity in the liquid phase (expressed as equilibrium partial pressure of Fe
in the gas phase) at 1300˚C, values are xNi

Fe–Ni–S 11 45
. Fig. 11
Fe-Ni-S. Calculated Fe activity in the liquid phase for the Ni3S2-FeS and FeS-Ni joins

46 11 Fe–Ni–S
. Fig. 12a
Fe-Ni-S. Calculated S activity in the liquid phase (expressed as equilibrium partial pressure of S2
in the gas phase) at Fe/Ni ratio of 0.25

Fe–Ni–S 11 47
. Fig. 12b
in the gas phase) at Fe/Ni ratio of 1.0

48 11 Fe–Ni–S
. Fig. 12c
in gas phase) at Fe/Ni ratio of 4.0

Fe–Ni–S 11 49
. Fig. 13a
Fe-Ni-S. Calculated S activity in the monosulfide phase (expressed as equilibrium partial
pressure of S2 in the gas phase) at various Fe/Ni ratios and temperatures around 700˚C; values
indicate Fe/Ni ratio

50 11 Fe–Ni–S
. Fig. 13b

Fe–Ni–S 11 51
. Fig. 13c

52 11 Fe–Ni–S
. Fig. 13d
pressure of S2 in the gas phase) at various Fe/Ni ratios and temperatures aroud 850˚C; values

Fe–Ni–S 11 53
. Fig. 13e

54 11 Fe–Ni–S
. Fig. 14
Fe-Ni-S. Calculated activity of FeS and Ni3S2 along the FeS-Ni3S2 join

Fe–Ni–S 11 55
References
[1930Vog] Vogel, R., Tonn, W., “About the Ternary System Iron-Nickel-Sulfur” (in German), Arch. Eisenhuet-
tenwes., 3(12), 769–780 (1930) (Experimental, Phase Relations, Magn. Prop., 5)
[1938Ura] Urazov, G.G., Filin, N.A., “Investigation of Alloys of the Fe-Ni-S System” (in Russian), Metallurg, 2,
3–19 (1938) (Experimental, Morphology, Phase Diagram, Phase Relations, 21)
[1943Haw] Hawley, J.E., Colgrove, G.L., Zurbrugg, H.F., “The Fe-Ni-S System. An Introduction with New Data on
the Crystallization of Pyrrhotite and Pentlandite”, Econ. Geol., 38(5), 335–388 (1943) (Crys. Structure,
Experimental, Phase Diagram, Phase Relations, Thermodyn., 73)
[1947Lun] Lundqvist, D., “X-Ray Studies in the Ternary System Fe-Ni-S”, Arkiv Kemi, Mineral. Geol., 24A(22)
1–12 (1947) as quoted in [1973Mis2]
[1949Jae] Jaenecke, E., “S-Fe-Ni” (in German) in “Kurzgefasstes Handbuch aller Legierungen”, Winter Verlag,
[1955Cor] Cordier, J.A., Chipman, J., “Activity of Sulphur in Liquid Fe-Ni Alloys”, Trans. Amer. Inst. Min. Met.
Eng., Inst. Metals Div., 203(8), 905–907 (1955) (Experimental, Phase Relations, 7)
[1955Eli] Eliseev, E.N., “Chemical Composition and Crystal Structure of Pentlandite” (in Russian), Zap. Vses.
Mineral. Obshchest., 84, 53–62 (1955) (Experimental, Crystal Structure, Phase Diagram, Phase Rela-
tions, 21)
[1955Van] Vanyukov, V.A., Vanyukov, A.V., Tarashchuk, N.T., “The Fe-Ni-S Constitution Diagram” (in Russian),
Tsvet. Met., (4), 23–27 (1955) (Experimental, Phase Diagram, Phase Relations, 3)
[1956Kul] Kullerud, G., “Subsolidus Phase Relations in the Fe-Ni-S System”, Carnegie Inst. Washington, Yearbook,
55, 175–180 (1956) (Experimental, Phase Relations, 1)
[1957Van] Vanyukov, V.A., Vanyukov, A.V., Tarashchuk, N.T., “Phase Diagram of the System Fe-Ni-S” (in
Russian), Sb. Nauch. Tr. Moskovskii Inst. Tsvet. Metallov i Zolota, (26), 108–119 (1957) (Experimental,
[1960Alc] Alcock, C.B., Cheng, L.L., “A Thermodynamic Study of Dilute Solutions of Sulphur in Liquid Iron,
Cobalt and Nickel and Binary Alloys between these Metals”, J. Iron Steel Inst., 195(2), 169–173 (1960)
(Experimental, Thermodyn., 18)
[1960Cla] Clark, S.P., Kullerud, G., “The System Fe-Ni-S”, Carnegie Inst. Washington, Yearbook, 59, 141–144
[1961Kno] Knop, O., Ibrahim, M.A., “Chalcogenides of the Transition Elements. II. Existence of the π Phase in the
M9S8 Section of the System Fe-Co-Ni-S”, Canad. J. Chem., 39, 297–317 (1961) (Experimental, Phase
Relations, 44)
[1961Nis] Nishimara, K., Kondo, Y., “Studies on the Ni Matte. I. The Ni-Fe-S System”, Mem. Fac. Eng. Kyoto
Univ., 22, 242–263 (1961) (Experimental, Phase Diagram, Phase Relations, Thermodyn., 25)
[1961Stu] Stumpfl, E.F., “Some New Platinoid-Rich Minerals, Identified with the Electron Microanalyser”,
Mineral. Mag., 32(254), 833–847 (1961) (Experimental, Morphology, Phase Relations, 19)
[1962Kle] Klemm, D.D., “Investigations on Solid Solution Formation in the Ternary FeS2-CoS2-NiS2 and its
Relation to the Constitution of Natural “Bravoite”” (in German), Neues Jahrb. Mineral. Monatsh., 3–4
(3-4), 76–91 (1962) (Experimental, Phase Relations, 61)
[1962Vay] Vaysbrud, S.E., Verner, B.F., Heyfetz, V.L., “Activity of the Iron in the Fe-Ni-S Melts” (in Russian), Izv.
Vyss. Uchebn. Zaved., Chern. Metall., (1), 59–67 (1962) (Kinetics, Phase Diagram, Phase Relations,
Experimental, 5)
[1963Cla] Clark, L.A., Kullerud, G., “The Sulfur-Rich Portion of the Fe-Ni-S System”, Econ. Geol., 58, 853–885
(1963) (Experimental, Phase Relations, Thermodyn., 38)
[1963Kan] Kaneko, H., Nishizawa, T., Tamaki, K., “Study on Phase Diagrams of Sulphides in Steels” (in Japanese),
Nippon Kinzoku Gakkai Shi, 27(7), 312–319 (1963) (Experimental, Phase Relations, 23)
[1963Kul1] Kullerud, G., “The Fe-Ni-S System”, Carnegie Inst. Washington, Yearbook, 175–189 (1963) (Experimen-
tal, Phase Diagram, Phase Relations, 1)
[1963Kul2] Kullerud, G., “Thermal Stability of Pentlandite”, Canad. Mineral., 7, 353–366 (1963) (Experimental,
[1964Kul] Kullerud, G., “Review and Evaluation of Recent Research on Geologically Significant Sulfide-Type
Systems”, Fortschritte Mineral., 41(2), 221–270 (1964) (Phase Diagram, Phase Relations, Review, 109)
[1964Mor] Morimoto, N., Kullerud, G., “Pentlandite: Thermal Expansion”, Carnegie Inst. Washington, Yearbook,

56 11 Fe–Ni–S
[1966Nal] Naldrett, A.J., Kullerud, G., “Limits of the Fe1–xS-Ni1–xS Solid Solution between 600 and 250˚C”,
Carnegie Inst. Washington, Yearbook, 65, 320–326 (1966) (Experimental, Phase Relations, 1)
[1967Nal] Naldrett, A.J., Craig, J.R., Kullerud, G., “The Central Portion of the Fe-Ni-S System and its Bearing on
Pentlandite Exsolution in Iron-Nickel-Sulphide Ores”, Econ. Geol., 62, 826–847 (1967) (Experimental,
Morphology, Phase Diagram, Phase Relations, Thermodyn., 36)
[1968Chm] Chmelar, I., Buzek, Z., Hlineny, J., “Determination of the Sulfur Activity in the Fe-X-S Systems Using a
Laboratory Electroslag Furnace” (in Czech), Sborn. Ved. Praci Vysoke Skoly Banske Ostrave, 14(3),
175–181 (1965) (Experimental, Thermodyn., 8)
[1968Cra] Craig, J.R., Naldrett, A.J., Kullerud, G., “The Fe-Ni-Sulphide System. 400˚C Isothermal Diagram”,
Carnegie Inst. Washington, Yearbook, 66, 440–441 (1968) (Experimental, Phase Relations, 1)
[1968Jos] Josey, G.A., Floridis, T.P., “Solubility of S in Fe Alloys at 1000˚C”, Trans. Met. Soc. AIME, 242, 161–162
[1969Ban] Ban-ya, S., Chipman, J., “Sulfur in Liquid Iron Alloys: II – Effects of Alloying Elements”, Trans. Met.
Soc. AIME, 245(1), 133–143 (1969) (Experimental, Thermodyn., 18)
[1969Kul] Kullerud, G., Yund, R.A., Moh, G.H., “Phase Relations in the Cu-Fe-S, Cu-Ni-S, and Fe-Ni-S Systems”,
Magmat. Ore Deposits, Symp., 4, 323–343 (1969) (Experimental, Phase Diagram, Phase Relations, 48)
[1969Vai] Vaisbrud, S.E., Remen, T.F., Sheinin, A.B., “Thermodynamic Activity of Iron in System Iron-Nickel-
Sulphur at 1300˚C”, Russ. J. Phys. Chem. (Engl. Transl.), 43(12), 1780–1781 (1969) (Experimental, Phase
Relations, 4)
[1970Khe] Khejfec, V.L., Vajsburd, S.E., Remen, T.F., “About Experimental Identification of the Metal Activity in
the Multicomponent Melts” (in Russian), Tr. Proekt. Nauch.-Issled. Inst. “Gipronikel”, 46, 39–46 (1970)
(Experimental, Kinetics, Thermodyn., 14)
[1970Kno] Knop, O., Huang, C.-H., Woodhams, F.W.D., “Chalcogenides of the Transition Elements. VII. A
Mössbauer Study of Pentlandite”, Amer. Mineral., 55(7-8), 1115–1130 (1970) (Experimental, Crys.
Structure, Magn. Prop., 37)
[1970She] Shewman, R.W., Clark, L.A., “Pentlandite Phase Relations in the Fe-Ni-S System and Notes on
Monosulfide Solid Solution”, Canad. J. Earth Sci., 7, 67–85 (1970) (Experimental, Phase Relations,
Physical Properties, Thermodyn., 28)
[1970Sug] Sugaki, A., “Recent Studies on the Phase Equilibria of Sulphide Minerals” (in Japanese), Kozan
Chishitsu, 20(101), 237–257 (1970) (Review, Phase Relations, 59)
[1970Vay] Vaysbrud, S.E., Remen, T.F., Novikova, N.N., “Thermodynamic Properties of Liquid Slags and Mattes
and Component Distribution between Them” (in Russian), Tr. Proekth. Nauchno-Issled. Inst. “Gipro-
nikel”, 46, 5–31 (1970) (Experimental, Thermodyn., 41)
[1971Cra] Craig, J.R., “Violarite Stability Relations”, Am. Mineral, 56, 1303–1311 (1971) (Experimental, Phase
Diagram, Phase Relations, Thermodyn, 13)
[1971Gra] Graterol, M., Naldrett, A.J., “Mineralogy of the Marbridge No.3 and No.4 Nickel-Iron Sulfide
Deposits”, Econ. Geol., 66, 886–900 (1971) (Experimental, Crys. Structure, Phase Diagram, Phase
Relations, 16)
[1972Bye] Byerley, J.J., Takebe, N., “Thermodynamics of the Fe-Ni-S System at 1250˚C”, Metall. Trans., 3(2),
[1972Har] Harris, D.C., Nickel, E.H., “Pentlandite Compositions and Associations in some Mineral Deposits”,
Canad. Mineral., 11, 861–878 (1972) (Experimental, Phase Diagram, Phase Relations, 29)
[1972Nic] Nickel, E.H., “Nickeliferous Smythite from Some Canadian Occurrences”, Canad. Mineral., 11,
514–519 (1972) (Experimental, Morphology, 11)
[1972Tay] Taylor, L.A., Williams, K.L., “Smythite, (Fe,Ni)9S11 - a Redefinition.”, Am. Mineral, 57(11-12),
1571–1577 (1972) (Experimental, Phase Relations, Crys. Structure, 13)
[1972Vay] Vaysbrud, S.E., Burylev, B.P., Zedina, I.N., Remen, T.F., “Thermodynamic Properties of Sulfide Melts
and their Quantitative Description” (in Russian), Zhurn. Fiz. Khim., 46(6), 1528–1531 (1972) (Experi-
mental, Thermodyn., 9)
[1973Buz] Buzek, Z., “Effect of Alloying Elements on the Solubility and Activity of Oxygen and Sulphur in Liquid
Iron at 1600˚C” in “Metall. Chem. – Appl. Ferrous Metall.”, Int. Symp., Sheffield, July 1971, Iron and Steel
Inst., London, 173–177 (1973) (Experimental, Review, Crys. Structure, 8)
[1973Cra] Craig, J.R., “Pyrite-Pentlandite Assemblages and Other Low Temperature Relations in the Fe-Ni-S
System”, Amer. J. Sci., 273A, 496–551 (1973) (Experimental, Morphology, Phase Relations, 26)

Fe–Ni–S 11 57
[1973Hal] Hall, S.R., Stewart, J.M., “The Crystal Structure of Argentian Pentlandite (Fe,Ni)8AgS8 Compared with
the Refined Structure of Pentlandite (Fe,Ni)9S8”, Canad. Mineral., 12, 169–177 (1973) (Crystal Struc-
ture, Experimental, 20)
[1973Mis1] Misra, K.C., Fleet, M.E., “Unit Cell Parameters of Monosulfide, Pentlandite and Taenite Solid
Solutions Within the Fe-Ni-S System”, Mater. Res. Bull., 8, 669–678 (1973) (Experimental, Phase
[1973Mis2] Misra, K.C., Fleet, M.E., “The Chemical Compositions of Synthetic and Natural Pentlandite
Assemblages”, Econ. Geol., 68, 518–539 (1973) (Experimental, Phase Relations, Thermodyn., 89)
[1973Raj] Rajamani, V., Prewitt, C.T., “Crystal Chemistry of Natural Pentlandites”, Canad. Mineral., 12, 178–187
(1973) (Crys. Structure, Phys. Prop., Experimental, 26)
[1973Ven] Venal, W.V., Geiger, G.H., “The Thermodynamic Behavior of Sulfur in Molten Nickel and Nickel-Base
Alloys”, Metall. Trans., 4(11), 2567–2573 (1973) (Experimental, Thermodyn., 24)
[1974Khe] Kheifets, V.L., Vaysbrud, S.E., “About some Properties of Sulfide Melts of Iron Group Metals” (in
Russian) in “Elektrokhim. Rasplavy”, Nauka, Moscow, 118–122 (1974) (Review, Thermodyn., 21)
[1974Mis] Misra, K.C., Fleet, M.E., “Chemical Composition and Stability of Violarite”, Econ. Geol., 69, 391–403
(1974) (Crys. Structure, Experimental, Interface Phenomena, Morphology, Phase Relations, 33)
[1974Sig] Sigworth, G.K., Elliott, J.F., “The Thermodynamics of Liquid Dilute Iron Alloys”, Met. Sci., 8, 298–310
(1974) (Review, Thermodyn., 249)
[1974Vau] Vaughan, D.J., Craig, J.R., “The Crystal Chemistry and Magnetic Properties of Iron in the
Monosulphide Solid Solution of the Fe-Ni-S System”, Am. Mineral, 59(9-10), 926–933 (1974) (Experi-
[1976Bar] Barthelemy, E., Chavant, C., Collin, G., Gorochov, O., “Metal-Non Metal Transition of Ni1–xS and NiS
Substituted by Se, As and Fe: Transport Properties and Structural Aspect”, J. Physique, Colloq., 37, 17–22
(1976) (Crys. Structure, Experimental, Phys. Prop., 21)
[1976Chi] Chizhikov, D.M., Gulyanitskaya, Z.F., Blagoveshchenskaya, N.V., Blokhina, L.I., “The Ni3S2-Fe System”,
Russ. J. Inorg. Chem., 21(7), 1052–1054 (1976), translated from Zh. Neorg. Khim., 21(7), 1913–1916
[1976Fra] Francis, C.A., Craig, J.R., “Pyrrhotite: The nA (or 2A, 3C) Superstructure Reviewed”, Am. Mineral, 61,
21–25 (1976) (Experimental, Phase Diagram, Phase Relations, Phys. Prop., 18)
[1976Gul] Gulyanitskaya, Z.F., Blokhina, I.I., Blagoveshchenskaya, N.V., “Phase Composition and Transforma-
tions in Some Sulphide Systems” (in Russian), in “Tsvetn. Metall.”, Nauka, Moscow, 291–298 (1976)
(Experimental, Phase Relations, 26)
[1976Kas] Kasahara, Y., Nitta, T., Hayakawa, S., “Electrical and Magnetic Properties of Fe-Ni Sulphide Ceramics”,
J. Am. Ceram. Soc., 59, 204–206 (1976) (Experimental, Crys. Structure, Electr. Prop., Magn. Prop., 7)
[1976Kno] Knop, O., Huang, C.-H., Reid, K.I.G., Carlow, J.S., Woodhams, F.W.D., “Chalcogenides of the
Transition Elements. X. X-Ray, Neutron, Mössbauer and Magnetic Studies of Pentlandite and the π
Phases π (Fe, Co, Ni, S), Co8MS8 and Fe4Ni4MS8 (M = Ru, Rh, Pd)”, J. Solid State Chem., 16(1-2),
97–116 (1976) (Experimental, Crys. Structure, Phase Relations, 38)
[1977Nis] Nishihara, Y., Ogawa, S., Adachi, K., Tohda, M., “Mössbauer Study of Fe0.5Ni0.5S2. Hyperfine Field
at 57Fe in Fe0.5Ni0.5S2”, J. Phys. Soc. Jpn., 42(4), 1180 (1977) (Experimental, Crys. Structure, Magn.
Prop., 13)
[1977Tow] Townsend, M.G., Gosselin, J.R., Horwood, J.L., Ripley, L.G., Tremblay, R.J., “Violarite, a Metallic
Natural Spinel”, Phys. Status Solidi, 40A, K25–K29 (1977) (Experimental, Crys. Structure, Magn.
Prop., 8)
[1978Len] Lenz, J.G., Conard, B.R., Sridhar, R., Warner, J.S., “The Liquidus Surface and Tie-Lines in the Iron-
Nickel-Sulfur System Between 1473 and 1673 K”, Metall. Trans. B, 9(3), 459–462 (1978) (Experimental,
[1979Sha] Shatynski, S.R., Hirth, J.P., Rapp, R.A., “Solid-State Displacement Reactions between Selected
Metals and Sulfides”, Metall. Trans. A, 10A(5), 591–598 (1979) (Experimental, Phase Relations,
Morphology, 16)
[1980Vol] Vollstadt, H., Seipold, U., Kraft, A., “Structural and Electrical Relations of Monosulphide Solid
Solution in the Fe-Ni-S System at High Pressures and Temperatures”, Phys. Earth Planet. Interiors, 22
(3-4), 267–271 (1980) (Experimental, Phase Diagram, Phase Relations, Thermodyn., 4)
[1981Fit] Fitzner, K., Chang, Y.A., “The Activity Coefficient of Sulfur in Dilute Binary Liquid Metal Alloys”,
Chem. Metal. - Tribute Carl Wagner, Proc. Symp., 119–135 (1981) (Review, Thermodyn., 45)

58 11 Fe–Ni–S
[1981Mar] Marcus, P., Bouruet, A., Oudar, J., “Dissolution and Passivation of Nickel-Iron Alloys - Influence of
Sulfur”, Mem. Sci. Rev. Metall., 78(9), 509–512 (1981) (Experimental, Thermodyn., 11)
[1981Oht] Ohtani, T., Kosuge, K., Kachi, S., “Metal-Semiconductor Transition with Anomalous Thermal
Hysteresis Observed in Hexagonal (Ni1–xFe)1–yS, (0 ≤ x ≤ 0.30, 0 ≤ y ≤ 0.035)”, Bull. Chem. Soc. Jap.,
54(2), 568–575 (1981) (Experimental, Electr. Prop., Kinetics, Magn. Prop., 35)
[1982Hsi] Hsieh, K.-C., Chang, Y.A., Zhong, T., “The Fe-Ni-S System Above 700˚C”, Bull. Alloy Phase Diagrams,
3(2), 165–172 (1982) (Phase Diagram, Phase Relations, Review, 17)
[1982Net] Netter, P., Barbouth, N., Oudar, J., “Sulfur Diffusion in 25%, 50% and 75% Iron-Nickel Alloys” (in
French), Compt. Rend. Acad. Sci. Paris, Ser. 2, 295(10), 867–869 (1982) (Experimental, Interface
Phenomena, 15)
[1983Chu1] Chuang, Y.Y., Chang, Y.A., “A Thermodynamic Analysis of Ternary Cu-Ni-S and Fe-Ni-S” in “Adv.
Sulfide Smel.”, Proc. Int. Sulf. Smel. Symp. Extr. Proc. Met. Soc. AIME, 1, 73–79 (1983) (Experimental,
Thermodyn., 14)
[1983Chu2] Chuang, Y.Y., Chang, Y.A., “Thermodynamic Behavior of Metal-Sulfur Melts” in “Molten Salt Chem.
Technol.”, Proc. Int. Symp. Electrochem. Soc. Jpn., 1, 201–208 (1983) (Experimental, Phase Relations,
Thermodyn., 12)
[1983Net1] Netter, P., Barbouth, N., “Investigation of Sulfur Solubility in Iron-Nickel Alloys” (in French), Mem.
Etud. Sci. Rev. Metall., 80(12), 701–703 (1983) (Experimental, Phase Relations, 10)
[1983Net2] Netter, P., Barbouth, N., Oudar, J., “Thermodynamic Study of Iron-Nickel-Sulphur Solid Solutions”,
Scr. Metall., 17(9), 1083–1085 (1983) (Experimental, Thermodyn., 7)
[1983Van] Vanyukov, A.V., Khamin, A.G., Aleksandrov, M.E., Syromyatnikova, A.S., Asabin, A.N., “Phase
Equilibrium in the Nickel-Iron-Sulphur System” (in Russian), Nauchn. Trudy Moskov. Inst. Stali i
Splavov, 146(146), 50–54 (1983) (Experimental, Thermodyn., 6)
[1984Bee] Beek, J.A., Kok, P.M.T., Loo, F.J.J., “Solid-State Displacement Reactions in the Iron-Nickel-Sulfur and
Copper-Nickel-Sulfur Systems Between 400 and 500˚C”, Oxid. Met., 22(3–4), 147–160 (1984) (Experi-
mental, Phase Relations, 16)
[1984Khe] Khestanov, T.Kh., Kamyanov, V.K., Bystrov, V.P., “Equilibrium Vapour Pressure of Sulphur Over
Sulphides of the Iron-Nickel-Sulphur System Near NiS” (in Russian), Izv. Vyss. Uchebn. Zaved., Tsvetn.
Metall., (2), 54–59 (1984) (Experimental, Thermodyn., 5)
[1984Mar1] Marcus, P., Teissier, A., Oudar, J., “The Influence of Sulfur on the Dissolution and the Passivation of a
Nickel-Iron Alloy-1. Electrochemical and Radiotracer Measurements”, Corros. Sci., 24(4), 259–268
(1984) (Experimental, Thermodyn., 11)
[1984Mar2] Marcus, P., Olefjord, I., Oudar, J., “The Influence of Sulfur on the Dissolution and the Passivation of a
Nickel-Iron Alloy-II. Surface-Analysis by ESCA”, Corros. Sci., 24(4), 269–278 (1984) (Experimental,
Thermodyn., 12)
[1984Ros] Rossiter, P.L., Jago, R.A., “Towards a True Fe-Ni Phase Diagram”, Mater. Res. Soc. Symp. Proc., 21,
407–411 (1984) (Phase Diagram, Phase Relations, Review, 26)
[1984Sel] Sellamuthu, R., Goldstein, J.I., “Measurement and Analysis of Distribution Coefficients in Fe-Ni Alloys
Containing S and/or P: Part I. KNi and KP”, Metall. Trans. A, 15(9), 1677–1685 (1984) (Experimental,
Morphology, Phys. Prop., Thermodyn., 11)
[1986Jac] Jacob, K.T., Hajra, J.P., “Electromagnetic Levitation Study of Sulfur in Liquid Iron, Nickel and Iron-
Nickel Alloys”, Trans. Ind. Inst. Met., 39(1), 62–69 (1986) (Experimental, Phase Relations, 35)
[1987Con] Conard, B.R., Meyer, G.A., Timberg, L., Warner, J.S., Hynek, P., “Thermodynamic Activities of
Components in Homogeneous Ni-Fe-S Mattes at 1473-1673K”, Canad. Metall. Quart., 26, 299–309
(1987) (Experimental, Phase Diagram, Phase Relations, Thermodyn., 32)
[1987Fle] Fleet, M., “Structure of Godlevskite, Ni9S8”, Acta Crystallogr., C43, 2255–2257 (1987) (Crys. Structure,
Experimental, 12)
[1987Hsi1] Hsieh, K.-C., Kao, M.Y., Chung, A.Y. “Thermochemical Description of the Ternary Iron-Nickel-Sulfur
System”, Can. Metall. Quart., 26(4) 311–327 (1987) (Thermodyn., Phase Diagram, Theory, 33)
[1987Hsi2] Hsieh, K.-C., Vlach, K.C., Chang, Y.A., “The Fe-Ni-S System. I. A Thermodynamic Analysis of the
Phase Equilibria and Calculation of the Phase Diagram from 1173 to 1623 K”, High Temp. Sci., 23,
17–38 (1987) (Calculation, Experimental, Phase Diagram, Phase Relations, Thermodyn., 27)
[1987Hsi3] Hsieh, K.-G., Schmid, R., Chang, Y.A., “The Fe-Ni-S System. II. A Thermodynamic Model for the
Ternary Monosulfide Phase with the Nickel Arsenide Structure”, High Temp. Sci., 23, 39–52 (1987)
(Thermodyn., Calculation, 8)

Fe–Ni–S 11 59
[1987Hsi4] Hsieh, K.-Ch., Kao, M.-Y., Chang, Y.A., “A Thermogravimetric Investigation of the Fe-Ni-S System
from 700 to 900˚C”, Oxid. Met., 27(3–4), 123–141 (1987) (Experimental, Phase Diagram, Phase
Relations, 13)
[1987Ina] Inaba, M., Teshima, K., “Effects of Phosphorus and Sulphur on Thermal Expansion and Mechanical
Properties of Fe-36Ni”, J. Mater. Sci. Lett., 6(6), 727–728 (1987) (Experimental, Mechan. Prop., 9)
[1988Rag] Raghavan, V., “The Fe-Ni-S (Iron-Nickel-Sulphur) System” in “Phase Diagrams of Ternary Iron Alloys”,
Indian Inst. Met., Calcutta, 2, 196 (1988) (Review, Phase Relations, 8)
[1989Bar] Barbouth, N., Oudar, J., “Solubility and Diffusion of Sulfur in Pure Metals and Alloys” (in French),
Mem. Sci. Rev. Metall., 86(12), 777–788 (1989) (Review, Thermodyn., Phase Relations, 60)
[1989Bat] Battle, T.P., Pehlke, R.D., “Equilibrium Partition Coefficients in Iron-Based Alloys”, Metall. Trans. B,
20B, 149–160 (1989) (Experimental, Thermodyn., 61)
[1989Orc1] Orchard, J.P., Young, D.J., “Morphological Evolution During Sulfidation of an Iron-Nickel
Alloy”, Oxid. Met., 31(1-2), 105–121 (1989) (Experimental, Interface Phenomena, Morphology, Ther-
modyn., 17)
[1989Orc2] Orchard, J.P., Young, D.J., “Sulfidation Behavior of an Iron-Nickel Alloy”, J. Electrochem. Soc., 136(2),
545–550 (1989) (Experimental, Mechan. Prop., Phase Relations, Thermodyn., 32)
[1990Jon] Jones, J.H., Malvin, D.J., “A Nonmetal Interaction Model for the Segregation of Trace Metals during
Solidification of Fe-Ni-S, Fe-Ni-P, Fe-Ni-S-P Alloys”, Metall. Trans. B, 21B, 697–706 (1990) (Theory,
[1991Kes] Kesler, Y.A., Smirnov, S.G., Pokholok, K.V., Viting, B.N., “Peculiarities of the Electronic Structure of
Co, Ni-Thiospinel”, Inorg. Mater. (Engl. Transl.), 27, 977–980 (1991), translated from Izv. Akad. Nauk
SSSR. Neorg. Mater., 27(6), 1162–1165 (1991) (Experimental, Crys. Structure, 18)
[1991Swa] Swartzendruber, L.J., Itkin, V.P., Alcock, C.B., “Fe-Ni (Iron-Nickel)” in “Phase Diagrams of Binary
Nickel Alloys”, Nash, P. (Ed.), ASM International, Materials Park, OH, 110–132 (1991) (Phase Diagram,
[1991Tay] Taylor, J.R., Dinsdale, A.T., “Application of the Calculation of Phase Equilibria to the Pyrometallurgical
Extraction from Sulphide Ores” in “User Aspects of Phase Diagrams”, Proc. Conf., Petten, Netherlands
June 1990, Hayes, F.H. (Ed.), The Inst. Metals, UK, 209–224 (1991) (Calculation, Phase Diagram, Phase
Relations, 62)
[1993Lee] Lee, H.-K., Frohberg, M.G., Hajra, J.P., “Surface-Tension Measurements of Liquid Iron-Nickel-Sulfur
Ternary-System Using the Electromagnetic Oscillating Droplet Technique”, ISIJ Int., 33(8), 833–838
(1993) (Experimental, Interface Phenomena, 37)
[1994Sto] Stolen, S., Fjellvag, H., Gronvold, F., Seim, H., Westrum, E.F., “Phase Stability and Structural
Properties of Ni7±δS6 and Ni9S8 Heat Capacity and Thermodynamic Properties of Ni7S6 at Tempera-
tures from 5 K to 970 K and Ni9S8 from 5 K to 673 K”, J. Chem. Thermod., 26, 987–1000 (1994)
[1995Ma] Ma, L., Williams, D.B., Goldstein, J.I., “Phase-Decomposition in the Iron-Rich Iron-Nickel-Sulfur
System from 900 to 300˚C. - Application to Meteoritic Metal”, Meteoritics, 30(5), 538–539 (1995)
[1997Dre] Drebushchak, V.A., Fedorova, Z.N., Sinyakova, E.F., “Decay of (Fe1–xNix)0.96S - DSC Investigation”, J.
Therm. Anal., 48(4), 727–734 (1997) (Experimental, Kinetics, Phase Relations, Magn. Prop., 12)
[1997Nas] Nasch, P.M., Manghnani, M.H., Secco, R.A., “Anomalous Behavior of Sound Velocity and Attenuation
in Liquid Fe-Ni-S”, Science, 277(5323), 219–221 (1997) (Experimental, Thermodyn., 32)
[1998Kar] Karup-Moller, S., Makovicky, E., “The Phase System Fe-Ni-S at 900˚C”, Neues Jahrb. Mineral.,
Monatsh., 8, 373–384 (1998) (Experimental, Phase Relations, Thermodyn., 12)
[1998Kon] Kongoli, F., Dessureault, Y., Pelton, A.D., “Thermodynamic Modelling of Liquid Fe-Ni-Cu-Co-S
Mattes”, Metall. Mater. Trans. B, 29B, 591–601 (1998) (Assessment, Calculation, Phase Relations,
Thermodyn., 107)
[1998Ma] Ma, L., Williams, D.B., Goldstein, J.I., “Determination of the Fe-rich Portion of the Fe-Ni-S Phase
Diagram”, J. Phase Equilib., 19(4), 299–309 (1998) (Experimental, Phase Relations, 28)
[1998Sin] Sinyakova, E.F., Kosyakov, V.I., Shestakov, V.A., “Fe0.96S-Ni0.96S Join of the Fe-Ni-S System”, Inorg.
Mater. (Engl. Trans.), 34(5), 432–433 (1998) (Experimental, Phase Relations, 9)
[1999Kon] Kongoli, F., Pelton, A.D., “Model Prediction of Thermodynamic Properties of Co-Fe-Ni-S Mattes”,
Metall. Mater. Trans. B, 30B, 443–450 (1999) (Calculation, Phase Relations, Thermodyn., 51)

60 11 Fe–Ni–S
[1999Nko] Nkoma, J.S., Ekosse, G., “X-Ray Diffraction Study of Chalcopyrite CuFeS2, Pentlandite (Fe, Ni)9S8 and
Pyrrhotite Fe1–xS Obtained from Cu-Ni Ore Bodies”, J. Phys.: Condens. Matter, 11, 121–128 (1999)
(Experimental Crys. Structure, 10)
[1999Sin] Sinyakova, E.F., Kosyakov, V.I., Shestakov, V.A., “Investigation of the Surface of the Liquidus of the
Fe-Ni-S System at XS < 0.51”, Metall. Mater. Trans. B, 30B, 715–722 (1999) (Experimental, Phase
Relations, 20)
[2000Kim] Kim, E.C., “Crystallographic and Magnetic Properties of Iron Sulfides Doped with 3d Transition
Metals”, J. Mater. Sci. Letter., 19, 693–694 (2000) (Crys. Structure, Magn. Prop., Experimental, 8)
[2000Uen] Ueno, T., Ito, S.-I., Nakatsuka, S., Nakano, K., Harada, T., Yamazuaki, T., “Phase Equilibria in the
System Fe-Ni-S at 500 and 400˚C”, J. Mineral. Petrol. Sci., 95, 145–161 (2000) (Phase Diagram, Phase
Relations, Experimental, 28)
[2001Far] Farrell, S.P., Fleet, M.E., “Sulfur K XANES Study of Local Electronic Structure in Ternary Monosulfide
Solid Solution {(Fe, Co, Ni)0.923S}”, Phys. Chem. Miner., 28, 17–27 (2001) (Experimental, Crys.
Structure, Electronic Structure, 56)
[2001Kos] Kosyakov, V.I., Sinyakova, E.F., Nenashev, B.G., “A Mechanism of Pentlandite Formation in the Fe-Ni-
S System” (in Russian), Dokl. Akad. Nauk, Geokhimiya, 381(9), 1113–1115 (2001) (Experimental, Phase
Relations, 11)
[2001Sin1] Sinyakova, E.F., Kosyakov, V.I., “600˚C Section of the Fe-FeS-NiS-Ni Phase Diagram”, Inorg. Mater.
(Engl. Trans.), 37(11), 1130–1137 (2001), translated from Neorg. Mater., 37(11), 1327–1335 (2001)
(Experimental, Morphology, Phase Relations, Phase Diagram, 32)
[2001Sin2] Sinyakova, E.F., Kosyakov, V.I., Kolonin, G.R., “Behavior of Platinum Group Metals on Crystallization
of Melts of the Fe-Ni-S System (FexNi0.49–xS0.51 Section)” (in Russian), Geol. Geofiz., 42(9), 1354–1370
(2001) (Experimental, Morphology, Phase Relations, 35)
[2002Cha] Chauke, H.R., Nguyen-Manh, D., Ngoepe, P.E., Pettifor, D.G., Fries, S.G., “Electronic Structure and
Stability of the Pentlandites Co9S8 and (Fe,Ni)9S8”, Phys. Rev. B, 66(15), 155105 (2002) (Crys. Structure,
Experimental, 14)
[2003Cha] Chabot, N.L., Jones, J.H., “The Parameterization of Solid Metal-Liquid Metal Partitioning of
Siderophile Elements”, Meteor. Planet. Sci., 38(10), 1425–1436 (2003) (Experimental, Thermodyn., 46)
[2003Kos] Kosyakov, V.I., Sinyakova, E.F., Shestakov, V.A., “Dependence of Sulfur Fugacity on the Composition
of Phase Associations in the Fe-FeS-NiS-Ni System at 873 K”, Geochem. Int., 41(7), 660–669 (2003)
[2004Dis] Distler, V.V., Yudovskaya, M.A., Mitrofanov, G.L., Prokofév, V.Y., Lishnevskii, E.N., “Geology,
Composition, and Genesis of the Sukhoi Log Noble Metals Deposit, Russia”, Ore Geol. Rev., 24, 7–44
(2004) (Phase Diagram, Phase Relations, Review, 61)
[2004Ets] Etschmann, B., Pring, A., Putnis, A., Grguric, B., Studer, A., “A Kinetic Study of the Exsolution of
Pentlandite (Ni,Fe)9S8 from the Monosulfide Solid Solution (Fe,Ni)S”, Am. Mineral., 89, 39–50 (2004)
(Crys. Structure, Experimental, Kinetics, 42)
[2004Kos] Kosyakov, V.I., Sinyakova, V.F., “Investigation of Monovariant Peritectic Reaction in the Fe-Ni-S
Ternary System Using Oriented Crystallization Method” (in Russian), Zh. Neorg. Khim., 49(7),
[2004Rag] Raghavan, V., “Fe-Ni-S (Iron-Nickel-Sulfur)”, J. Phase Equilib. Diffus., 25(4), 373–381 (2004) (Phase
[2004Wal1] Waldner, P., Pelton, A.D., “Thermodynamic Modelling of the Ni-S System”, Z. Metallkd., 95(8)
672–681 (2004) (Assessment, Phase Diagram, Thermodyn., 49)
[2004Wal2] Waldner, P., Pelton, A.D., “Critical Thermodynamic Assessment and Modeling of the Fe-Ni-S System”,
Metall. Mater. Trans. B, 35b(5), 897–907 (2004) (Assessment, Phase Diagram, Thermodyn., 35)
[2005Nam] Nam, H.D., Kim, E.C., Han, J.S., “Mössbauer Study of Iron Sulfides Doped with 3d-Transition Metals”,
Solid State Commun., 135(5), 327–329 (2005) (Experimental, Crys. Structure, Electronic Structure,
Phase Relations, 8)
[2006Leh] Lehner, S.W., Savage, K.S., Ayers, J.C., “Vapor Growth and Characterization of Pyrite (FeS2) Doped
with Co, Ni, and As: Variations in Semiconducting Properties”, J. Cryst. Growth, 286(2), 306–317 (2006)
(Experimental, Electr. Prop., Semicond.,38)
[2006Rag] Raghavan, V., “Fe-Ni-S (Iron-Nickel-Sulfur)”, J. Phase Equilib. Diffus., 27(3), 293–295 (2006) (Review,
Calculation, Phase Diagram, Phase Relations, 4)

Fe–Ni–S 11 61
[2006Sin] Sinyakova, E.F., Kosyakov, V.I., “Phase Relationships and Sulfur Fugacity in the System Fe-FeS-NiS-Ni
at 900˚C” (in Russian), Russ. Geol. Geophys., 47(7), 835–846 (2006) (Experimental, Morphology, Phase
Relations, 34)
[2006Wal1] Waldner, P., “Thermodynamic Analysis of High-Temperature Heazlewoodite”, Z. Metallkd., 97(1)
17–21 (2006) (Calculation, Thermodyn., Phase Diagram, Phase Relations, 33)
[2006Wal2] Waldner, P., Sitte, W., “Thermodynamic Modeling of High-Temperature Fe-Ni-Heazlewoodite”, Ad-
vanced Eng. Mater., 8(11), 1161–1164 (2006) (Calculation, Experimental, Phase Diagram, Phase Rela-
tions, Thermodyn., 21)
[2008Fer] Ferro, R., Bochvar, N., Sheftel, E., Ding, J.-J., “Fe-S (Iron-Sulfur)”, MSIT Binary Evaluation Program, in
MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services, GmbH, Stuttgart;
to be published (2008) (Crys. Structure, Phase Diagram, Phase Relations, Assessment, 28)
(1990)

Fe–Ni–Sb 12 1
Iron – Nickel – Antimony

Marina Bulanova, Yulia Fartushna
Introduction
The Fe-Ni-Sb system is of practical importance for different fields of application. Thus,
Sb-induced embrittlement of alloy steels results from antimony segregation at the grain
boundaries of (αFe,Ni,Sb), which, in turn, strongly depend on the Ni content. Last two
decades much attention is focused on skutterudite thermoelectric materials, where Fe-Ni-Sb
is one of the boundary system. So, understanding of phase equilibria in this system gives
possibilities to control the properties of Fe-Ni-Sb-based materials.
First information on the system appeared in 1943, when [1943Age1, 1943Age2] reported a
continuous solid solution between FeSb and NiSb. [1970Bje] found the ternary compound
Fe0.5Ni0.5Sb3 (τ) and a limited mutual solid solubility of FeSb2 and NiSb2. Later [2003Zha]
reported on a new semi-Heusler phase FeNiSb, which seems to be metastable.
Phase relations in the Fe-Ni-Sb system were studied by [1973Pan, 1997Ric1, 1997Ric2,
2003Voi] and resulted in a partial liquidus surface [1997Ric1], isothermal sections at 1150
[2003Voi] and 600˚C [1997Ric1], a number of vertical sections [1973Pan, 1997Ric1,
1997Ric2], reaction scheme [1997Ric1]. Note, that the work of [1997Ric1] is the key-paper
on phase relations in the system, giving the comprehensive information concerning the phase
equilibria at more than 50 at.% Sb. Experimental data are given also for the samples with 35,
42 and 46 at.% Sb, however phase equilibria in the concentration range < 50 at.% Sb are not
established in details. Thermodynamics of alloys is given by [1997Ric2, 2003Voi].
Solubility of Sb in (αFe,Ni) and the nature of precipitates was studied by [1974Nag,
1976Nag]. The grain boundary segregation and cosegregation in (αFe,Ni,Sb) is given by
[1986Gas].
[1977Gal, 1980Gel] reported the structure and magnetic properties of the (Fe,Ni)Sb (ε)
phase. Magnetic properties of metal-enriched monoantimonide (Fe1–yNiy)1+xSb are given by
[1984Har]. [1973Kje] and [1974Kje] studied the Mössbauer effect in the ternary compound τ
and in the FeSb2-based phase FexNi1–xSb2, respectively.
[1992Rag, 2004Rag1, 2004Rag2] reviewed the Fe-Ni-Sb system.
The structure and properties of skutterudites were studied by [2003Mor, 2005Cha,
2005Mi].
The experimental researches of phase relations and related questions in the ternary Fe-Ni-
Sb system are summarized in Table 1.
Binary Systems
The Fe-Ni and Fe-Sb binary systems are accepted from [2008Kuz] and [1995Pei], respectively.
The Ni-Sb phase diagram is taken basically from [Mas2]. The composition and temperatures

2 12 Fe–Ni–Sb
of invariant points of liquid in the Sb rich part are accepted from [1989Fes] to accord with
experimental results of [1997Ric1] on the ternary system.
Solid Phases
The Fe-Ni-Sb solid phases are reported in Table 2. The ternary compound Fe0.5Ni0.5Sb3 (τ),
first found by [1970Bje], forms by a P type peritectic reaction at 642˚C [1997Ric1] and
crystallizes in a cubic CoAs3 type structure. It has a narrow homogeneity range due to the
mutual substitution of Fe and Ni, so that the formula can be written as Fe0.5-0.46Ni0.5-0.54Sb3.
Despite band calculations predicted unstable ferromagnetic state and crystal structure,
[2003Zha] prepared a new semi-Heusler phase FeNiSb by melt-spinning technique and
studied its electronic structure, magnetic and transport properties. The phase is ferromagnetic
and melts at 991˚C without any phase transformation at lower temperatures. However,
according to the preparation method, the phase might be metastable.
[1943Age1, 1943Age2] reported a continuous solid solubility of FeSb and NiSb at 600˚C
(ε phase). The metal-rich part of the solid solution is of interstitial type, the Sb rich part has a
defect structure. Figure 1a shows the lattice parameters of the phase as measured by
[1997Ric1] for the isoconcentrate 46 at.% Sb. The data are in reasonable agreement with
data [1977Gal], Table 2. Essential narrowing of the homogeneity region of the phase in Sb
content in a middle part (see isothermal section at 600˚C, Fig. 6) allowed [1997Ric1] to make
an assumption of the possible arising of the miscibility gap at lower temperatures.
Isostructural FeSb2 and NiSb2 do not form a continuous solid solution. According to
[1970Bje], at 600˚C the solubility of Ni in FeSb2 is about 16.7 at.%, the phase is written by the
formula (FexNi1–x)Sb2 (0.5 < x < 1). This value is confirmed by [1997Ric1]. According to the
last paper, the solubility of Fe in NiSb2 is no more than 2 at.%. The concentration dependence
of the lattice parameters of FexNi1–xSb2 is shown in Fig. 1b. [1997Ric1] has shown that the
solubility of Fe in Ni5Sb2 at 600˚C is about 5 at.%.
Quasibinary Systems
According to [1997Ric1, 1997Ric2], the Fe-Ni-Sb system is triangulated by the (Fe,Ni)Sb
phase into two subsystems: Fe-FeSb-NiSb-Ni and FeSb-Sb-NiSb. Thus, the section FeSb-NiSb
is quasibinary. However, the quasibinarity does not occur along the equiatomic isoconcentrate
50 at.% Sb, but along the section passing via distectic points Fe0.573Sb0.427-Ni0.511Sb0.489.
By the methods of thermal analysis, metallography and hardness measurements [1973Pan]
constructed the section Fe-NiSb, which was claimed to be quasibinary. This, meanwhile, is not
so, as (1) it does not go via the distectic point of NiSb; (2) if it was, extremes at the solidus
surfaces (γFe,Ni)+ε and (δFe,Ni)+ε should take place, that is questionable.
Four invariant equilibria were established [1997Ric1] at above 600˚C in the Sb rich subsystem.
These are a P type equilibrium at 642˚C, two U type equilibria at 625 and 620˚C and a E type
equilibrium at 616˚C. The compositions of the phases taking part in these equilibria were
Fe–Ni–Sb 12 3
determined. All the equilibrium points of liquid are located at more than 90 at.% Sb. Invariant
equilibria, coordinates of invariant points, compositions of the coexisting solid phases are
shown in Table 3. Based on the experimental data of [1997Ric1, 1997Ric2] and on the
boundary binaries it is possible to propose the character of invariant equilibria with partici-
pation of the liquid for the Sb-poor subsystem, as well. Here two U type equilibria should
occur: L + Ni5Sb2 ⊊Ð⊊ ε + γ and L + γ Ð ε + δα. The temperature decreases slowly from
1072˚C in the eutectic l Ð⊊ Ni5Sb2+ε to 998˚C in the eutectic l Ð ε + (δFe). So, the
temperature of the above four phase equilibria appears in this temperature interval, and the
temperature 1000˚C declared by [1997Ric1] and [1973Pan] as the temperature of an invariant
equilibrium (according to [1973Pan], of the invariant three-phase equilibrium l Ð εαffl + γ),
might be the temperature of the monovariant equilibrium l ⊊Ð⊊ εαffl + γ, which decreases very
slowly. These equilibria are also shown in Table 3. The resulted reaction scheme is given in
Fig. 2. Experimental results [1997Ric1] are given in solid, resulting of our assessment are given
in dotted lines. The scheme is limited from below by the temperature 600˚C.
Based on the boundary binary systems, [1991But] predicted full liquid miscibility in the
system. This was confirmed later. By the DTA method [1997Ric1] constructed the liquidus
isotherms via 20˚C at 40 to 90 at.% Sb, as shown in Fig. 3a. These are limited by the
temperature 1140˚C. Coordinates of the invariant points of liquid, determined in this work,
allowed [2004Rag1] to plot a liquidus projection in the Sb corner (>90 at.% Sb), Fig. 3b. Data
[1997Ric1, 1997Ric2, 2003Voi] and the boundary binary systems allowed us to assess the
liquidus projection for the Sb poor subsystem. It is shown in Fig. 4 together with few
isotherms in the Sb rich field. According to the observations of [1973Pan], the monovariant
curve l Ð⊊ εαffl + γ is located at about 30 at.% Sb. Isotherms of [1997Ric1, 2003Voi] are shown
by solid curves, those assessed by us are given as dashed ones.
The solidus surface of the Fe-Ni-Sb system was not specially studied. However, composi-
tions of the phases taking part in invariant equilibria in the Sb rich subsystem [1997Ric1],
Table 3, allowed us to plot a partial solidus surface, shown in Fig. 5.
According to [1974Nag], 1 at.% Ni in the alloy Fe-4Sb decreases solubility at 600˚C of Sb in
(αFe) from 2.5 to 1.6 at.% resulting in precipitation of the ε phase. [1976Nag] reported that
after ageing at 550˚C for 120 h a precipitation takes place over the entire volume, in contrast to
the Ni-free alloy. According to [1997Ric1], at 600˚C (αFe,Ni) and (γFe,Ni) dissolve, respec-
tively, 1 and 2 at.% Sb.
Isothermal Sections
Two isothermal sections are reported in the Fe-Ni-Sb system. From X-ray diffraction and
EPMA results [1997Ric1] constructed the isothermal section at 600˚C. To achieve equilibrium
state the samples for EPMA examination were annealed at this temperature for 6 months.
The section shown in the paper [1997Ric1] covers the composition interval 40 to 100 at.% Sb
(Sb rich subsystem). However, the EPMA results given involve the whole concentration
interval. This allowed us to plot the whole isothermal section at 600˚C. Three-phase regions
δα + γ + ε and γ + Ni5Sb3 + Ni3Sb are added by us. A similar plot was done by [2004Rag1].
However, it is somewhat inconsistent with the accepted here Fe-Ni binary system. The section
4 12 Fe–Ni–Sb
is shown in Fig. 6 due to experimental data [1997Ric1] (in solid) and our assessment (in
dashed).
By quenching from the solid-liquid state, and using the methods of metallography and
EPMA, [2003Voi] constructed the isothermal section at 1150˚C. This involves equilibria of
liquid with δα and with (γFe,Ni). In [2003Voi], however, the two modifications of the solid
solution are not specified. [2004Rag2] includes this correction, as shown in Fig. 7. Solid curves
correspond to the original work [2003Voi], dashed ones - to [2004Rag2].
[1997Ric1] constructed the isopleths below liquidus along the isoconcentrates 66.7, 70, 75 and
85 at.% Sb, and [1997Ric2] reported the vertical section along FeNi-Sb at 40-90 at.% Sb. The
sections at 70 and 85 at.% Sb and FeNi-Sb are shown in Figs. 8a to 8c.
Thermodynamics
By isothermal isopiestic method [2003Voi] measured activities of Sb at 1150˚C, the isoactivity

curves were constructed, showing negative deviation from the ideal behavior and a negative
gradient against the Fe content, thus, specifying stronger chemical affinity for Ni-Sb than for
Fe-Sb. By the Gibbs-Duhem integration method isoactivity lines for Fe and Ni were estimated.
By the same method [1997Ric2] determined partial molar enthalpies and activities of Sb in
the ε phase at Fe:Ni = 1:1 and 45.5-51.5 at.% Sb for 900˚C.
[1977Gal, 1980Gel] studied magnetic properties of the monoantimonide phase along the
sections FeSb-NiSb, Fe1.2Sb-Ni1.2Sb, Fe1.2Sb-NiSb. Ferromagnetism was absent in the alloys
along the first section, and had the highest level along the second one. It is accounted for by
location of the metal atoms in the bipyramidal interstitials of the crystal lattice [1977Gal].
[1980Gel] has shown that magnetic moments of the Fe-atoms at the d-sites are ferromagne-
tically ordered. Substitution of Fe- by Ni-atoms at the a-sites results in collinear antiferro-
magnetism. By using X-ray diffraction and Mössbauer spectra of (Fe1–yNiy)1+xSb
(0.02≤y≤0.42, 0.08≤x≤0.16), [1984Har] has shown that the Neel temperature decreases linearly
when y increases. This results, as well, in two magnetic hyperfine fields, which are about 40 and
80% lower than in the Fe1–xSb. The value of the fields does not depend on Ni content.
Magnetization vs temperature of a new semi-Heusler phase FeNiSb [2003Zha] is inter-
preted in the spin-wave theory, electrical resistivity follows a T5 behavior.
[1986Gas] gives diffusion parameters of Fe, Ni and Sb in (αFe,Ni,Sb).
Miscellaneous
[1973Kje] has shown the predominant covalent nature of the chemical bonding in the ternary
compound τ. According to [1974Kje], an increase of the Ni content in FexNi1–xSb2 results in an
increase of the Ni-Sb interatomic distances.

Fe–Ni–Sb 12 5
Nanostructured ternary unfilled skutterudite Fe0.5Ni0.5Sb3 was synthesized at 240˚C for 48

h by a solvothermal method [2005Mi] with particles size about 50 nm and metallic electrical
properties. Neutron diffraction and transmission electron microscopy were used by [2005Cha,
2003Mor], respectively, to study partially filled skutterudite structure in the Ce-Fe-Ni-Sb
system.
. Table 1
Investigations of the Fe-Ni-Sb Phase Relations, Structures and Thermodynamics

[1943Age1] Homogenization at 600˚C for three days, 600˚C / FeSb-NiSb continuous solid
slow cooling; optical microscopy, solution
electrical conductivity measurements,
powder XRD
[1943Age2] Homogenization at 600˚C for three days, 600˚C / FeSb-NiSb continuous solid
slow cooling; optical microscopy, solution
electrical conductivity measurements,
powder XRD
[1970Bje] Preparation from FeSb2 and NiSb2 by 600˚C / FeSb2-NiSb2 section; ternary
annealing, crashing and reanealling at compound FeNiSb6 (τ)
600˚C for several times to reach
homogeneity; powder XRD with KCl
internal standard
[1973Pan] DTA, optical microscopy, hardness and Vertical section Fe-NiSb
magnetic susceptibility measurements
[1974Nag] Homogenization treatment 975˚C / 94 h 975, 650, 600˚C / Fe-1Ni-4Sb / solubility of
+ 850˚C / 6 h; powder XRD Sb in (αFe,Ni), lattice parameters
[1976Nag] Homogenization treatment 975˚C / 94 h; Fe-1Ni-8.3Sb / solubility of Sb in (αFe,Ni)
optical microscopy, SEM, TEM
[1977Gal] Heat treatment 600˚C/ 30 h; XRD; 600˚C / (Fe,Ni)Sb phase along the
temperature-field dependencies, sections Fe1.2Sb-Ni1.2Sb, FeSb-NiSb,
magnetic intensity, susceptibility Fe1.2Sb-NiSb, lattice parameters
measurements; Mössbauer spectra
[1997Ric1] Synthesis in quartz ampoules at 1200˚C, 900˚C / ε phase (FeyNi1–y)1±xSb / lattice
homogenization at 900˚C / 3 weeks, or at parameters; 600˚C / isothermal section
600˚C / 6 weeks; DTA, metallography, for Sb-subsystem / lattice parameters of
XRD, EPMA ε phase and of (Fe,Ni)Sb2; liquidus
isotherms for Sb-subsystem, vertical
sections at 66.7, 70, 75, 85 at.% Sb;
reaction scheme

6 12 Fe–Ni–Sb

[1997Ric2] Synthesis in quartz ampoules at 1100˚C, Vertical section FeNi-Sb at 42-90 at.% Sb;
homogenization at 500˚C / 3 weeks; DTA, antimony vapor pressure in
XRD; isopiestic method (Fe0.5Ni0.5)1±xSb at 45.4-51.5 at.% Sb at
747-1037˚C; partial molar properties of Sb
at 1150˚C
[2003Voi] Synthesis in quartz ampoules at 1200˚C, 1150˚C / isothermal section; isoactivity
quenching from 1150˚C; metallography, curves of Sb; calculated isoactivity curves
EPMA; isopiestic method of Fe, Ni
[2003Zha] Melt-spinning; XRD; DTA; magnetization FeNiSb semi-Heusler phase, electrical and
and electrical resistivity measurements magnetic properties, lattice parameters
. Table 2
Pearson
Symbol/
δα, (δFe,αFe) cI2

Im3m
(δFe) W a = 293.15 [Mas2]
1538 - 1394
(αFe) a = 286.65 at 25˚C [Mas2]
< 912 a = 287.36 [V-C2], Fe0.96Sb0.04
a = 290.0 [V-C2], Fe0.95Sb0.05
(αFe,Ni,Sb) a = 287.81 [1974Nag], in alloy
Fe-1Ni-4Sb, 600˚C
a = 288.03 [1974Nag], in alloy
Fe-1Ni-4Sb, 650˚C
a = 289.24 [1974Nag], in alloy
Fe-1Ni-4Sb, 975˚C
γ, (γFe,Ni) cF4
Fm3m
(γFe) Cu a = 364.67 at 915˚C [V-C2, Mas2]
< 1394 - 912
(Ni) a = 352.40 at 25˚C [Mas2]
< 1455
P63/mmc c = 396.0
Mg

Fe–Ni–Sb 12 7
Pearson
Symbol/
(Sb) hR6 a = 450.67 [Mas2]

< 630.755 R3m α = 57.11˚
αAs
γ’, FeNi3 cP4 a = 355.23 63 to 85 at.% Ni [1991Swa]
< 517 Pm3m
AuCu3
γ’’, FeNi tP4 a = 357.9 [V-C2], metastable.
P4/mmm Metastable ordering temperature 320˚C at
51.2 at.% Ni [1984Ros]
AuCu
(FexNi1–x)Sb2 oP6 0.5 ≤ x ≤ 1
Pnnm a = 564.17 ± 0.09 x = 0.5 [V-C2]
FeS2 b = 644.02 ± 0.09
c = 338.55 ± 0.05
FeSb2 a = 583.28 ± 0.05 [V-C2]
< 738 b = 653.76 ± 0.05
c = 319.73 ± 0.03
FeSb4 cP1 - [Mas2], metastable
Pm3m
αPo
Ni15Sb - - [Mas2], ordering
< 460
Ni3Sb oP8 a = 532.07 ± 0.08 [V-C2]
< 715 Pmmm b = 428.08 ± 0.03
βTiCu3 c = 451.47 ± 0.04
Ni5Sb2 mC28 a = 1294.58 [V-C2]
1161 - 530 C2 b = 542.71
Ni5Sb2 c = 1145.68
β = 151.71˚
Ni7Sb3 t** - [Mas2]
< 600
NiSb2 oP6 a = 518.23 ± 0.05 [V-C2]
< 621 Pnnm b = 631.68 ± 0.07
FeS2 c = 384.03 ± 0.05

8 12 Fe–Ni–Sb
Pearson
Symbol/
ε, (FexNi1–x)Sb hP4 a = 393.8 [1977Gal]1), x = 0.3

P63/mmc c = 514.5 dpycn. = 8.531 g·cm–3
NiAs a = 394.7 [1977Gal], x = 0.2
c = 514.2 dpycn. = 8.535 g·cm–3
a = 393.8 [1977Gal], x = 0.1
c = 514.1 dpycn. = 8.544 g·cm–3
(FexNi1–x)1.2Sb a = 401.3 [1977Gal], x = 0.7
c = 520.1 dpycn. = 8.347 g·cm–3
a = 397.3 [1977Gal], x = 0.5
c = 513.2 dpycn. = 8.441 g·cm–3
a = 403.6 [1977Gal], x = 0.3
c = 518.4 dpycn. = 9.498 g·cm–3
a = 395.9 [1977Gal], x = 0.2
c = 511.4 dpycn. = 8.537 g·cm–3
a = 395.0 [1977Gal], x = 0.15
c = 514.2 dpycn. = 8.595 g·cm–3
a = 396.9 [1977Gal], x = 0.1
c = 515.5 dpycn. = 8.637 g·cm–3
Fe1.2xNi1–xSb a = 397.1 [1977Gal], x = 0.4
c = 513.5 dpycn. = 8.486 g·cm–3
a = 402.9 [1977Gal], x = 0.6
c = 511.9 dpycn. = 8.411 g·cm–3
FeSb a = 412.4 [V-C2], Fe0.56Sb0.44, 520˚C
< 1019 c = 517.3
a = 515.3 [1974Nag], in alloy Fe-1Ni-4Sb, 650˚C;
c = 403.2 ε phase contains about 13 at.% Ni
NiSb a = 393.25 [V-C2]
< 1147 c = 513.51
*τ, Fe0.5Ni0.5Sb3 cI32 Fe0.5-0.46Cu0.5-0.54Sb3
Im3 a = 909.02 ± 0.05 [1970Bje]
CoAs3 dpycn. = 7.411 g·cm–3 at 25˚C
a = 909.04 ± 0.05 FeNiSb6 [V-C2]
FeNiSb C1b a = 572 ± 2 [2003Zha] semi-Heusler phase, metastable
1)
Parameters a and c are replaced.

Fe–Ni–Sb 12 9
. Table 3
Composition (at.%)
Reaction T [˚C] Type Phase Fe Ni Sb Reference
L + ε + FeSb2 Ð τ 642 P L 3.5 2.5 94 [1997Ric1]

ε 1.5 46 52.5
FeSb2 16.7 16.7 66.7
τ 12 13 75
L + ε Ð NiSb2 + τ 625 U31) L 0.5 4.5 95 [1997Ric1]
ε 1 46 53
NiSb2 0 33.3 66.7
τ 11.5 13.5 75
L + FeSb2Ðτ + (Sb) 620 U42) L 1 3 96 [1997Ric1]
FeSb2 22.8 10.5 66.7
τ 12.5 12.5 75
(Sb) 0 0 100
L Ð NiSb2 + τ + (Sb) 615 E L 0 3 97 [1997Ric1]
NiSb2 0 33.3 66.7
τ 11.5 13.5 75
(Sb) 0 0 100
L + Ni5Sb2 Ð ε + γ 998<T<1072 U1 L - - - assessed
L + γ Ð ε + αffl δα 998<T<1072 U2 L - - - assessed
1)
Labeled IIa by [1997Ric1].
2)
Labeled IIb by [1997Ric1].

10 12 Fe–Ni–Sb
. Fig. 1a
Fe-Ni-Sb. Lattice parameters of the monoantimonide (FexNi1–x)54Sb46 as a function of Ni
concentration

Fe–Ni–Sb 12 11
. Fig. 1b
Fe-Ni-Sb. Lattice parameters of the diantimonide (Fe,Ni)Sb2 as a function of Ni concentration

12 12
Fe-Ni-Sb. Reaction scheme
. Fig. 2
Fe–Ni–Sb

Fe–Ni–Sb 12 13
. Fig. 3a
Fe-Ni-Sb. The liquidus isotherms in the Sb rich subsystem

14 12 Fe–Ni–Sb
. Fig. 3b
Fe-Ni-Sb. A fragment of the liquidus surface projection above 90 at.% Sb

Fe–Ni–Sb 12 15
. Fig. 4
Fe-Ni-Sb. Assessed liquidus surface projection

16 12 Fe–Ni–Sb
. Fig. 5
Fe-Ni-Sb. Partial solidus surface projection

Fe–Ni–Sb 12 17
. Fig. 6
Fe-Ni-Sb. Isothermal section at 600˚C

18 12 Fe–Ni–Sb
. Fig. 7
Fe-Ni-Sb. Isothermal section at 1150˚C

Fe–Ni–Sb 12 19
. Fig. 8a
Fe-Ni-Sb. Vertical section at 70 at.% Sb

20 12 Fe–Ni–Sb
. Fig. 8b
Fe-Ni-Sb. Vertical section at 85 at.% Sb

Fe–Ni–Sb 12 21
. Fig. 8c
Fe-Ni-Sb. Partial vertical sections along the FeNi – Sb join

22 12 Fe–Ni–Sb
References
[1943Age1] Ageev, N.V., Makarov, E.S., “Continuous Transition Between the Daltonide and the Berthollide Phases
in the System Iron-Nickel-Antimony”, Compt. Rend. Sci. Acad. URSS, 38, 20–21 (1943), translated from
Izv. Akad Nauk SSSR (Khim.), 161 (1943) (Experimental, Phase Relations, 6)
[1943Age2] Ageev, N.V., Makarov, E.S., Zhur. Obshchey Khimii, 13, 242 (1943)
[1970Bje] Bjerkelund, E., Kjekshus, A., “Compounds with the Marcasite Type Crystal Structure”, Acta Chem.
Scand., 24, 3317–3325 (1970) (Crys. Structure, Experimental, 35)
[1973Kje] Kjekshus, A., Nicholson, D.G., Rakke, T., “Compounds with the Skutterudite Type Crystal Structure”,
Acta Chem. Scand., 27, 1315–1320 (1973) (Crys. Structure, Experimental, 19)
[1973Pan] Panteleimonov, L.A., Babanskaya, I.A., “The Interaction Compound NiSb with Iron and Cobalt”, Vestn.
Moskov. Univ., (Khim.), 14, 373 (Phase Relations, Phase Diagram, Experimental, 1973)
[1974Kje] Kjekshus, A., Rakke, T., “Compounds with the Marcasite Type Crystal Structure. X. 57Fe Mössbauer
Studies of Some Ternary Pnictides”, Acta Chem. Scand., Ser. A, 28A(9), 1001–1010 (1974) (Crys.
[1974Nag] Nageswararao, M., McMahon, C.J., Herman, H., “The Solubility and Solution Behaviour of Sb and Sn
in α-Fe and the Effects of Ni and Cr Additions”, Metall. Trans., 5, 1061–1068 (1974) (Experimental,
[1976Nag] Nageswararao, M., Herman, H., McMahon, C.J., “On the Decomposition of Supersaturated Fe-Sb, Fe-
Sn, Fe-Sb-Ni Solid Solutions”, Met. Sci., 10(7), 249–252 (1976) (Experimental, Phase Relations, 9)
[1977Gal] Galperina, T.N., Zelenin, L.P., Fedorova, T.A., Sidorenko, F.A., Geld, P.V., “The Magnetic Properties of
the Mutual Solid Solutions of the Mono-Antimonides”, Phys. Met. Metallogr., 43, 183–185 (1977),
translated from Fiz. Metal. Metalloved., 43(3) 661–663 (1977) (Experimental, Magn. Prop., 7)
[1980Gel] Geld, P.V., Galperina, T.N., Babanova, E.N., Sidorenko, F.A., “Magnetic and Atomic Structure of the
Monoantimonide Phases Fe1+xSb and (Fe1–yNiy)1.2Sb”, Sov. Phys.-Dokl. (Engl. Transl.), 253, 545–546
(1980), translated from Dokl. Akad. Nauk SSSR, 253, 85–87 (1980) (Experimental, Crys. Structure,
Magn. Prop., 3)
[1984Har] Harchand, K.S., Kumar, R., Vishwamittar, Kumar, D., Chandra, K., “Influence of Nickel Substitution in
an Fe-Sb Triangular Antiferromagnetic System”, Phys. Rev. B., 30(3) 1527–1533 (1984) (Phase Relations,
Experimental, 15)
[1984Ros] Rossiter, P.L., Jago, R.A., “Towards a True Fe-Ni Phase Diagram”, Mater. Res. Soc. Symp. Proc.,
21, 407–411 (1984) (Phase Diagram, Review, 26)
[1986Gas] Gas, P., Poize, S., Bernardini, J., “Influence of Cosegregation on Grain Boundary Diffusion:
Experimental Study in Ultra High Purity Fe-Ni-Sb Solid Solutions”, Acta Metall., 34(3), 395–403 (1986)
(Phase Relations, Experimental, 17)
[1989Fes] Feschotte, P., Lorin, D., “Binary Systems Fe-Sb, Co-Sb and Ni-Sb” (in French), J. Less-Common Met.,
155, 255–269 (1989) (Phase Diagram, Phase Relations, Experimental, 12)
[1991But] Butt, M.T.Z., Bodsworth, C., “Liquid Immisicibility in Ternary Metallic Systems”, Mater. Sci. Technol.,
7(9), 795–802 (1991) (Experimental, Phase Relations, Phase Diagram, Review, 39)
[1991Swa] Swartzendruber, L.J., Itkin, V.P., Alcock, C.B., “The Fe-Ni (Iron-Nickel) System”, J. Phase Equilib., 12(3),
288–312 (1991) (Assessment, Phase Diagram, Phase Relations, 89)
[1992Rag] Raghavan, V., “The Fe-Ni-Sb (Iron-Nickel-Antimony) System” in “Phase Diagrams of Ternary Iron
Alloys”, Indian Inst. Met., Calcutta, 6B, 1061–1062 (1992) (Crys. Structure, Phase Diagram, Phase
[1995Pei] Pei, B., Bjorkman, B., Sundman, B., Jansson, B., “A Thermodynamic Assessment of the Iron-Antimony
System“, Calphad, 19(1), 1–15 (1995) (Phase Diagram, Phase Relations, Thermodyn., Assessment, 37)
[1997Ric1] Richter, K.W., Ipser, H., “An Experimental Investigation of the Fe-Ni-Sb Ternary Phase Diagram”,
J. Phase Equilib., 18(3), 235–224 (1997) (Experimental, Phase Relations, Review, #, 15)
[1997Ric2] Richter, K.W., Ipser, H., “The Section (Fe0.5Ni0.5)xSb1–x: Phase Relationships and Thermodynamic
Properties”, Z. Metallkd., 88(11), 873–879 (1997) (Experimental, Phase Relations, Thermodyn., #, 19)
[2003Mor] Morimura, T., Hasaka, M., “Partially Filled Skutterudite Structure in CefFe8–xNixSb24“, Scr. Mater., 48,
[2003Voi] Voisin, L., Hino, M., Itagaki, K., “Phase Relations and Activities in the Fe-Ni-As and Fe-Ni-Sb Systems
at 1423 K”, Mater. Trans., 44(12), 2654–2658 (2003) (Phase Relations, Thermodyn., Experimental, 13)

Fe–Ni–Sb 12 23
[2003Zha] Zhang, M., Liu, Zh., Hu, H., Cui, Y., Liu, G., Chen, J., Wu, G., Sui, Y., Qian, Zh., Li, Zh., Tao, H., Zhao,
B., Wen, H., “A New Semi-Heusler Ferromagnet NiFeSb: Electronic Structure, Magnetism and
Transport Properties”, Solid State Commun., 128(2-3), 107–111 (2003) (Calculation, Crys. Structure,
Electr. Prop., Electronic Structure, Experimental, Magn. Prop., 26)
[2004Rag1] Raghavan, V., “Fe-Ni-Sb (Iron-Nickel-Antimony)”, J. Phase Equilib. Diffus., 25(1), 89–91 (2004) (Phase
[2004Rag2] Raghavan, V., “Fe-Ni-Sb (Iron-Nickel-Antimony)”, J. Phase Equilib. Diffus., 25(6), 553 (2004) (Phase
[2005Cha] Chapon, L.C., Girard, L., Haidoux, A., Smith, R.I., Ravot, D., “Structural Changes Induced by Ce
Filling in Partially Filled Skutterudites”, J. Phys.: Condens. Matter, 17, 3525–3535 (2005) (Crys. Struc-
ture, Experimental, Phase Relations, Phys. Prop., 21)
[2005Mi] Mi, J.L., Zhao, X.B., Zhu, T.J., Tu, J.P., Cao, G.S., “Solvothermal Synthesis of Nanostructured Ternary
Skutterudite Fe0.5Ni0.5Sb3”, J. Alloys Compd., 399(1-2), 260–263 (2005) (Electr. Prop., Experimental,
Morphology, 15)
(1990)

Fe–Ni–Si 13 1
Iron – Nickel – Silicon

Elena Semenova
Introduction
Fe-Ni-Si alloys belong to the group of soft magnetic materials having high permeability
(permalloy effect). This and other special characteristics have led to these alloys being widely
used in industry. As the properties of the alloys were found to depend on chemical composi-
tion, heat treatment and the method of preparation, their investigation has been accompanied,
in many cases, by the study of their phase relationships.
The constitution of the Fe-Ni-Si system was critically evaluated by [1988Ray]. The
assessment covers all known investigations of phase relationships up to 1980 [1938Alt,
1943Gre, 1955Tak, 1960Tak, 1960Iwa, 1961Wit, 1962Gla, 1965Mir, 1965Bor, 1965Bur,
1968Dmi, 1968Mir, 1968Sid1, 1968Sid2, 1969Mir, 1970Gom, 1972Fro, 1977Nic, 1979Ind,
1980Cha]. The isothermal section at 600˚C, hypothetical liquidus projection and scheme of
possible reaction sequence were proposed by [1988Ray] as part of the review. A thermody-
namic assessment of the system was undertaken by [1980Cha] who based their calculations on
experimental studies which were later also considered by [1988Ray] in the critical evaluation.
The reviews by [1994Rag, 2003Rag] added new information on the phase diagram of the
system, including [1994Koz] and the experimental study of [1998Ike] and thermodynamic
assessment of [1999Mie], which was based mainly on the data of [1998Ike].
[1943Gre] studied the constitution of ternary alloys in the Fe-Ni-Si system in the region
50-100 at.% Fe. In addition to the phases based on the modifications of iron and on the FeSi
binary compound, two ternary phases were found at 600˚C in the two-phase alloys where the
second phase was α. They were indexed as cubic and tetragonal phases and regarded by
[1943Gre] as only tentative. Seeking for an explanation for the striking magnetic properties
observed for Fe-Ni-Si alloys, [1955Tak, 1960Tak] investigated the ternary phase diagram in the
region of Fe rich alloys, and a phase of the composition Fe11Ni5Si4 was found. [1960Iwa]
determined the crystal structure of the Fe11Ni5Si4 ternary phase. The data presented by
[1955Tak, 1960Tak, 1960Iwa] are consistent with one of the ternary phases found by
[1943Gre]. The probable course of monovariant lines on the liquidus surface projection for
Fe-Ni based alloys containing up to 40 at.% Si and a number of vertical sections were proposed
by [1960Tak]. [1965Bor] observed a ternary phase which was determined to be isostructural
with Au4Al, in an alloy of the composition 50Fe-30Ni-20Si (at.%) after annealing at 800˚C, the
composition being similar to that indicated by [1943Gre, 1955Tak, 1960Tak]. An isothermal
section at 600˚C was proposed, and it was stated that the phase equilibria did not differ from
those at 900˚C. The existence of a ternary phase with a tetragonal crystal structure, observed by
[1943Gre], was not confirmed by [1965Bor]. The mutual solubility of mono- and disilicides in
the Fe-Ni-Si ternary system was studied by [1961Wit, 1962Gla, 1965Bor, 1968Dmi, 1968Mir,
1968Sid1, 1968Sid2, 1969Mir]. [1965Bur] determined the change in the position of the γ/γ+α
and γ+α/α phase boundaries in the Fe-Ni-Si system with varying temperature. Two vertical
sections of the ternary phase diagram were constructed at 4 and 5 mass% Si. The investigation

2 13 Fe–Ni–Si
by [1994Koz] of the Fe-Ni-Si ternary system in the Fe-rich region was carried out using
experimental and theoretical methods. Two isothermal sections at 650˚C were proposed, based
on microstructural analysis and calculation, respectively. Isothermal sections for 800, 1000,
1100 and 1200˚C and vertical sections at 5, 10 and 15 at.% Ni were constructed, and the three-
phase equilibria involving the ternary phase, τ1, at 800˚C and equilibria involving the liquid at
1100 and 1200˚C were determined by [1998Ike].
Some information relating to the phase relations in the Fe-Ni-Si system were not consid-
ered in the reviews of [1988Ray, 1994Rag, 2003Rag]. [1990Li, 1991Zha] determined the Fe
solubility in Ni3Si, and [1975Ver] the Ni in Fe3Si. Precipitation during the decomposition of
martensite in Fe-Ni based alloys containing 1-5 mass% Si on ageing at 300-500˚C, the shape
and crystal structure of the precipitates and the effect of annealing on atomic structure were
studied by [1975Yas, 1982Yed, 1983Zay, 1980Rod]. The precipitates observed in a Fe-18Ni-5Si
alloy after ageing at 350 and 400˚C were identified by [1975Yas] as the (Fe,Ni)3Si phase, and
those observed at 500˚C as the (Fe,Ni)5Si2 phase. [1998Lan] reported on the synthesis of a new
ternary compound with the composition FeNiSi. Its crystal structure was determined as
orthorhombic with the Co2Si structure type.
The component elements of this system are constituents of more complex nanocrystalline
alloys that are expected to exhibit excellent magnetic properties. The influence of Ni on the
formation of a nanocrystalline phase in Fe735–xNixCu1Nb3Si13.5B9 alloys was studied by
[2001Duh]. The Fe3NiSi1.5 ternary phase, with a tetragonal crystal structure, was observed
at 500-550˚C. Taking into account the fact that the magnetic permeability of Fe-Ni based alloys
decreases with increase in the degree of order in the γ phase present, and in view of the
importance of high magnetic permeability in these alloys, [2004Him] studied the influence of
Si on the phase equilibria between the γ and γ’ phases in FeNi3-Ni3Si alloys. As a continuation
of the studies of [1998Ike, 2002Him, 2004Him] into the stability of the phases based on the α
and γ modifications of Fe, which can be affected by magnetic ordering, and considering alloys
based on the Ni3Si phase as having a potential application as high strength materials,
[2005Him] investigated the phase relationships in the Ni rich portion of the Fe-Ni-Si system.
Isothermal sections for 700, 800 and 900˚C were constructed and the α+γ+γ’ ternary equilib-
rium was determined. The metastable relationships were also shown.
Experimental techniques and information on the composition and temperature intervals
studied are shown in Table 1.
Binary Systems
The Fe-Si and Ni-Si binary systems are accepted from [Mas2]. The Fe-Ni system is taken from
the recent MSIT assessment by [2008Kuz].
Solid Phases
The details of crystallography and ranges of stability of the phases in the Fe-Ni-Si system are
listed in Table 2. The ternary phase, τ1, having a composition close to Fe11Ni5Si4, a cubic
crystal structure and being formed by a solid state reaction, was observed by [1943Gre,
1955Tak, 1960Tak, 1960Iwa, 1994Koz, 1998Ike]. [1965Bor] found the ternary phase of the
composition Fe5Ni3Si2 and indexed it also as cubic. Taking into account the same crystal
Fe–Ni–Si 13 3
structure, lattice parameter and close compositions that these two phases have, it is clear that
they are the same phase. According to the observations of [1955Tak], τ1 phase forms from the
phase based on (αFe). [1960Tak] was more precise, suggesting that τ1 phase forms by
the peritectoid reaction, α + γ Ð τ1, at about of 920˚C. [1965Bor] confirmed the formation
of the ternary phase via a solid state reaction. Based on the findings of [1965Bor, 1955Tak,
1960Tak, 1998Ike], the τ1 phase lies on the 20 at.% Si composition line from 24 to 30 at.% Ni.
A second ternary phase, τ2, with the composition Fe3NiSi1.5, was found by [2001Duh] on
the decomposition of multicomponent nanocrystalline Fe735–xNixCu1Nb3Si13.5B9 alloys after
annealing at 550-500˚C. This new phase appeared to be in equilibrium with the α2 phase
(Fe3Si). The Fe3NiSi1.5 ternary phase is included in Table 2 although its existence as a stable
phase should be confirmed through further investigations of the Fe-Ni-Si system.
The interpretation by [1982Yed] that the precipitates appearing in Fe-Ni based alloys after
ageing are a ternary phase of the composition (Fe,Ni)22Si7 with a cubic crystal structure, but
without consideration of the reflection intensity, is questionable. These precipitates, as
observed by [1975Yas], were identified as the phase known at that time as Ni5Si2. According
to [Mas2], it is the Ni31Si12 phase.
The solubility of Fe in the Ni2Si phase with the Co2Si crystal structure type, was found by
[1938Alt, 1972Fro] to be about 33.3 at.%. It would therefore seem reasonable that the new
phase with the Co2Si crystal structure type observed by [1998Lan] in an equiatomic single-
phase alloy can be interpreted as the limit of the homogeneity region of the Ni2Si phase. The
lattice parameters, shown in [1998Lan] and [1938Alt] for the equiatomic composition,
confirm the suggestion that it falls into the homogeneity range of the Ni2Si phase. The Fe2Si
phase dissolves about 3.3 at.% Ni at 1100˚C maintaining its cubic crystal structure, but at a
composition of 20 at.% Ni this structure distorts trigonally [1938Alt, 1972Fro]. At the same
time, Fe2Si-30 mol% Ni2Si alloys remained single-phase [1972Fro]. In order to accurately
ascertain the limits of the two-phase region along the section Fe2Si-Ni2Si, additional investi-
gations should be undertaken.
The high silicides of the Fe-Ni-Si system, FeSi2 and αNiSi2, dissolve about 1.7 at.% Ni
at 800˚C [1961Wit] and about 12 at.% Fe at 850˚C [1965Mir, 1968Mir, 1969Mir, 1968Sid2],
respectively. The latter group of authors showed that the αNiSi2 phase in the Ni-Si binary
system had a true composition of Ni1.04Si1.93, and its homogeneity range in the ternary system
has a complex shape having a width of less than 0.5% in the binary system, widening with
respect to Si content with increasing Fe. The high Fe solubility in αNiSi2 reported by [2002Fet]
of about 30 at.% is an erroneous conclusion from their experimental results, which showed
that an alloy with 9 at.% Fe was single-phase αNiSi2, while an alloy with 13 at.% contained two
phases at 750˚C. Actually, this study supported the value given above (about 12 at.%) for the
homogeneity range of the αNiSi2 phase.
According to [1961Wit, 1965Bor], the mutual solubility of the equiatomic phases at
600-800˚C is approximately 25 at.% Ni in FeSi and 5 at.% Fe in NiSi. [1968Dmi, 1968Sid1]
confirmed that about 5 at.% Fe dissolves in NiSi and [1968Sid1] showed that about 20 at.% Ni
could be dissolved in FeSi at 900˚C. The values of the mutual solubility of monosilicides given
by [1962Gla] are substantially lower than those stated by [1965Bor, 1961Wit]. The solubility of
Fe in Ni31Si12 at 800˚C, reported by [1979Ind] as being about 29 at.%, is not in conflict with
the value of about 7.9 at.% at 900˚C given later by [2005Him], as the latter value was obtained
from the analysis of a two-phase (ν+γ) sample and is related to an intermediate composition
of the homogeneity range.

4 13 Fe–Ni–Si
The homogeneity range of the Ni3Si phase at 900˚C as determined by [1990Li, 1991Zha] is
consistent with that shown by [2005Him] for 800˚C. Approximately 6.7 at.% Fe dissolves in
Ni3Si at 900˚C and 6.4 at.% Fe at 800˚C, Fe substituting for Ni and Si.
The solubility of nickel in the α1 phase at 1000˚C was given by [1975Ver] to be up to 15
at.% along the 25 at.% Si concentration line, the lattice parameter of the phase increasing. The
solubility was estimated by [1977Nic] as being 20-25 at.% at 25 at.% Si at room temperature.
Further experimental studies by [1998Ike] showed that it was 17 at.% at 18 at.% Si when α1
was in equilibrium with the γ and τ1 phases at 800˚C.
The Si solubility in the γ solid solution decreases with temperature decreasing from 900 to
700˚C and with Fe content increasing up to 34 at.% in Ni rich alloys. For the Fe rich alloys, it
increases with temperature in the interval 800-1100˚C and increasing Ni content up to about
27 at.% [2005Him].
Quasibinary Systems
According to [1968Sid1], the FeSi-NiSi section is quasibinary at about 900˚C with a significant
region of immiscibility, about 20-45 at.% Ni.
The critical temperatures of the γ+γ’/γ’ and γ/γ+γ’ transitions for the FeNi3-Ni3Si alloys in
the range of 0-20 at.% Si are plotted in Fig. 1 after [2004Him]. The transformation tempera-
ture of FeNi3 increases on substitution of Si for Ni. The section can be considered as
quasibinary in the range of temperature and compositions studied.
The τ1 phase forms by the peritectoid reaction, α + γ Ð τ1, at about 920˚C [1960Tak]. The
compositions of the phases taking part in the equilibrium at this temperature are shown in
Table 3 according to the [1960Tak] data.
Liquidus Surface
A few experimental and calculated determinations of the liquidus surface of the Fe-Ni-Si
system have been undertaken. A hypothetical projection of the Fe-Ni-Si liquidus surface of the
whole composition range was given by [1988Ray]. It was based partly on the experimental data
of [1960Tak] and partly deduced from available information on the Fe-Ni-Si phase diagram in
the solid state. The applicability of this approach to the Fe-Ni-Si system is questionable for a
number of reasons. Firstly, solidus equilibria considered by [1988Ray] were shown by
[1965Bor] as only tentative and they included low temperature modifications of the FeSi2
and NiSi2 phases which do not exist at subsolidus temperatures. An increase in temperature
leads not only to a change in the crystal structure of these phases, but in the case of FeSi2, to a
change in the composition and homogeneity range (and stability) in the binary system
[Mas2]. Hence, the equilibria including the high-temperature modifications are different
from those existing at low temperature. Moreover, the low temperature studies of
[1968Mir, 1968Sid2] not discussed by [1988Ray], present phase relationships between the
mono- and disilicides different from those in [1988Ray]. For the above reasons, the liquidus
Fe–Ni–Si 13 5
projection suggested by [1988Ray] is not reproduced here. Figure 2 presents monovariant

curves separating the fields of primary crystallization of the α and γ, α and ε phases shown by
[1960Tak] with corrections to the field of primary crystallization of the Fe2Si phase to be
consistent with the accepted Fe-Si binary system [Mas2].
A calculated projection of the primary crystallization surfaces of the α and γ phases made
by [1998Mie] occurred in a reasonable correlation with the experimental data of [1960Tak].
Isothermal Sections
The temperature at which the portions for the Fe rich and Ni rich part of the Fe-Ni-Si ternary
system were studied by [1998Ike, 1999Mie, 2004Him, 2005Him] and earlier by [1961Wit,
1979Ind] was 800˚C. Taking this into account, together with the suggestion by [1965Bor] that
the phase equilibria in the ternary system at 900˚C were little different from those at 600˚C,
these data, along with those of [1965Bor, 1968Dmi, 1968Mir, 1968Sid1, 1968Sid2, 1969Mir]
on the solubility of Fe and Ni along the FeNi-NiSi and FeSi2-αNiSi2 sections (shown for
850˚C) are used in the construction of an isothermal section for 800˚C, which is presented in
Fig. 3. Dashed lines are used for hypothetical phase boundaries where no data on phase
relations exist. The Fe solubility in the Ni2Si phase, up to the equiatomic composition in
the ternary system was taken from [1972Fro]. The data relate to 1100˚C, and hence the phase
relationships are only approximate at this temperature. The fragment of the section at 650˚C
given by [1994Koz] showing the three-phase equilibrium α+γ+τ1 does not contradict, in
principle, the Fe rich region at 600˚C given by [1965Bor], although the phase compositions
at the vertices of the α+γ+τ1 triangle are different.
The results of the metallographic study of the solubility of Fe in the αNiSi2 phase carried
out by [1968Sid2] leads to an understanding of the phase diagram in relation to the ζβ and
αNiSi2 phases. There is a three-phase equilibrium FeSi2+αNiSi2+Si, for which the composition
of the αNiSi2 phase was determined to be between 11.6 and 13.5 at.% Fe along the FeSi2-NiSi2
section. From the observation by [1968Mir, 1968Sid2] of the presence of the NiSi phase along
with the αNiSi2 and ζβ phases in an alloy with 13.5 at.% Fe lying on the FeSi2-Ni1.04Si1.93
section, it follows that the equilibrium FeSi2+αNiSi2+NiSi, rather than FeSi2+αNiSi2+FeSi as
given in [1988Ray], is present in the ternary system.
The position of the Ni3Si+γ+ν three-phase triangle in Fig. 3 is given in accordance with the
data of [2005Him]. It differs from that shown for 800˚C by [1979Ind, 1988Ray]. In other
respects, the section is close to that proposed in [1988Ray] for 600˚C.
[1980Cha] assessing the available experimental data, calculated partial isothermal sections
for the Fe-Ni-Si system in the range up to 30 at.% Si at 427, 527 and 627˚C. Ternary
interactions were not incorporated into the calculations. However, the ternary phase τ1, did
not appear in the results of the calculations. This was due to the fact that [1980Cha] used only
data for the binary systems for an extrapolation into the ternary system.
By using the new experimental data of [1998Ike] and thermodynamic data on silicon
activity in liquid Fe-Ni-Si alloys presented by [1964Bow], [1999Mie] reassessed the thermo-
dynamic description for the solution phases, improving the ternary interaction parameters for
the liquid, α and γ phases that had been optimized in an earlier study, [1998Mie]. A series of
isothermal sections for the Fe corner of the ternary diagram, at 1200, 1100, 1000 and 800˚C, as
well as vertical sections at 4 and 5 mass% Si were calculated, which agree reasonably well
with the data of [1998Ike] and [1965Bur], respectively, observing that the thermodynamic
6 13 Fe–Ni–Si
parameters obtained were valid only for the Fe-rich corner. These parameters did not
represent a complete assessment of the system owing to the lack of experimental phase
diagram data involving the silicides and liquid.

The vertical sections of the Fe-Ni-Si phase diagram through the 71Fe-29Ni binary alloy and
the 59.9Fe-10.1Ni-Si ternary alloy, and an isopleth at 10 at.% Ni given by [1998Ike] are shown
in Figs. 4 and 5. The first section shows boundaries of the two- and three-phase regions
including the τ1 ternary phase, as well as two-stage atomic ordering taking place in the (αFe)
based phase. The second one depicts the change in the γ+(αFe) based phase fields with respect
to temperature.
Thermodynamics
Thermodynamic data on silicon activity in liquid Fe-Ni-Si alloys has been presented by
[1964Bow].
Thermodynamic assessments of the Fe-Ni-Si system were performed by [1980Cha] and
[1999Mie], see discussion above in the section Isothermal Sections.
Ageing Fe-Ni-Si alloys with 25-32 at.% Ni and 2.5-4.2 at.% Si at 400 and 500˚C after
quenching from 1100˚C leads to an increase in the hardness of matrix, which increases with
annealing time [2001Him, 2002Him]. This was due to the precipitation of γ’ particles at both
temperatures. Ageing at 500˚C leads to the precipitation of ferrite and Ni31Si12 as well. The
emergence of γ’ phase precipitates also contributed to a reduction in the martensitic transfor-
mation temperature of the alloy. A partial shape memory effect has been observed in a
Fe-25.5Ni-4Si (at.%) alloy, the effect increasing with a decrease in the deformation tempera-
ture from –30˚C to –196˚C, when it reached 38% [2002Him]. The alloy with the composition
40 at.% Fe-10 at.% Ni has the highest value of hardness at about 1170 kg·mm–2 (11474 MPa)
[1965Bor]. This value decreases to 670 kg·mm–2 (6570 MPa) on reducing the iron content to
10 at.% Fe. The maximum increase in hardness (ΔHv=30) for a Fe-18Ni-1.5Si (mass%) alloy
was observed after heating at 400˚C [1983Zay]. Increasing the silicon content to 3% resulted in
a shift in the hardness maximum occurring at a temperature between 475-500˚C. The study of
the maraging kinetics of Fe-18Ni-(1.5-3)Si (mass%) alloys revealed a continuous additional
increase in the hardness as well as the specific resistivity with time in the temperature range of
400-450˚C, and a rapid growth in hardness and specific resistivity, even after short heating
[1983Zay]; the higher the temperature, the greater the growth. The increase in hardness after
heating at 450 and 500˚C for 1 min is 60 and 120 Hv (588.4 and 1177 MPa) respectively.
Alloys with 3 and 5 mass% Si in Fe-(73-75)Ni-Si (mass%) alloys were shown by [1933Dah]
to demonstrate a behavior of hardness, electrical resistivity and magnetic characteristics
different from that of Fe-Ni binary alloys and of ternary alloys with lower Si contents.

Fe–Ni–Si 13 7
Magnetic susceptibility is at a minimum in FeSi2-Ni1.04Si1.93 alloys with an Fe content of

about 13 at.% [1969Mir]. The change in the microhardness of FeSi2-Ni1.04Si1.93 alloys experi-
enced on increasing the Fe concentration correlates with the change in lattice parameter and
falls to a minimum at about 7 at.% Fe. A minimum in the specific electrical resistivity of these
alloys occurs at an Fe content of 5-7 at.%. On increasing the Fe content in a solid solution
based on Ni1.04Si1.93, the coefficient of thermal expansion decreases [1968Sid2]. The specific
resistivity of NiSi increases with the addition of FeSi, while thermoelectromotive force falls
[1968Dmi].
Powders with an average grain size of 8-19 nm were synthesized by high-energy ball milling
[2005Hos]. The grain size produced in a 85Fe-5Ni-10Si (at.%) alloy was found to decrease on
increasing the milling time to 70 h. At the same time, the magnetic characteristics of the alloy
(coercivity and saturation magnetization) reached a minimum and maximum, respectively.
The 87Fe-10Si-5Ni (at.%) alloy was the optimal composition showing a fine particle structure
and good soft magnetic properties in the Fe based metastable solid solution [2005Hos].
[1965Bur] observed an improvement in the ductility of Fe-(3-6)Si on increasing the Ni
content up to 5.5-7.5 mass%.
The values of the magnetization of a Ni-doped (1 at.%) ζβ single crystal were positive and
quite small for the temperature range 5-300 K [2004Aru].
[1980Sri] studied properties of electrodeposited magnetic films. Fe-(1-15%)Si-(2-80%)Ni
(Ni : Si ≥ 2) alloys were electroplated, and the deposits, containing 15% Si and 40% Ni, were
found to possess a tensile strength of 50 kg f·mm–2, an elongation of 10% and their corrosion
rate was less than 0.1 mm /year in 95% H2SO4, 35% HCl, 70% HNO3 or 30% NaOH.
A strong relationship between the chemical and magnetic ordering of γ and γ’ phases in the
Ni3Fe-Ni3Si subsystem was found by [2004Him]. The Curie temperature for the ordered γ’
phase was estimated to be 680˚C by extrapolating the TC value from the Ni3Fe-Ni3Si system.
The paramagnetic γ/γ’ transition temperature for the Ni3Fe phase was evaluated to be about
330˚C [2004Him].
With the view to the potential use of Fe-Ni-Si ternary alloys in optoelectronic devices,
[2002Fet] undertook ion implantation of two metals (Fe, Ni) into a silicon substrate and
examined the phases formed. In parallel, the phase relationships in bulk alloys were studied.
The phase compositions of alloys annealed at 750˚C was shown to depend on Fe (Ni)
concentration.
Miscellaneous
[1955Tak] attributed the striking Perminvar characteristics of Fe-(8-12)Ni-(14-18)Si (mass%)

alloys to the precipitation of dispersed τ1 ternary phases in the αFe matrix on cooling from
about 900˚C.
The small grain size and good ductility at 100˚C of Fe-Ni-Si alloys with 5 mass% Si and
≥5.5 mass% Ni was achieved by [1965Bur] through hot rolling in the α+γ region. For the
Fe-6.5Si composition, 2 or 4 mass% Ni was not found to be effective in improving the ductility
of hot forged and hot rolled specimens [1976Nar, 1978Nar]. The maximum permeability of
these alloys was found to decrease with increasing nickel addition and annealing temperature.
By studying the effect of tensile fracture on the microstructure of a Fe-18Ni-55Si (mass%)
alloy aged at 350-400˚C, [1975Yas] demonstrated the difficulty for cross slip, which results in
stress concentration occurring at grain boundaries leading to embrittlement, while on ageing
8 13 Fe–Ni–Si
at the higher temperature of 450-500˚C, it was the precipitation of the Ni31Si12 based phase
that brought about the embrittlement.
Si substitutes for Ni in the Ni3Fe superstructure because of its preferred interaction with Fe
atoms, Si not affecting the value of the long-range order parameter [1970Gom]. Using
electronic structure calculations, [1995Slu] concluded that Fe dissolving in Ni3Si would
preferentially substitute for Ni when magnetic effects were ignored, but when they were
considered in the calculations, Fe was predicted to have no site preference.
Magnetic ordering increases the stability of the γ’ phase (ordered) rather than γ phase
(disordered), while chemical ordering stabilizes the ferromagnetic phase rather than paramag-
netic [2004Him].
γ’ phase precipitates were observed to form in γ alloys during ageing at 700˚C, in
compositions with more than 60 at.% Fe. The Ni3Si phase field extended to the Fe3Si phase
(as well as to FeNi3 phase), forming a metastable (Fe,Ni)3Si phase [2005Him].
The activation energy of the maraging process in a Fe-16.3Ni-5.7Si (mass%) alloy,
calculated from data on the variation of the resistivity with temperature, is 130 kJ·mol–1 at
about 400˚C and around 150-170 kJ·mol–1 at about 600˚C [1983Zay]. The activation energy of
the annealing process in a Fe-33.4Ni-4.9Si (mass%) alloy at temperatures below 500˚C,
calculated from studies of the variation of the hyperfine magnetic field with temperature,
was found by [1980Rod] to be about 96 kJ·mol–1.
According to [1968Sid1], the change in the lattice constant across the homogeneity region
of FeSi based alloys with Ni substituting for Fe was not linear, while [1961Wit] reported on a
smooth change in the lattice parameter in alloys of up to 25 at.% Ni.
The equilibrium partition ratios of solutes in a 3.06 Fe-Ni-5.09Si (mass%) alloy quenched
from the solid-liquid region were 0.51 for silicon and 1.18 for iron, indicating a preference for
Fe to partition to the solid and Si to the liquid [1990Kag].
The calculated structural parameters of the ζβ phase were shown by [2002Tan] to depend
on the sites replaced by Ni. Data obtained for the undoped ζβ phase and a (Fe0.875Ni0.125)Si2
alloy for two types of Ni positions are presented in Table 2.
. Table 1
Investigations of the Fe-Ni-Si Phase Relations, Structures and Thermodynamics
Temperature/Composition/
Reference Method/Experimental Technique Phase Range Studied
[1943Gre] X-ray, chemical analysis (50-100)Fe-50Ni-50Si (at.%), 600˚C

[1955Tak] Microscopic observation, magnetic, Fe-(14-18) Ni-(8-12) Si (mass%)
dilatometry, electric resistivity, intensity of
magnetization
[1960Iwa] XRD, pycnometer method Fe-28.8Ni-11.0Si (mass%)
[1960Tak] Microscopic observation, magnetic and Fe-(5-60)Ni-(3-20)Si (mass%)
dilatometry
[1961Wit] X-ray 800 to 1100˚C, FeSi-NiSi, FeSi2-NiSi2
[1962Gla] Melting in corundum crucibles, X-ray, optical FeSi-NiSi
microscopy analyses

Fe–Ni–Si 13 9
[1965Bor] Melting in a resistance furnace, X-ray, Fe-Ni-Si 600-900˚C

microstructure and microhardness analyses
[1965Bur] Vacuum melting, optical microscopy, tensile Fe-(4.5-7.5)Ni-(5)Si (mass%) 700-
test 1250˚C
[1965Mir] Induction melting, microstructure and X-ray FeSi2.3-NiSi2
analyses
[1968Dmi] X-ray, microstructure, specific electrical FeSi-NiSi
resistivity, emf
[1968Mir] Induction melting, optical microscopy, X-ray NiSi2-FeSi2 FeSi2 -Ni1.04Si1.93
analyses Fe1.04Si1.93-Ni1.04Si1.93 (0-40 mass%
FeSi2) at 850˚C
[1968Sid1] Induction melting, X-ray, microstructure FeSi-NiSi, 900˚C
analyses
[1968Sid2] Induction melting, microstructure and X-ray FeSi2-Ni1.04Si1.93, FeSi2-NiSi2
analyses Fe1.04Si1.93-Ni1.04Si1.93 (up to 40 mol%
FeSi)
[1969Mir] Induction melting, microstructure and X-ray FeSi2-Ni1.04Si1.93 FeSi2-NiSi2,
analyses Fe1.04Si1.93-Ni1.04Si1.93
[1970Gom] Neutron diffraction (FeNi3)1–xSix, 0.02 ≤ x ≤ 0.05
[1972Fro] Induction melting, microstructure and X-ray Fe2Si-Ni2Si, 1100˚C
analyses
[1975Ver] Induction melting, optical microscopy, X-ray, (Fe1–xNix)3Si, 0 ≤ x ≤ 1
homogenization at 1000˚C with slow cooling
to room temperature
[1975Yas] TEM, SEM, tensile test Fe-18Ni-5Si (mass%)
[1977Nic] X-ray diffraction Fe1–xNixSi, 0.8 ≤ x ≤ 1
[1980Cha] Calculation Fe-Ni-(0-30)Si (at.%), 427, 527, 627˚C
[1982Yed] Electron microscopy Fe-18Ni-3Si (mass%)
[1983Zay] Induction melting, X-ray, nuclear γ resonance, Fe-18Ni-(1.5-3)Si (mass%) 1000˚C
calorimetry
[1990Li] Induction melting, EPMA 900˚C, Fe-Ni-(23.5-26)Si (at.%)
[1991Zha] Induction melting, EPMA 900˚C, Fe-Ni-(23,5-26)Si (at.%)
[1994Koz] Induction arc melting, TEM, calculation 650˚C up to 30 at.% Ni and to 20 Si
(at.%)
[1998Ike] Induction melting, modified solid diffusion Fe-(0-39.5)Ni-(0-24.6)Si (at.%)
couples, optical microscopy, EDS, TEM
[1998Lan] Induction melting in a copper boat, neutron FeNiSi
diffraction

10 13 Fe–Ni–Si
[1998Mie] Calculation, substitutional solution model Fe-(0-25)Ni-(0-10)Si (mass%) 1200,

[1999Mie] 1100, 1000, 800˚C
[1999Sun] EPMA of solid and quenched liquid after 3.06Fe-Ni-5.09 Si (mass%)
isothermal annealing
[2001Duh] TEM, ED, X-ray, electrical resistivity, Mössbauer Fe73.5–x-NixCu1Nb3Si13.5B9, x = 10, 20,
spectrometry 30, 40 (at.%)
[2001Him] Induction melting, hot rolling, annealing, Fe-2.5Ni-7.5Si (mass%) 400 to 700˚C
quenching, aging, DSC, optical microscopy,
TEM, hardness testing
[2002Fet] Induction melting, TEM, Mössbauer Ni1–xFexSi2, 0.28 ≤ x ≤ 0.97 1000˚C
spectroscopy, XRD, RBSC
[2002Him] Induction melting, optical microscopy, DSC, Fe-(24-30)Ni-(5-8)Si (mass%)
TEM, ED, electrical resistivity
[2002Tan] First principle pseudopotential calculations Lattice parameter (Fe0.875Ni0.125)Si2
[2004Him] Induction melting, optical microscopy, TEM, Ni3Fe-Ni3Si, 500 to 900˚C
EPMA, XRD, DSC, electrical resistivity, vibrating
magnetometry
[2005Him] Induction melting, optical microscopy, EDX, Ni-(0-63.3)Fe-(7-22)Si (at.%), 500 to
EPMA, TEM, electrical resistivity 1300˚C
[2005Hos] Mechanical alloying, XRD, SEM, VSM Fe-(3-10)Mi-(10-25)Si (at.%)
. Table 2
Pearson
Symbol/
γ, Fe1–x–yNixSiy cF4 at x = 0, 0 ≤ y ≤ 0.038 [Mas2]

< 1517 Fm3m at y = 0, 0 ≤ x ≤ 1
Cu at x + y = 1, 0 ≤ y ≤ 0.158 [Mas2]
at 0 ≤ y ≤ 0.121 [2005Him]
at 0 ≤ x ≤ 15
maximum of Si solubility is at 1100˚C [1998Ike]
(γFe) a = 364.67 at 915˚C [Mas2, V-C2]
1394 - 912
(Ni) a = 352.4 at 25˚C [Mas2, V-C2]
< 1455

Fe–Ni–Si 13 11
Pearson
Symbol/
α, Fe1–x–yNixSiy cI2 at x = 0, 0 ≤ y ≤ 0.195

Im3m at y = 0, 0 ≤ x ≤ 0.038 (δFe)
W at y = 0, 0 ≤ x ≤ 0.046 (αFe)
(δFe) a = 293.15 at x = 0, y = 0 and 1394˚C [Mas2, V-C2]
1538 - 1394
(αFe) a = 286.65 at x = 0, y = 0 and 25˚C [Mas2, V-C2]
< 912
P63/mmc c = 396.0
Mg
(Si) cF2 a = 543.06 at 25˚C [V-C2, Mas2]
< 1414 Fd3m
C (diamond)
γ’, FeNi3 cP4 63 to 83 at.% Ni at 347˚C [2008Kuz]
< 517 Pm3m a = 355.23 paramagnetic γ/γ’ transition temperature is
AuCu3 about 330˚C [2004Him]
a = 354.3 20Fe-75Ni-5Si (at.%)
a = 351.4 3Fe-75Ni-22Si (at.%) at RT [2004Him]
γ’’FeNi tP4 a = 357.9 [V-C2]
metastable P4/mmm Metastable ordering temperature 320˚C at 51.2
AuCu at.% Ni [2008Kuz]
β, Fe2Si hP6 ~33.0 to ~34.3 at.% Si [1982Kub]
1212 - 1040 P3m1 a = 405.2 ± 0.2 [V-C2]
Fe2Si c = 508.55 ± 0.03 dissolves 3.3 at.% Ni at 1100˚C without changing
the crystal structure [1972Fro]
α1, Fe3Si cF16 ordered D03 modification of Fe with 11 to 30
≲ 1235 Fm3m at.% Si [1982Kub, Mas2]
BiF3 a = 565 [V-C2]
dissolves about 20-25 at.% Ni at 800-1200˚C
[1977Nic, 1998Ike]
α2, Fe4Si cP2 ordered B2 modification of Fe with 10 to 22 at.%
≲ 1280 Pm3m Si [1982Kub, Mas2]
CsCl a = 281.0 [V-C2]
dissolves 10-15 at.% Ni at 800˚C [1998Ike]
η, Fe5Si3 hP16 37.5 at.% Si [1982Kub]
1060 - 825 P63/mcm a = 675.9 ± 0.5 [V-C2]
Mn5Si3 c = 472.0 ± 0.5

12 13 Fe–Ni–Si
Pearson
Symbol/
ε, FeSi cP8 49.6 to 50.8 at.% Si [1982Kub]

< 1410 P213 a = 451.7 ± 0.5 [V-C2]
FeSi dissolves 25 at.% Ni at 800˚C [1961Wit] and
24 at.% Ni at 600˚C [1965Bor]
ζβ, FeSi2(r) oC48 a = 986.3 ± 0.7 at 66.7 at.% Si [V-C2, Mas2]
< 982 Cmca b = 779.1 ± 0.6 dissolves 1.7 at.% Ni at 800˚C [1961Wit]
FeSi2 c = 783.3 ± 0.6
a = 987.1 calculated by [2002Tan]
b = 777.7
c = 783.7
a = 997.5 Fe0.875Ni0.125Si2 (FeIsite)
b = 779.8
c = 787.4
a = 999.3 Fe0.875Ni0.125Si2 (FeIIsite) [2002Tan]
b = 779.0
c = 786.4
ζα, FeSi2(h) tP3 69.5 to 73.5 at.% Si [1982Kub]
1220 - 937 P4/mmm a = 269.01 [V-C2]
FeSi2 c = 513.4
Ni4Si cP4 a = 350.6 at 23.5 at.% Si [2005Him]
< 1035 Pm3m dissolves about 8 at.% Fe at 427˚C [V-C2]
AuCu3 dissolves 6.7 at.% Fe at 900˚C, Fe substitutes for
both Ni and Si atoms [1990Li, 1991Zha]
dissolves 6.4 at.% Fe at 21.1 at.% Si and 800˚C
[2005Him]
β2, Ni3Si (h1) mC16 ~24.5-25.5 at.% Si [Mas2]
< 1115 - 990
β3, Ni3Si (h2) mC16 ~24.5-25.5 at.% Si [Mas2]
< 1170 - 1115
ν, Ni31Si12 hP43 a = 666.7 ± 0.2 [V-C2], hP14 in [Mas2] at 27.9 at.% Si
< 1242 P321 c = 1228 ± 0.2 [Mas2]
Ni31Si12 γ = 120˚ dissolves >7.9 at.% Fe at 800˚C [2005Him]
δ, Ni2Si oP12 a = 502.2 ± 0.1 at 33.3 at.% Si [V-C2, Mas2] dissolves 33.3 at.% Fe
< 1255 Pnma b = 374.1 ± 0.1 at 1100˚C [1972Fro]
Co2Si c = 708.8 ± 0.1
θ, Ni2Si hP6 a = 383.6 ± 0.1 [V-C2]
1306 - 825 P6322 c = 494.8 ± 0.1 33.4 to 41 at.% Si [Mas2]
Ni2Si

Fe–Ni–Si 13 13
Pearson
Symbol/
σ, Ni3Si2 oC80 a = 1222.9 [V-C2]

< 830 Cmc2 b = 1080.5 oP80 in [Mas2]
Ni3Si2 c = 692.4 39.0 to 41 at.% Si [Mas2]
σ’, Ni3Si2 39.2 to 41 at.% Si [Mas2]
845 - 800
NiSi oP8 a = 562.8 ± 0.2 [V-C2]
< 992 Pnma b = 519.0 ± 0.1 dissolves about 5 at.% Fe [1961Wit, 1968Dmi,
1968Sid2]
MnP c = 333.0 ± 0.1
αNiSi2 cF12 a = 540.74 ± 0.05 Ni1.04Si1.93 [1968Mir, 1968Sid2]
< 981 Fm3m dissolves 10 at.% Fe at 800˚C [1961Wit] and
about 12 at.% Fe at 850˚C [1968Mir]
CaF2
βNiSi2 - - [Mas2]
993 - 981
* τ1, Fe11Ni5Si4 c* at 20 at.% Si, 24 to 30 at.% Ni
< 920 a = 613.1 [1943Gre]
a = 613.5 ± 0.4 [1965Bor]
a = 614.8 [1960Iwa]
54.8Fe-25.2Ni-20Si at.% [1955Tak, 1960Tak,
1994Koz, 1998Ike]
* τ2, Fe3NiSi1.5 t* a = 832.5 [2001Duh]
~500 c = 903 the existence needs a confirmation
. Table 3
Composition (at.%)
Reaction T [˚C] Type Phase Fe Ni Si
α + γ Ð τ1 920 p α 57.8 20.6 21.5

γ 43.0 43.7 13.3
τ1 54.8 25.2 20.0

14 13 Fe–Ni–Si
. Fig. 1
Fe-Ni-Si. Partial FeNi3-Ni3Si section

Fe–Ni–Si 13 15
. Fig. 2
Fe-Ni-Si. Partial liquidus surface projection in the Fe rich region

16 13 Fe–Ni–Si
. Fig. 3
Fe-Ni-Si. Isothermal section at 800˚C

Fe–Ni–Si 13 17
. Fig. 4
Fe-Ni-Si. Isopleth through the alloys 59.9Fe10.1Ni30Si - 71Fe-29Ni (at.%)

18 13 Fe–Ni–Si
. Fig. 5
Fe-Ni-Si. Isopleth through the 10 at.% Ni isoconcentrate

Fe–Ni–Si 13 19
References
[1933Dah] Dahl, O., Pfaffenberger, J., “Contribution to the Knowledge on Iron-Nickel Alloys” (in German),
Z. Metallkd., 25, 241–244 (1933) (Experimental, Mech. Prop., Magn. Prop., 4)
[1938Alt] Altgauzen, O.N., Metallurg, (3), 3–14 (1938) as quoted by [1988Ray]
[1943Gre] Greiner, E.S., Jette, E.R., Trans. Amer. Inst. Min. Met. Eng., 152, 48–63 (1943) (Crys. Structure,
Experimental, Phase Diagram, *, 13)
[1955Tak] Takeda, S., Iwama, Y., Muramoto, T., “Fundamental Research of Constant Permeability Alloys. I. On
the Cause of Perminvar Characteristics of the Senperm Alloys of the Fe-Ni-Si system” (in Japanese),
Nippon Kinzoku Gakkai-Si, 19, 123–136 (1955) (Phase Diagram, Experimental, Phys. Prop., *, 4)
[1960Iwa] Iwama, Y., Takeda, S., “Fundamental Research on Constant Permeability Alloys. III. Crystal Structure”,
Nippon Kinzoku Gakkai-Si, 24, 538–540 (1960) (Crys. Structure, Experimental, 4)
[1960Tak] Takeda, S., Iwama, Y., Sakakura, A., “Fundamental Research on Constant Permeability Alloys. II.
Equilibrium”, Nippon Kinzoku Gakkai-Si, 24, 534–538 (1960) (Morphology, Phase Diagram, Experi-
mental, *, 7)
[1961Wit] Wittmann, A., Burger, K.O., Nowotny, H., “Mono- and Disilicide Systems of the Fe Group”, Monatsh.
Chem., 92(5), 961–966 (1961) (Crys. Structure, Phase Diagram, Experimental, 14)
[1962Gla] Gladyshevskiy E.I., “Crystal Structure of Compounds and Phase Equilibria in Ternary System of Two
Transition Metals and Silicon” (in Russian), Poroshk. Metall., 410, 46–49 (1962) (Crys. Structure, Phase
[1964Bow] Bowles, P.J., Ramstad, H.F., Richardson, F.D., “Activities of Silicon in Metals and Alloys”, J. Iron Steel
Inst., 202, 113–121 (1964) as quoted by [1999Mie]
[1965Bor] Borusevich, L.K., Gladyshevsky, E.I., Kuzma Yu.B., Rozum, S.M., “The Fe-Ni-Si System” (in
Ukrainian), Visn. Lviv. Derzh. Univ., Ser. Khim., (8), 83–87 (1965) (Crys. Structure, Phase Diagram,
Experimental, *, 13)
[1965Mir] Miroshnikov, L.A., Sidorenko, E.A., “The Quasibinary Section α-lebeauite-NiSi2” (in Russian), Trudy
Uralsk. Politekhn. Inst., (144), 78–81 (1965) (Crys. Structure, Phase Relations, Experimental, 3)
[1965Bur] Burr, D.J., Butt, R.J., Wakeman, D.W., “Effect of Ni Additions on the Structure and Ductility of Fe-Si
Alloys”, J. Iron Steel Inst., 203, 500–501 (1965) (Crys. Structure, Phase Relations, Calculation, Experi-
mental, Mechan. Prop., 6)
[1968Mir] Miroshnikov, L.A., Sidorenko, F.A., Gel’d, P.V., “To Solubility of FeSi2 and CoSi2 in Disilicide of Nickel”
(in Russian), Tr. Ural’sk. Politekhn. Inst., (167), 65–68 (1968) (Phase Diagram, Experimental, 5)
[1968Sid1] Sidorenko, A.F., Dmitriev, E.A., Apasova, E.A., “Crystal Lattice Constants in Some Quasibinary Alloys
Based on FeSi” (in Russian), Tr. Ural’sk. Politekhn. Inst., (167), 124–127 (1968) (Crys. Structure, Phase
[1968Dmi] Dmitriev, E.A., “Solid Solutions of FeSi in NiSi” (in Russian), Tr. Ural’sk. Politekhn. Inst., (167),
127–128 (1968) (Phys. Prop, 2)
[1968Sid2] Sidorenko, F.A., Miroshnikov, L.A., Geld, P.V., “Range of Homogeneity and Structural Characteristics
of Solid Solutions of the Higher Silicides of Nickel and Iron” (in Russian), Poroshk. Metall., (4), 53–59
(1968) (Crys. Srtucture, Phase Relations, Experimental, Phys. Prop., 6)
[1969Mir] Miroshnikov, L.A., Sidorenko, F.A., Geld, P.V., “Electronic Structure and Phase Diagrams of Quasibinary
Systems Based on the Higher Silicides of Nickel and Cobalt” in “Teor. Eksp. Metody Issled. Diagramm
Sostoyaniya Metal. Sist.” (in Russian), Dokl. Soveshch., Ageev, N.V., Ivanov, O.S., Grigorovich, V.K.,
(Eds.), Nauka, Moscow, 25–28 (1969) (Crys. Structure, Phase Relations, Theory, Experimental, Magn.
Prop., 6)
[1970Gom] Goman’kov, V.I., Puzey, I.M., Mal’tsev, E.I., “Effect of Alloying Elements on the Superstructure of
Ni3Fe” (in Russian), Dokl. Akad. Nauk SSSR, 194(2), 309–311 (1970) (Crys. Structure, Experimental, 6)
[1972Fro] Frolov, A.A., Sidorenko, F.A., Krentsis, R.P., Geld, P.V., “Structural Characteristics of Fe2Si-Ni Silicide
Solid Solutions” (in Russian), Zh. Neorg. Khim., 17, 2574–2575 (1972) (Crys. Structure, Phase Relations,
Experimental, 5)
[1975Yas] Yasunaka, T., Araki, T., “Effect of Microstructure on the Tensile Fracture in Fe-18Ni-5Si Alloy”, Trans.
Nat. Res. Inst. Met., 17(5), 277–284 (1975) (Crys. Structure, Phase Relations, Experimental, Mechan.
Prop., 17)

20 13 Fe–Ni–Si
[1975Ver] Vereshchagin, Yu.A., “Procedure for Synthesis, Homogeneity Regions and Lattice Spacings of Fe” (in
Russian), Fiz. Metody Issled. Tverdogo Tela, (1), 40 (1975) (Crys. Structure, Phase Relations, Experi-
mental, 9)
[1976Nar] Narita, K., Enokizono, M., “Effects of Ni, Al and Mn Addition on the Mechanical and Magnetic
Properties of 6.5% Si-Fe Sheets”, IEEE Trans. Magn., 12(6), 873–873 (1976) (Mechan. Prop., Magn.
Prop., 0)
[1977Nic] Niculescu, V., Budnick, J.I., “Limits of Solubility, Magnetic Properties and Electron Concentration in
Fe3–xTxSi System”, Solid State Commun., 24(9), 631–634 (1977) (Crys. Structure, Experimental, Magn.
Prop., 17)
[1978Nar] Narita, K., Enokizono, M., “Effect of Nickel and Manganese Addition on Ductility and Magnetic
Properties of 6.5 % Silicon-Iron Alloy”, IEEE Trans. Magn., 14(4), 258–262 (1978) (Morphology,
Experimental, Magn. Prop., Mech. Prop., 5)
[1979Ind] Inden, G., “Zwischenbericht 4”, 1979, Düsseldorf, Max-Planck-Institut für Eisenforschung as quoted by
[1988 Ray]
[1980Sri] Srivastava, S.C., “Electrodeposition of Ternary Alloys: Developments in 1972 - 1978”, Surf. Technol.,
10, 237–257 (1980) (Review, Electrochemistry, Magn. Prop., 121)
[1980Rod] Rodionov, Y.L., Isfandiyarov, G.G., Zambrzhitskiy, V.N., “Influence of Annealing on the Redistribution
of Atoms in the Austenite of Fe-Ni-Mo and Fe-Ni-Si”, Phys. Met. Metallogr., 49(2), 94–100 (1980)
(Experimental, Kinetics, 8)
[1980Cha] Chart, T., Putland, F., Dinsdale, A., “Calculated Phase Equilibria for the Cr-Fe-Ni-Si System - I Ternary
Equilibria”, Calphad, 4(1), 27–46 (1980) (Phase Diagram, Calculation, 75)
[1982Kub] Kubaschewski, O., “Iron - Silicon” in “Iron Binary Phase Diagrams”, Springer Verlag, Berlin, 136–139
[1982Yed] Yedneral, A.F., Rusanenko, V.V., Smirnova, A.V., “On the Structure of the Intermetallic Phase
Precipitated During Maraging of the Alloy Fe -18% Ni - 3% Si”, Phys. Met. Metall., 53(3), 111–117
(1982), (Crys. Structure, Experimental, 7)
[1983Zay] Zaytseva, R.D., Zakharova, N.A., Perkas, M.D., Rusanenko, V.V., Shaposhnikov, N.G., “Investigation of
the Maraging of Fe-Ni-Si Alloys and the Influence of Cobalt on the Process”, Phys. Met. Metall., 55(1),
117–123 (1983), (Crys. Structure, Experimental, Kinetics, Phys. Prop., 11)
[1988Ray] Raynor, G.V., Rivlin, V.G., “Fe-Ni-Si” in “Phase Equilibria in Iron Ternary Alloys”, Inst. Metals, London,
416–432 (1988) (Crys. Structure, Phase Diagram, Assessment, 20)
[1990Kag] Kagawa, A., Hirata, M., Sakamoto, Y., J. Mater. Sci., 25, 5063–5069 (1990) as quoted by [1999Sun]
[1990Li] Li, Y., Zhang, T., Zheng, Z., Zhu, Y., “Solution Behaviour of Various Alloying Elements in Ni3Si” (in
Chinese), Acta Metall. Sin., 26(3), A172–A176 (1990) (Phase Diagram, Experimental, 9)
[1991Zha] Zhang, T., Li, Y., Zheng, Z., Zhu, Y., “Alloying Behavior of Ni3Si and the 900˚C Isotherms of Several
Ni-Si-X Systems at Ni-Rich Corner” in “High-Temp. Ordered Intermetallic Alloys IV”, Mater. Res. Soc.
Symp. Proc., 213, 137–142 (1991) (Phase Diagram, Experimental, 7)
[1994Rag] Raghavan, V., “Fe-Ni-Si (Iron-Nickel-Silicon)”, J. Phase Equilib., 15(6), 629–630 (1994) (Phase Dia-
gram, Review, 4)
[1994Koz] Kozakai, T., Miyazaki, T., “Experimental and Theoretical Investigations on Phase Diagrams of Fe
Base Ternary Ordering Alloys”, ISIJ Int., 34(5), 373–383 (1994) (Phase Diagram, Calculation, Magn.
Prop., 18)
[1995Slu] Sluiter, M., Kawazone, Y., “Site Preference of Ternary Additions in Ni3Si” in “High-Temperature
Ordered Intermetallic Alloys VI”, Mater. Res. Soc.. Symp. Proc., 364(Pt.2), 1064–1069 (1995) (Experi-
mental, Calculation, Theory, 13)
[1998Ike] Ikeda, O., Himuro, Y., Ohnuma, I., Kainuma, R., Ishida, K., “Phase Equilibria in the Fe-Rich Portion of
the Fe-Ni-Si System”, J. Alloys Compd., 268, 130–136 (1998) (Phase Relations, Experimental, *, 13)
[1998Lan] Landrum, G.A., Hoffmann, R., Evers, J., Boysen, H., “The TiNiSi Family of Compounds: Structure and
Bonding”, Inorg. Chem., 37(22), 5754–5763 (1998) (Crys. Structure, Experimental, 34)
(1998) (Phase Relations, Assessment, Calculation, 83)
[1999Sun] Sung, P.K., Poirier, D.R., “Liquid-Solid Partition Rations in Nickel-Base Alloys”, Metall. Mater. Trans. A,
30A, 2173–2181 (1999) (Crys. Structure, Experimental, 41)
[1999Mie] Miettinen, J., “Thermodynamic Description of Solution Phases of Systems Fe-Cr-Si and Fe-Ni-Si with
Low Silicon Contents and with Application to Stainless Steels”, Calphad, 23(2), 249–262 (1999) (Phase
Relations, Thermodyn., Calculation, 28)

Fe–Ni–Si 13 21
[2001Duh] Duhaj, P., Svec, P., Sitek, J., Janickovic, D., “Thermodynamic, Kinetic and Structural Aspects of the
Formation of Nanocrystalline Phases in Fe73.5–xNixCu1Nb3Si13.5B9 Alloys”, Mater. Sci. Eng. A, 304–306,
[2001Him] Himuro, Y., Ikeda, O., Kainuma, R., Ishida, K., “Effect of Ausaging on the Morphology of Martensite in
an Fe-25%Ni-7.5%Si Alloy”, J. Phys. IV, France, 11(PR8), 205–210 (2001) (Phase Relations, Morpholo-
gy, Experimental, Mechan. Prop., 14)
[2002Tan] Tani, J.-I., Kido, H., “First Princple Calculation of the Geometrical and Electronic Structure of
Impurity-Doped β-FeSi2 Semiconductors”, J. Solid State Chem., 163, 248–252 (2002) (Crys. Structure,
Calculation, Phys. Prop., 23)
[2002Him] Himuro, Y., Kainuma, R., Ishida, K., “Martensitic Transformation and Shape Memory Effect in
Ausaged Fe-Ni-Si Alloys”, ISIJ Int., 42(5), 184–190 (2002) (Phase Relations, Experimental, 21)
[2002Fet] Fetzer, C., Dezsi, I., Vantomme, A., Wu, M.F., Jin, S., Bender, H., “Ternary CoxFe(1–x)Si2 and
NixFe(1–x)Si2 Formed by Ion Implantation in Silicon”, J. Appl. Phys., 92(7), 3688–3693 (2002) (Crys.
Structure, Phase Relations, Experimental, Electronic Structure, 27)
[2003Rag] Raghavan, V., “(Iron-Nickel-Silicon)”, J. Phase Equilib., 24(3), 269–271 (2003) (Crys. Structure, Phase
Diagram, Assessment, 14)
[2004Aru] Arushanov, E., Nenkov, K., Eckert, D., Vinzelberg, H., Roessler, U.K., Behr, G., Mueller, K.-H.,
Schumann, J., “Magnetic and Electrical Properties of Cr- and Ni-doped β-FeSi2 Single Crystals”, J. Appl.
Phys., 96(4), 2115–2121 (2004) (Phase Relations, Experimental, Electr. Prop., Magn. Prop., 31)
[2004Him] Himuro, Y., Tanaka, Y., Kamiya, N., Ohnuma, I., Kainuma, R., Ishida, K., “Stability of Ordered L12
Phase in Ni3Fe-Ni3X (X: Si and Al) Pseudobinary Alloys”, Intermetallics, 12(6), 635–643 (2004) (Crys.
Structure, Morphology, Phase Diagram, Experimental, Electr. Prop., Magn. Prop., *, 19)
[2005Him] Himuro, Y., Tanaka, Y., Ohnuma, I., Kainuma, R., Ishida, K., “Phase Equilibrua and γ’-L12 Phase
Stability in the Ni-rich Portion of Ni-Fe-Si and Ni-Fe-Al Systems”, Intermetallics, 13, 620–630 (2005)
(Crys. Structure, Phase Diagram, Experimental, 19)
[2005Hos] Hosseini Madaah, H.R., Bahrami, A., “Preparation of Nanocrystalline Fe-Si-Ni Soft Magnetic Powders
by Mechanical Alloying”, Mat. Sci. Eng. B, 123, 74–79 (2005) (Morphology, Experimental, Magn.
Prop., 17)
[2008Kuz] Kuznetsov, V., “Fe-Ni (Iron-Nickel)”, MSIT Binary Evaluation Program in MSIT Workplace, G. (Ed.),
MSI, Materials Sciens International Servises GmbH, Stuttgart, to be published (2008) (Crys. Structure,
Phase Diagram, Phase Relations, Thermodyn., Assessment, Phys. Prop., #, 41)
(1990)

Fe–Ni–Ti 14 1
Iron – Nickel – Titanium

Gautam Ghosh
Introduction
A fairly large number of experimental studies have been carried out to establish the ternary
phase equilibria [1938Vog, 1941Vog, 1963Spe, 1967Dud, 1981Loo, 1999Abr, 2006Ria]. The
first comprehensive study of phase equilibria was carried out by [1938Vog]. They used
metallography, thermal analysis and X-ray diffraction techniques. [1963Spe] reported partial
isothermal sections, representing phase equilibria of Fe corner, at 700 and 1100˚C. [1967Dud]
established a quasibinary section, TiFe-TiNi, using twenty-one ternary alloys prepared using
elements of purity greater than 99.94%. They used metallography, thermal analysis, X-ray
diffraction techniques to determine the phase equilibria. [1981Loo] employed diffusion
couples technique to determine the isothermal section at 900˚C. They prepared alloys using
elements of following purity: 99.95% Fe, 99.99% Ni and 99.97% Ti. Three types of diffusion
couples, element/element, element/alloy, alloy/alloy, and fifteen in total, were prepared by
solid state resistance welding. The couples were then sealed in evacuated silica tubes and
annealed at 900˚C for up to 900 h. Except [1981Loo], other experimental studies were
restricted to alloys containing less than 50 at.% Ti. The results of these phase equilibrium
studies were reviewed earlier [1949Jae, 1985Gup, 1991Gup].
More recently, [1994Ali1] reported the phase equilibria of alloys containing more than 50
at.% Ti. They used Armco Fe, N-00 grade electrolytic Ni, and iodide Ti to prepare alloys by arc
melting in an inert atmosphere. They prepared a number of ternary alloys in the Ni and Fe
atomic ratios of 1:3, 1:1, and 3:1. The phase equilibria were determined using thermal analysis,
metallography and X-ray diffraction. [1994Ali2] carried out rapid solidification of ternary
alloys containing up to 33.85 at.% Fe and 26.8 at.% Ni. The alloys were subsequently annealed
at 900˚C for 25 h, and the microstructures were compared. [1994Jia] measured the partition-
ing of Fe and Ti between (Ni) and TiNi3 (or the tie lines) at 1000, 1100 and 1200˚C. They
prepared diffusion couples between 5Fe-Ni (mass%) and 21Ti-1Fe-Ni (mass%) alloys. The
couples were annealed for up to 300 h followed by quenching into iced brine. The composi-
tions of the phases were measured by electron probe microanalysis.
[1999Abr] determined the isothermal section at 1000˚C using both bulk alloys and
diffusion couples. They prepared bulk alloys using iodide grade Ti, electrolytic grade Ni and
carbonyl grade Fe in an arc furnace. The bulk alloys were equilibrated at 1200˚C for 150 h.
They also prepared a large number of couples using Fe-Ni, Fe-Ti and Ni-Ti alloys that were
welded at 1200˚C and at a pressure of 19.6 MPa. The couples were subsequently annealed at
1200˚C. The diffusion paths and phase compositions were established by means of electron
probe microanalysis. Besides graphical representation, [1999Abr] tabulated the tie line and tie
triangle compositions. Based on diffusion couple results, [1999Abr] identified six two-phase
regions (TiNi-TiFe2, TiNi-TiNi3, TiNi3-TiFe2, γ(Fe,Ni)-TiNi3, γ(Fe,Ni)-TiFe2) and three
three-phase regions (γ(Fe,Ni)-TiFe2-TiNi3, TiFe2-TiNi-TiNi3, (βTi)-TiFe-Ti2Ni).

2 14 Fe–Ni–Ti
[2006Ria] studied phase relations in six ternary alloys, with composition along Ti2Ni-
Ti2Fe, using SEM-EDS and DTA methods. The alloys were prepared by arc melting using 99.99
mass% Fe, 99.99 mass% Ni and 99.98 mass% Ti. They were homogenized at 900˚C for 15 days.
The authors reported phase compositions and a tentative isopleth.
[1999Efi, 2000Efi] studied microstructures of TiFe/Ni diffusion couples annealed at
1200˚C for up to 1.5 h. Based on the dynamics of interfacial microstructure, they derived
the interdiffusion coefficients.
Besides phase equilibria studies at high temperatures, the effect of Fe on the low tempera-
ture martensitic transformations of TiNi has also been studied extensively [1982Hwa1,
1982Hwa2, 1982Nis, 1983Sav, 1984Ano, 1984Pus, 1985Goo, 1985Sav, 1986Edm, 1987Chu,
1987Kha, 1987Sas, 1989Ano1, 1989Ano2, 1990Rao, 1991Pro, 1992Ruz, 1992Shi, 1993Mat,
1995Air, 1995Gue, 1997Har, 1998Tam, 1999Zha, 2000Chu, 2000Lap, 2000Vor, 2000Xu,
2001Mur, 2002Ish, 2005Cho, 2005Wan, 2006Fan, 2007Pro].
[2001Gup] reviewed some of the results of recent phase equilibria studies. Additional
reviews have also been published by [2006Cac] and [2006Gho].
A summary of experimental studies on phase relations is given in Table 1.
Binary Systems
The Fe-Ti, Fe-Ni and Ni-Ti binary phase diagrams are accepted from [1991Mur], [2008Kuz]
and [2008Ted], respectively.
Solid Phases
The solubility of Fe in (βTi) can be increased from 24 to 29.5 at.% by rapid solidification
[1994Ali2] where the cooling rate was estimated to be 106 ˚C·s–1. Rapid solidification also
suppresses the eutectoid reaction (βTi) Ð (αTi) + TiFe. In the ternary alloys, up to 25.95 at.%
Fe and 8.23 at.% Ni can be dissolved in (βTi) by rapid solidification.
[1968Abr] reported the lattice parameter of two sets of austenitic alloys: Fe-27Ni (at.%)
containing up to 10 at.% Ti and Fe-30Ni (at.%) containing up to 6 at.% Ti. Powders of these
alloys were solution treated at 1024˚C and quenched to room temperature. Variation of lattice
parameter gives the solubility limit of Ti in austenite at 1024˚C. For example, it is about 5.4
at.% Ti in Fe-27Ni (at.%) alloy.
Fcc to bcc martensitic transformation in Fe rich alloys has been investigated extensively
[1963Yeo, 1969Abr, 1972Kok, 1974Whi, 1977Hal, 1978Uva, 1984Kab, 1984Tad]. With the
addition of Ti in Fe-Ni alloys, the crystal symmetry of martensite changes from bcc to bct due
to clustering and/or precipitation of metastable coherent precipitates (L12-Ni3Ti) [1969Abr,
1974Whi, 1977Hal]. The c/a ratio of bct martensite increases linearly with Ti content in the
alloy; however, the degree of tetragonality depends on the Ni content in the alloy.
TiFe and TiNi form a continuous solution in the solid state [1967Dud, 1981Loo], and the
lattice parameter decreases linearly from TiNi to TiFe [1967Dud]. Using a linear muffin-tin
orbital method, [2002Boz] calculated the formation energies associated with dilute additions
of Ni in B2-TiFe. In the dilute limit of Ni, the formation energy of (Fe,Ni)0.5Ti0.5 is predicted
to be more negative than Fe0.5(Ti,Ni)0.5 implying that Ni atoms prefer to occupy the Fe
sublattice in TiFe.
Fe–Ni–Ti 14 3
At 900˚C, TiFe2 dissolves up to 28 at.% Ni, TiNi3 dissolves up to 14 at.% Fe, and Ti2Ni
dissolves up to 26 at.% Fe [1981Loo]. The solubility of Fe in TiNi3 increases to 15.4 ±⊊0.8
at.% Fe at 1200˚C [1999Efi]. In TiNi3 and NiTi2, Fe resides primarily on the Ni sublattice. In
TiFe2, Ni resides primarily on the Fe sublattice.
Binary B2-TiNi undergoes martensitic transformation at low temperature to a monoclinic
structure, commonly known as B19’ martensite [1992Shi, 1995Gue]. However, at slightly Ni
rich composition, the presence of dislocations, or the presence of metastable Ti3Ni4 precipi-
tates are known to promote another displacive transformation to a rhombohedral structure
preceding B19’ transformation, commonly known as the R phase [1987Sas, 1995Air, 1997Har,
1998Tam, 2001Mur, 2002Ish, 2005Ste, 2006Cho, 2006Fan, 2006Yam]. Depending on the
composition and thermal history of binary TiNi, and with the addition of Fe, the transforma-
tion temperatures B2 → R → B19’ may be well separated. The presence of the R-phase is very
useful for shape memory applications which rely on small thermal hysteresis.
[1994Jia] reported the partitioning ratio of Fe, defined by xFe(TiNi3)/xFe(Ni), where xFe is
the mole fraction of Fe, between (Ni) and TiNi3. The partitioning ratios at 1000, 1100 and
1200˚C were 0.41, 0.44 and 0.61, respectively.
There is no ternary phase in this system. The details of the crystal structures and lattice
parameters of the solid phases are listed in Table 2.
Quasibinary Systems
Even though there are no true quasibinary sections, two sections have been reported as quasi-
binary. [1938Vog] reported the TiFe2-TiNi3 section with the eutectic reaction L Ð TiFe2 +
TiNi3 at 1320˚C. [1967Dud] established the section TiFe-TiNi, which is shown in Fig. 1. The
continuous solid solubility between TiFe and TiNi was confirmed by lattice parameter and
hardness measurements. [1967Dud] established only the solidus boundary. However, in the
TiFe-end both liquid+TiFe2 and liquid+TiFe2+Ti(Fe,Ni) phase regions should appear due to
formation of TiFe. The liquidus line expected by [1967Dud] appears to be inconsistent with
the investigated solidus. Also, in agreement with the comments by [1991Gup] it is here
reported with a minimum so that B2-Ti(Fe,Ni) melts congruently around 1270˚C.
Figure 2 shows the reaction scheme involving five invariant (U1, U2, E1, U3, U4) and a
maximum (e1) reactions. Among these, e1, U1 and E1 were reported by [1938Vog] while U3
and U4 were reported by [1994Ali1]. The invariant reaction U2 has not been experimentally
verified, but it was speculated by [1991Gup]. The composition of the phases participating in
e1, U1, E1 and U3 are listed in Table 3. These compositions were read from the superimposed
liquidus and projection diagrams provided by [1938Vog], [1994Ali1] and [2001Gup].
Liquidus Surface
The liquidus surface and projection diagram for the composition range Fe-TiFe2-TiNi3-Ni was
presented by [1938Vog]. The superimposed liquidus surface and projection diagram for the Ti
4 14 Fe–Ni–Ti
corner was reported by [1994Ali1], and slightly modified by [2001Gup]. Using these results
and the accepted binary phase diagrams, the liquidus surface shown in Fig. 3 was constructed.
Isothermal Sections
[1963Spe] reported partial isothermal sections of the Fe corner at 700 and 1100˚C; however,
did not provide details of the experimental techniques and procedures. Figure 4 shows a
partial isothermal section of the Fe rich corner at 1100˚C [1963Spe]. Figure 5 and 6 show
isothermal sections at 1000 [1999Abr] and 900˚C [1981Loo], respectively. The results of
[1981Loo] and [1999Abr] agree very well; however, a major discrepancy is that [1999Abr]
observed very little solubility of Fe in Ti2Ni while [1981Loo] reported that about 78 % Ni sites
in Ti2Ni can be substituted by Fe i.e., the solid solubility is about 26 at.% Fe. In another
investigation, [1994Ali2] reported that only about 1.5 at.% Fe dissolves in Ti2Ni where rapidly
solidified Fe-Ni-Ti alloys were annealed at 900˚C for only 25 h compared to up to 900 h by
[1981Loo]. It is not clear if a short annealing treatment used by [1994Ali2] is responsible for
the much lower solubility of Fe in Ti2Ni compared to [1981Loo]. The continuous solubility of
TiFe and TiNi observed by [1981Loo] and [1999Abr] confirms the earlier results of
[1967Dud]. In Figs. 5 and 6, the widths of TiNi and TiNi3 fields have been adjusted to make
them consistent with the accepted Ni-Ti phase diagram. The solubility of Fe in TiNi3 at 900˚C
is about 15 at.% [1981Loo] which is much higher than reported by [1938Vog]. Figure 7 shows
a partial isothermal section of the Fe corner at 700˚C [1963Spe].
Several temperature-composition sections have been reported. Figures 8, 9 and 10 show

polythermal sections at 8, 12 and 14.4 mass% Ti [1938Vog], respectively, and Fig. 11 shows
an isopleth at 66.67 at.% Ti [2006Ria]. While the later authors identified a two-phase field,
Ti2(Fe,Ni)+Ti(Fe,Ni), in the isopleth based on the microstructural observations, this is most
likely to have caused by non-stoichiometric alloy composition. To be consistent with the
isothermal section at 900C in Fig. 6, the above mentioned two-phase field is considered as a
single-phase field Ti2(Fe,Ni) in Fig. 11. Figures 12 and 13 show temperature-composition
sections at constant Fe:Ni mass ratios of 90:10 and 40:60, respectively [1938Vog]. The
existence of two invariant reactions at 1200˚C (U1) and at 1120˚C (E1) is reflected in Figs. 8
to 10. The partial isopleths of the Ti corner and at constant Fe:Ni atomic ratios of 1:3, 1:1 and
3:1 are shown in Figs. 14, 15 and 16, respectively [1994Ali1]. On the basis of these three
isopleths, [1994Ali1] gave a superimposed partial liquidus surface and projection diagram for
the Ti corner. Due to the existence of (βTi)+Ti(Fe,Ni) phase field in Fig. 14, the original
projection diagram was slightly modified by [2001Gup].
Thermodynamics
[1975Ost] reported the enthalpy of dissolution of Ti in Fe-Ni melts. [1991Lue] measured the
enthalpy of mixing of liquid Tix(Fe0.89Ni0.11)1–x, 0.295 ≤ x ≤ 0.041, at 1600˚C using a high-
vacuum high-temperature calorimeter. They also modeled the molar heat of mixing of the
Fe–Ni–Ti 14 5
entire Fe-Ni-Ti system using various extrapolation methods. Subsequently, these experimental
data were used to validate “thermodynamic adapted” power series for the extrapolation of
thermodynamic quantities [1995Tom]. [1999Thi] also carried out calorimetric measurement
of heat of mixing of liquid alloys in three composition ranges: (i) (Fe84Ti16)1–xNix, 0.02 < x <
0.35 at 1621˚C, (ii) (TiFe2)1–xNix, 0.02 < x < 0.4 at 1643˚C, and (iii) (TiNi)1–xFex, 0.02 < x <
0.8 at 1645˚C. [1999Thi] used an associate model to describe the heat of mixing of ternary
alloys. Two associates, TiNi3 and TiFe, were assumed to be present in the liquid. In the entire
composition range, the model calculations agree very well with the experimental data imply-
ing that binary interactions are sufficient to describe the excess heat of mixing. Their model
calculations also agree very well with the experimental data of [1991Lue]. The functional
representation of experimental heat of mixing along four composition sections is provided in
Table 4. Figure 17 shows the isoenthalpy (mixing) contours at 1643˚C [1999Thi]. [1991Lue]
also reported isoenthalpy (mixing) contours by an extrapolation method, but their results
differ significantly from [1999Thi].
[1990Kum] calculated phase boundaries involving bcc, fcc ((αFe), (γFe)) and Ti2Ni by
CALPHAD method. They did not consider any ternary interaction parameter, and partial
isothermal sections were calculated at 850, 950, 1050 and 1150˚C. Later, [1998Mie] also
applied CALPHAD method to calculate phase equilibria involving liquid, (αFe) and (γFe)
phases. He introduced asymmetric ternary interaction parameters for the liquid phase and a
symmetric ternary interaction parameter for the bcc phase, but no ternary interaction
parameter for the fcc phase. The calculated isothermal sections of Fe corner at 1100 and
1200˚C were found to be in good agreement with the experimental data.
A summary of experimental investigation of properties is given in Table 5.

Ti0.5(Fe1–xNix)0.5 alloys are known to exhibit shape memory effect [1999Zha, 2000Jia,
2000Xu, 2005Wan, 2006Cho, 2007Pro]. [2000Xu] obtained a maximum shape recovery strain
of 5.6% after deforming Ti50Fe2Ni48 alloy at –70˚C. The damping behavior [2006Fan],
resistivity [1987Chu, 2005Cho] and magnetic susceptibility [2005Cho, 2005Yam] of B2-TiNi
(Fe) alloys have also been reported. The hot deformation behavior and anomalous ductility of
Ti50Fe2Ni48 has been studied by Nishida et al. [2003Nis].
The single crystal elastic constants (c’ and c44) of B2-TiNi(Fe) alloys have been studied by
ultrasonic resonance method [1987Kha, 1999Zha]. It has been shown that both c’ and c44
decrease sharply near the martensitic transformation temperature.
Hydriding behavior of TiFe(Ni) phase has been investigated [1999Lee, 2003Miy, 2004Jan,
2005Jan]. [1999Lee] studied hydriding behavior of TiFe1–xNix for x = 0.1, 0.15 and 0.2. They
found that partial substitution of Fe by Ni in TiFe does not change the hydriding behavior,
except that these alloys can be hydrided without the activation treatment. Nanocrystalline
TiFe0.25Ni0.75 alloy has 1.5 times the discharge capacity of TiFe [2004Jan, 2005Jan].
C14-Ti(Fe1–xNix)2 is antiferromagnetic, and the Néel temperature of C14-Ti(Fe1–xNix)2
decreases with increasing Ni content [2005Yam].

6 14 Fe–Ni–Ti
Miscellaneous
Discontinuous precipitation in ternary metastable alloys has been studied several times
[1963Spe, 1973Zem, 1979Fou, 1979Zem, 1981Zem, 1995Zem]. [1963Spe] investigated an
Fe-5.8Ti-29.7Ni (mass%) alloy in the temperature range of 400 to 975˚C, and [1979Fou]
investigated an Fe-6.5Ti-28.5Ni (mass%) alloy in the temperature range of 400 to 900˚C.
[1979Zem] used Fe-(2 to 5)Ti-(25 to 26)Ni (mass%) alloys heat treated at 790˚C. According to
[1963Spe], ternary alloys may exhibit two types discontinuous precipitations
g ! g1 þ TiNi3
g1 ! g2 þ ðFe; NiÞ2 Ti;
where γ1 and γ2 are austenitic solid solutions with different solute contents. Both
[1979Fou] and [1979Zem] observed only the first discontinuous reaction where TiNi3 is a
metastable phase because the alloys lie in the γ+TiFe2 phase field. The second discontinuous
reaction is very sluggish [1963Spe].
[1988Sag, 1992Sag] studied the effect of severe plastic deformation of austenitic 2.6Ti-Fe-
36Ni alloy containing equilibrium TiNi3 (η, D024) and metastable TiNi3 (γ’, L12) precipitates
which were obtained by adjusting the aging treatments. Upon severe plastic deformation both
types of precipitates dissolve in the matrix due to strong interaction with dislocations
[2002Kuz].
[1995Ali] carried out rapid solidification of 29 alloys in the composition range Ti-TiFe-
TiNi. They reported the phases present after rapid solidification and also after aging at 900˚C
for 25 h.
The hot deformation of austenitic alloys and the resulting properties were studied by
[1989Gor, 1991Pro]. The martensitic transformation (γ→α) start temperature (Ms) of
Fe-22.5Ni (mass%) [1963Yeo], Fe-27Ni (mass%) [1969Abr] and Fe-29.5Ni (mass%)
[1969Abr] alloys decreases with the addition of Ti.
The effect of Fe on the martensitic transformations (B2 → R → B19’) in TiNi has been
studied extensively [1982Hwa1, 1982Hwa2, 1982Nis, 1983Sav, 1984Ano, 1984Pus, 1985Goo,
1985Sav, 1986Edm, 1987Chu, 1987Kha, 1987Sas, 1989Ano1, 1989Ano2, 1990Rao, 1991Pro,
1992Ruz, 1992Shi, 1993Mat, 1995Air, 1995Gue, 1997Har, 1998Tam, 1999Zha, 2000Chu,
2000Lap, 2000Vor, 2000Xu, 2001Mur, 2002Ish, 2005Cho, 2005Wan, 2006Fan, 2007Pro].
Addition of Fe decreases both pre-martensitic and martensitic transformation temperatures,
and stabilizes the R phase (rhombohedral).
[1999Efi] reported the interdiffusion coefficient of ternary solid solutions (γ) at 1200˚C
with nickel contents of 87 to 99 at.%.
[1985Val] found that the average magnetic moment of γ’FeNi3 decreases when Fe is
replaced by Ti.

Fe–Ni–Ti 14 7
. Table 1
Investigations of the Fe-Ni-Ti Phase Relations, Structures and Thermodynamics
Method/Experimental
Reference Technique Temperature/Composition/Phase Range Studied
[1938Vog] LOM, DTA Fe-Ni-Ni3Ti-Fe3Ti, vertical sections

[1941Vog] LOM 900-1220˚C, Ni-17Fe-14Ti (mass%)
[1963Spe] LOM, TEM, XRD Partial isothermal sections at 700 and 1100˚C,
Fe-30Ni-6Ti (mass%)
[1967Dud] DTA, XRD, hardness TiNi-TiFe
[1968Abr] XRD Fe-(27-30) at.% Ni-(1-10) at.% Ti
[1975Ost] Calorimetry 1600˚C, liquid
[1981Loo] LOM, XRD, EPMA Isothermal section at 900˚C
[1991Lue] Calorimetry 1600C, liquid
[1994Ali1, DTA, XRD, metallography Ti-TiFe-TiNi; vertical sections
1994Ali2]
[1994Jia] EPMA 1000 to 1200˚C, partitioning ratio between (Ni) and
Ni3Ti
[1995Ali] XRD 900C; Ti-TiFe-TiNi
[1999Abr] EPMA Isothermal section at 1000˚C
[1999Efi] EPMA, hardness 1200C, interdiffusion
[1999Thi] Calorimetry 1624-1645˚C, liquid
[2000Efi] EPMA, hardness 1100-1250˚C, interdiffusion
[2006Ria] SEM-EDS, DTA Ti2Ni-Ti2Fe

8 14 Fe–Ni–Ti
. Table 2
Pearson
Phase/ Symbol/
Temperature Group
Range Space/ Lattice Parameters
[˚C] Prototype [pm] Comments/References
(δFe)(h2) cI2 a = 293.15 pure Fe at 1390˚C [Mas2]

1538 - 1394 Im3m
W
γ, (γFe,Ni) cF4 a = 358.37 Fe71.74Ni27.07Ti1.19, at 20˚C [1968Abr]

Fm3m a = 359.13 Fe68.27Ni26.96Ti4.77, at 20˚C [1968Abr]
Cu a = 358.90 Fe68.32Ni30.38Ti1.3, at 20˚C [1968Abr]
a = 359.39 Fe64.39Ni29.65Ti5.96, at 20˚C [1968Abr]
a = 359.0 Fe31Ni63Ti6, at 20˚C [1981Loo]
a = 365.2 Fe31Ni63Ti6, at 900˚C [1981Loo]
(γFe)(h1) a = 364.67 pure Fe [Mas2]
1394 - 912
(Ni) a = 352.32 pure Ni at 20˚C [V-C2]
< 1455
(αFe)(r) cI2 a = 286.65 pure Fe at 20˚C [V-C2]
< 912 Im3m
W
(εFe) hP2 a = 246.8 at 25˚C, 13 GPa [V-C2]
P63/mmc c = 396.0
Mg
(βTi)(h) cI2 a = 330.65 [Mas2]
1670 - 882 Im3m
W
(αTi)(r) hP2 a = 295.06 pure Ti at 25˚C [Mas2]
≤ 882 P63/mmc c = 468.25
Mg
γ’FeNi3 cP4 a = 355.23 63 to 85 at.% Ni [2008Kuz]
≤ 517 Pm3m
AuCu3
TiFe2 hP12 a = 478.7 24.0 to 36.0 at.% Ti [V-C2]
≤ 1427 P63/mmc c = 781.5
MgZn2 dissolves up to 28 at.% Ni [1981Loo]
Ti(Fe,Ni) cP2 a = 300.0 Fe10.2Ni39.8Ti50, at 20˚C [1967Dud]
Pm3m a = 298.91 Fe25.3Ni24.7Ti50, at 20˚C [1967Dud]
CsCl a = 298.18 Fe35.3Ni14.7Ti50, at 20˚C [1967Dud]
TiFe a = 297.6 49.8 to 51.8 at.% Ti [V-C2]
≤ 1317
TiNi a = 299.8 to 301.0 49.5 to 57 at.% Ni [2008Ted]
≤ 1311

Fe–Ni–Ti 14 9
Pearson
Phase/ Symbol/
Temperature Group
Range Space/ Lattice Parameters
Ti2Ni cF96 a = 1127.8 to 1132.4 33 to 34 at.% Ni [2008Ted]

≤ 984 Fd3m
Ti2Ni dissolves up to 26 at.% Fe [1981Loo]
TiNi hP18 a = 735.8 Ni50.23Ti49.77, at 20˚C [1997Har].
(martensite)
P3 c = 528.55 X-ray diffraction. Known as R phase.
-
TiNi mP4 a = 289.8 Ni49.2Ti50.8, at 20˚C [1992Shi].
(martensite)
P21/m b = 410.8 Single crystal X-ray diffraction. Known as
B19’ martensite.
TiNi c = 464.6
β = 97.78˚
TiNi3 hP16 a = 510.28 75 to 80.1 at.% Ni at 1300˚C [2008Ted]
≤ 1380 P63/mmc c = 827.19
TiNi3
a = 510.3 ± 0.5
c = 832.0 ± 0.8 dissolves up to 14 at.% Fe [1981Loo]
a = 517.0 Fe4Ni72Ti24, at 20˚C [1981Loo]
c = 846.8 Fe4Ni72Ti24, at 900˚C [1981Loo]
. Table 3
Composition (at.%)
Reactions T [˚C] Type Phase Fe Ni Ti
L Ð TiFe2 + TiNi3 1320 e1 L 31.80 39.10 29.10

TiFe2 52.46 16.61 30.93
TiNi3 0.50 73.26 26.24
L + (αFe) Ð (γFe) + TiFe2 1200 U1 L 66.46 17.55 15.99
(αFe) 79.40 11.33 9.26
(γFe) 76.94 13.90 9.16
TiFe2 59.71 8.21 32.01

10 14 Fe–Ni–Ti
Composition (at.%)
Reactions T [˚C] Type Phase Fe Ni Ti
L Ð (γFe) + TiFe2 + TiNi3 1113 E1 L 36.35 40.61 23.04

(γFe) 55.29 35.68 9.03
TiFe2 52.46 16.61 30.93
TiNi3 0.50 73.26 26.24
L + Ti(Fe,Ni) Ð (βTi) + Ti2Ni 960 U3 L 0.91 24.03 75.06
Ti(Fe,Ni) 18.02 28.57 53.41
(βTi) 0.95 4.04 95.01
Ti2Ni 1.11 32.64 66.25
. Table 4
Heat of Mixing (ΔHmix) of Fe-Ni-Ti Liquid Alloys. The Data Below are Due to Functional Repre-
sentation of Experimental Data [1999Thi]
Composition Section Temperature [˚C] ΔHmix, [kJ·(g-at.)–1]
(Fe84Ti16)1–yNiy 1621
y = 0.0 –9.291
y = 0.05 –9.843
y = 0.10 –10.433
y = 0.15 –10.787
y = 0.20 –11.024
y = 0.25 –11.083
y = 0.30 –11.024
y = 0.35 –10.945
(NiTi)1–yFey 1645
y = 0.0 –36.972
y = 0.05 –34.507
y = 0.10 –32.141
y = 0.15 –30.169
y = 0.20 –28.197
y = 0.25 –26.127
y = 0.30 –24.648
y = 0.35 –23.070

Fe–Ni–Ti 14 11
Composition Section Temperature [˚C] ΔHmix, [kJ·(g-at.)–1]
(Fe2Ti)1–yNiy 1643
y = 0.0 –17.362
y = 0.05 –17.872
y = 0.10 –18.191
y = 0.15 –18.511
y = 0.20 –18.511
y = 0.25 –18.415
y = 0.30 –18.670
y = 0.35 –17.681
(Fe89Ni11)1–yTiy 1600
y = 0.0 –1.892
y = 0.05 –5.081
y = 0.10 –8.108
y = 0.15 –10.811
y = 0.20 –13.514
y = 0.25 –15.892
y = 0.30 –17.946
y = 0.35 –20.004
. Table 5
Investigations of the Fe-Ni-Ti Materials Properties
Method/Experimental
[1987Chu] Internal friction and Internal friction and electrical resistance of B2-TiNi(Fe)
resistivity
[1987Kha] Ultrasonic resonance Elastic properties of B2-TiNi(Fe)
[1987Sas] Refraction and Optical properties of B2-TiNi(Fe)
absorption
[1989Gor] Mechanical tests Hardness, yield and tensile strengths, ductility and
fracture toughness of austenitic steels
[1991Pro] Mechanical tests Flow stress of B2-TiNi(Fe)
[1999Zha] Ultrasonic resonance Single crystal elastic constants of B2-TiNi(Fe)
[2000Jia] Mechanical tests Flow stress, shape memory behavior of B2-TiNi(Fe)
[2003Miy] Electrochemical tests Charge/discharge capacity of TiFe1–xNix

12 14 Fe–Ni–Ti
Method/Experimental
[2000Xu] Mechanical tests Shape memory behavior of B2-TiNi(Fe)

[2003Nis] Mechanical tests Stress-strain behavior of B2-TiNi(Fe)
[2004Jan, Electrochemical tests Charge/discharge capacity of TiFe0.25Ni0.75
2005Jan]
[2005Cho] Resistivity, susceptibility Electrical resistivity, magnetic susceptibility, specific heat
of B2-TiNi(Fe)
[2005Wan] Dilatometry Two-way shape memory behavior of B2-TiNi(Fe)
[2005Yam] Magnetometry Magnetization, Néel temperature of C14-Ti(Fe1–xNix)2
[2006Cho] Physical property Specific heat, Debye temperature of B2-TiNi(Fe)
measurement systems
[2006Fan] Dynamic mechanical Damping behavior of B2-TiNi(Fe)
alalyzer
[2007Pro] Mechanical tests Shape memory behavior of B2-TiNi(Fe)

Fe–Ni–Ti 14 13
. Fig. 1
Fe-Ni-Ti. The TiNi-FeTi quasibinary section

14 14
Fe-Ni-Ti. Reaction scheme
. Fig. 2
Fe–Ni–Ti

Fe–Ni–Ti 14 15
. Fig. 3
Fe-Ni-Ti. Liquidus surface projection

16 14 Fe–Ni–Ti
. Fig. 4
Fe-Ni-Ti. Partial isothermal section at 1100˚C

Fe–Ni–Ti 14 17
. Fig. 5
Fe-Ni-Ti. Isothermal section at 1000˚C

18 14 Fe–Ni–Ti
. Fig. 6

Fe–Ni–Ti 14 19
. Fig. 7

20 14 Fe–Ni–Ti
. Fig. 8
Fe-Ni-Ti. A polythermal section at a constant Ti content of 8 mass%

Fe–Ni–Ti 14 21
. Fig. 9
Fe-Ni-Ti. A polythermal section at a constant Ti content of 12 mass%

22 14 Fe–Ni–Ti
. Fig. 10
Fe-Ni-Ti. A polythermal section at a constant Ti content of 14.4 mass%

Fe–Ni–Ti 14 23
. Fig. 11
Fe-Ni-Ti. A polythermal section at a constant Ti content of 66.67 at.%

24 14 Fe–Ni–Ti
. Fig. 12
Fe-Ni-Ti. A polythermal section at a constant mass ratio of Fe:Ni=90:10

Fe–Ni–Ti 14 25
. Fig. 13
Fe-Ni-Ti. A polythermal section at a constant mass ratio of Fe:Ni=60:40

26 14 Fe–Ni–Ti
. Fig. 14
Fe-Ni-Ti. Partial polythermal section along the line of constant Fe:Ni atomic ratio of 1:3

Fe–Ni–Ti 14 27
. Fig. 15
Fe-Ni-Ti. Partial polythermal section along the line of constant Fe:Ni atomic ratio 1:1

28 14 Fe–Ni–Ti
. Fig. 16
Fe-Ni-Ti. Partial polythermal section along the line of constant Fe:Ni atomic ratio of 3:1

Fe–Ni–Ti 14 29
. Fig. 17
Fe-Ni-Ti. Enthalpy of mixing (in kJ·(mol-atom)–1) of liquid alloys at 1643˚C

30 14 Fe–Ni–Ti
References
[1938Vog] Vogel, R., Wallbaum, H.J., “The System Fe-Ni3Ti-Fe2Ti” (in German), Arch. Eisenhuettenwes., 12,
299–304 (1938) (Phase Diagram, Phase Relations, Experimental, #, *, 16)
[1941Vog] Vogel, R., “About Observation of Enforced Precipitation in the Solid Solution” (in German),
Z. Metallkd., 33, 376–377 (1941) (Experimental, Phase Relations, 1)
[1949Jae] Jaenecke, E., “Ni-Fe-Ti” (in German) in “Kurzgefasstes Handbuch aller Legierungen”, Winter Verlag,
[1963Spe] Speich, G. R., “Cellular Precipitation in an Austenitic Fe-30Ni-6Ti Alloy”, Trans. Met. Soc. AIME, 227,
754–762 (1963) (Crys. Structure, Experimental, Phase Relations, #, *, 31)
[1963Yeo] Yeo, R.G.B., “The Effects of Some Alloying Elements on the Transformation of Fe-22.5%Ni Alloys”,
Trans. Met. Soc. AIME, 227, 884–890 (1963) (Experimental, Phase Relations, 13)
[1967Dud] Dudkina, L.P., Kornilov, I.I., “An Investigation of the Equilibrium Diagram of the TiNi-TiFe System”,
Russ. Metall., (4), 98–101 (1967), translated from Izv. Akad. Nauk SSSR, Met., (4), 184–187 (1967)
(Experimental, Phase Relations, Phase Diagram, #, *, 13)
[1968Abr] Abraham, J.K., “Lattice Parameters as a Function of Ti in Austenitic Fe-Ni-Ti Alloys”, Trans. Met. Soc.
AIME, 242, 2365–2369 (1968) (Crys. Structure, Experimental, 10)
[1969Abr] Abraham, J.K., Pascover, J.S., “The Transformation and Structure of Fe-Ni-Ti Alloys”, Trans. Met. Soc.
AIME, 245, 759–768 (1969) (Crys. Structure, Experiment, 13)
[1972Kok] Kokorin, V.V., Gorbach, V.G., Samsonov, Yu.I., “Martensitic Transformations in Aged Alloys of
Fe-Ni-Ti” (in Russian), Metallofizika, (42), 87–96 (1972) (Crys. Structure, Experimental, 20)
[1973Zem] Zemtsova, N.D., Malyshev, K.A., “Continuous Decomposition of a γ-Solid Solution in Iron-Nickel-
Titanium Alloys”, Phys. Met. Metallogr. (Engl. Transl.), 35(5), 108–114 (1973) (Crys. Structure,
[1974Whi] Whiteman, J.A., Sarma, D.S., “Structure of Martensites in Fe-Ni-Ti Alloys”, Metall. Mater. Trans. A, 5
[1975Ost] Ostrovskii, O.I., Dyubanov, V.G., Stomakhin, A.Ya., Grigoryan, V.A., “Enthalpy of Dissolution of
Titanium in Iron-Nickel Melts”, Izv. Vyss. Uchebn. Zaved., Chern. Metall., (7), 67–70 (1975) (Experi-
[1977Hal] Hall, M.M., Winchell, P.G., “Tetragonality of Fe-Ni-Ti Martensite”, Acta Metall., 25(7), 735–750 (1977)
(Crys. Structure, Experimental, 27)
[1978Uva] Uvarov, A.I., “Martensite Transformation, Induced by Stressing, and the Mechanical Properties in
Iron-Nickel Based Aged Alloys” (in Russian), Metallofizika, (74), 109–111 (1978) (Crys. Structure,
Experimental, 7)
[1979Fou] Fournelle, R.A., “Discontinuous Coarsening of Lamellar Cellular Precipitates in an Austenitic Fe-
30Ni-6Ti Alloy”, Acta Metall., 27, 1135–1145 (1979) (Experimental, 18)
[1979Zem] Zemtsova, N.D., Mabyshev, K.A., Starchenko, Ye.I., “Cellular Decomposition in Undeformed Meta-
stable Fe-Ni-Ti Alloys”, Phys. Met. Metallogr., 48(2), 128–135 (1979) (Experimental, Thermodyn., 11)
[1981Loo] van Loo, F.J.J., Vroljik, J.W.G.A., Bastin, G.F., “Phase Relations and Diffusion Paths in the Ti-Ni-Fe
System at 900˚C”, J. Less-Common Met., 77, 121–130 (1981) (Experimental, Phase Relations, #, *, 11)
[1981Zem] Zemtsov, N.D., Starchenko, Ye.I., “Structure Mechanism of the Decomposition of Precipitation
Hardened Austenitic Iron-Nickel-Titanium Alloys”, Phys. Met. Metallogr. (Engl. Transl.), 52(4),
[1982Hwa1] Hwang, C.M., Meichle, M., Salmon, M.B., Wayman, C.M., “Transformation Behavior of Ti50Ni47Fe3
Alloy: I. Incommensurate and Commensurate Phases”, J. Phys., 43(12), C4-231–C4-236 (1982) (Crys.
[1982Hwa2] Hwang, C.M., Salmon, M.B., Wayman, C.M., “Transformation Behavior of Ti50Ni47Fe3 Alloy:
I. Martensitic Transformation”, J. Phys., 43(12), C4-237–C4-242 (1982) (Crys. Structure, Experi-
mental, 5)
[1982Nis] Nishida, M., Honma, T., “Phase Transformations in Ti50Ni50-xFex Alloys”, J. Phys., 43(12), C4-225–C4-
[1983Sav] Savvinov, A.S., Sivokha, V.P., Khachin, V.N., “Martensitic Transformations in B2-Type Titanium
Compounds” (in Russian), Metallofizika, 5(6), 30–36 (1983) (Crys. Structure, Electr. Prop., Experi-

Fe–Ni–Ti 14 31
[1984Ano] Anokhin, S.V., Lotkov, A.I., “Change in Electronic Structure and Crystal Structure in Ti(Ni, Fe) Alloys
Just before the Martensitic Transformation”, Sov. Phys.- Dokl.(Engl. Transl.), 34(8), 734–735 (1984)
[1984Kab] Kabanova, I.G., Zemtsova, N.D., Sagaradze, V.V., “Parameters of Shear Strain During γ-α and α-γ
Martensitic Transformations in an Aged Austenitic Fe-Ni-Ti Alloy”, Phys. Met. Metallogr. (Engl.
Transl.), 58(2), 120–130 (1984), translated from Fiz. Metal. Metalloved., 58(2), 344–454, 1984 (Crys.
[1984Pus] Pushin, V.G., Khachin, V.N., Savvinov, A.S., Kondratev, V.V., “Structural Phase Transformations and
Properties of the Alloys NiTi and NiTiFe”, Sov. Phys.- Dokl. (Engl. Transl.), 29(8), 681–683 (1984),
translated from Dokl. Akad. Nauk SSSR, 277, 1388–1391 (1984) (Crys. Structure, Experimental,
Kinetics, 11)
[1984Tad] Tadaki, T., Asayama, K., Shimizu, K., “Some Observations of Ausageing Effects on the Martensitic
Transformation in an Fe-Ni-Ti Alloy”, Trans. Jpn. Inst. Met., 25(2), 80–88 (1984) (Crys. Structure,
Experimental, 19)
[1985Goo] Goo, E., Sinclair, R., “The B2 to R Transformation in Ti50Ni47Fe3 and Ti49.5Ni50.5”, Acta Met., 33(9),
[1985Gup] Gupta, K.P., Rajendraprasad, S.B., Jena, A.K., Sharma, R.C., “The Iron-Nickel-Titanium System”, J.
Alloy Phase Diagrams, 1, 59–68 (1985) (Phase Diagram, Phase Relations, Review, #, *, 21)
[1985Sav] Savvinov, A.S., Sivokha, V.P., Khachin, V.N., “Martensitic Transformations in B2-Type Titanium
Compounds”, Phys. Metals, 5(6), 1107–1118 (1985), translated from Metallofizika, 5(6), 30–36 (1983)
(Crys. Structure, Electr. Prop., Experimental, Phase Relations, 7)
[1985Val] Valiyev, E.Z., Men’shikov, A.Z., Panakhov, T.M., “The Structural State of Alloys Ni3(Fe1–xTix) and
Ni3(Fe1–xNbx) During Atomic Ordering”, Phys. Met. Metallogr., 59(1), 123–129 (1985) (Crys. Structure,
Experimental, 14)
[1986Edm] Edmonds, K.R., Hwang, C.M., “Phase Transformations in Ternary TiNiX Alloys”, Scr. Metall., 20(5),
733–737 (1986) (Experimental, Phase Relations, 7)
[1987Chu] Chui, N.-Y., Huang, Y.-T., “A Study of Internal Friction, Electric Resistance and Shape Change in a
Ti-Ni-Fe Alloy During Phase Transformation”, Scr. Metall., 21, 447–452 (1987) (Crys. Structure,
Experimental, 8)
[1987Kha] Khachin, V.N., Muslov, S.A., Pushin, V.G., Chumlyakov, Yu.I., “Anomalies in the Elastic Properties of
TiNi-TiFe Single Crystals”, Sov. Phys. – Dokl., 32(7), 606–608 (1987) (Crys. Structure, Experimental,
Phys. Prop., 7)
[1987Sas] Saskovskaya, I.I., Pushin, V.G., “Optical Properties and Structure of TiNi and TiNiFe Alloys During
the B2-R Temperature and Concentrational Transformation”, Phys. Met. Metallogr. (Engl. Transl.), 64
(5), 56–64 (1987), translated from Fiz. Met. Metalloved. 64(5), 896–904 (1987) (Crys. Structure,
Experimental, Optical Prop., 12)
[1988Sag] Sagaradze, V.V., Makozov, S.V., “Dissolution of Spherical and Platelike Intermetallics in Fe-Ni-Ti
Austenitic Alloys During Cold Plastic Deformation”, Phys. Met. Metallogr., 66(2), 111–120 (1988)
[1989Gor] Gorbach, V.G., Jelenkowski, J., Filipiuk, J., “Microstructure and Mechanical Properties of Duplex
Martensitic-Austenitic Fe-Ni-Ti Steels”, Mat. Sci.Technol., 5(1), 36–39 (1989) (Experimental, Mechan.
Prop., 20)
[1989Ano1] Anokhin, S.V., Grishkov, V.N., Lotkov, A.I., “Martensitic Transformations in Ti(Ni,Fe) Alloys”, Sov.
Phys. J., 32(12), 961–964, (1989) (Crys. Structure, Experimental, 8)
[1989Ano2] Anokhin, S.V., Lotkov, A.I., “Change in Electronic Structure and Crystal Structure in Ti(Ni,Fe) Alloys
Just before the Martensitic Transformation”, Sov. Phys. – Dokl., 34(8), 734–735 (1989) (Crys. Structure,
Experimental, 8)
[1990Kum] Kumar, K.C.H., Raghavan, V., “BCC-FCC Equilibrium in Ternary Iron Alloys-IV”, J. Alloy Phase
Diagrams, 6(1), 31–49 (1990) (Experimental, Phase Diagram, Phase Relations, Thermodyn., 49)
[1990Rao] Rao, J., He, Y., Ma, R., “Study of Phase Transition in Ti50Ni47.5Fe2.5 Alloy”, Metall.Trans., 21A,
[1991Gup] Gupta, K.P., “The Fe-Ni-Ti (Iron-Nickel-Titanium) System” in “Phase Diagrams of Ternary Nickel
Alloys”, Indian Institute of Metals, Calcutta, India, 321–343 (1991) (Phase Diagram, Phase Relations,
Review, #, *, 12)
[1991Lue] Lueck, R., Wang, H., Predel, B., “Thermodynamic Investigation of Liquid Iron-Nickel-Titanium
Alloys” (in German), Z. Metallkd., 82, 805–809 (1991) (Experimental, Thermodyn., 17)

32 14 Fe–Ni–Ti
[1991Mur] Murray, J.L., “Fe-Ti (Iron-Titanium)” in “Phase Diagrams of Binary Iron Alloys”, ASM International,
Metals Park, Ohio, 414–425 (1991) (Phase Diagram, Review, #, *, 112)
[1991Pro] Prokoshkin, S.D., Kaputkina, L.M., Bondareva, S.A., Tikhomirova, O.Yu., Fatkullina, L.P., Oleynikova,
S.V., “Structure of Hot-Deformed Austenite and Properties of a Ti-Ni-Fe Alloy after HTMT”, Phys.
Met. Metallogr. (Engl. Transl.), 71(3), 143–148 (1991) (Experimental, Mechan. Prop., 4)
[1992Ruz] Ruzhang, M., “Mössbauer Studies of Ti-Ni-Fe Shape-Memory Alloy”, Philos. Mag. A, 65(1), 123–130
(1992) (Experimental, 10)
[1992Sag] Sagaradze, V.V., Morozov, S.V., “Mechanical Alloying of Fe-Ni-Ti Austenite During Low-Temperature
Deformation”, Mater. Sci. Forum, 88–90, 147–154 (1992) (Crys. Structure, Experimental, Phase Rela-
tions, 3)
[1992Shi] Shimizu, K., Tadaki, T., “Recent Studies on the Precise Crystal-Structural Analyses of Martensitic
Transformation”, Mater. Trans., JIM, 33(3), 165–177 (1992) (Crys. Structure, 101)
[1993Mat] Matveeva, N.M., Klopotov, A.A., Kormin, N.M., Sazanov, Y.A., “Lattice Parameters and the Sequence
of Transformations in Ternary TiNi-TiMe Alloys”, Russ. Metall. (Engl. Transl.), (3), 216–220 (1993),
translated from Izv. RAN, (3), 233–237 (1993) (Experimental, Phase Relations, Crys. Structure, 10)
[1994Ali1] Alisova, S.P., Budberg, P.B., Barmina, T.I., Lutskaya, N.V., “Ti-TiFe-TiNi System”, Russ. Metall. (Engl.
Transl.), (1), 117–121 (1994), translated from Izv. RAN, (1), 158–163 (1994) (Experimental, Phase
Relations, 9)
[1994Ali2] Alisova, S.P., Kovneristyi, Yu.K., Lutskaya, N.V., Budberg, P.B., “Structure of the Rapidly Solidified Ti-
TiFe-TiNi Alloys”, Russ. Metall. (Engl. Transl.), 146–149 (1994), translated from Izv. RAN Met., (1),
158–161, 1994 (Experimental, Phase Relations, 5)
[1994Jia] Jia, C.C., Ishida, K., Nishizawa, T., “Partitioning of Alloying Elements Between γ(A1) and θ(D024)
Phases in The Ni-Ti Base Systems” in “Experimental Methods Phase Diagram Determination”, Morral, J.
E., Schiffman, R.S., Merchant, S.M., (Eds.), The Minerals, Metals and Materials Society, Warrendale,
PA, 31–38 (1994) (Experimental, Phase Diagram, 8)
[1995Air] Airoldi, G., Carcano, G., Riva, G., Vanelli, M., “X-Ray Powder Diffraction Study of the R-Phase in a
Ti50Ni48Fe2 Alloy by a New Calibration Method”, J. Phys., Colloq., 5(C2), 281–286 (1995) (Crys.
[1995Ali] Alisova, S.P., Kovneristyi, Yu.K., Lutskaya, N.V., Budberg, P.B., “Structure of the Rapidly Solidified Ti-
TiFe-TiNi Alloys”, Russ. Metall. (Engl. Transl.), (1), 146–149 (1995), translated from Izv. Ross. Akad.
Nauk Met., (1), 158–161, 1995 (Experimental, Phase Diagram, 5)
[1995Gue] Guerin, G., “Martensitic Transformation and Thermomechanical Properties”, Key Eng. Mater.,
101–102, 339–392 (1995) (Crys. Structure, Phys. Prop., Review, 73)
[1995Tom] Tomiska, J., Wang, H., “On the Algebraic Evaluation of the Ternary Molar Heat of Mixing HE from
Calorimetric Investigations”, Ber. Bunsen-Ges. Phys. Chem., 99(4), 633–640 (1995) (Thermodyn., 27)
[1995Zem] Zemtsova, N.D., “Discontinuous Precipitation as a Factor Increasing the Plasticity of Aging Fe-Ni-Ti
Alloys”, Phys. Met. Metallogr., 79(3), 336–341 (1995) (Experimental, Kinetics, 10)
[1997Har] Hara, T., Ohba, T., Okunishi, E., Otsuka, K., “Structural Study of R-Phase in Ti-50.23Ni (at.%) and
Ti-47.75Ni-1.50Fe (at.%) Alloys”, Mater. Trans., JIM, 38(1), 11–17 (1997) (Crys. Structure, Experi-
mental, 18)
(1998) (Phase Relations, Thermodyn., 83)
[1998Tam] Tamiya, T., Shindo, D., Murakami, Y., Bando, Y., Otsuka, K., “In-situ Observations of R-Phase
Transformation in a Ti50Ni48Fe2 Alloy by Electron Microscopy”, Mater. Trans., 39(7), 714–723 (1998)
[1999Abr] Abramycheva, N.L., V’yunitskii, I.V, Kalmykov, K.B., Dunaev, S.F., “Isothermal Cross Section of the
Phase Diagram of the Fe-Ni-Ti System at 1273 K. - I”, Vestn. Mosk. Univ., Ser.2: Khim, 40(2), 139–143
(1999) (Experimental, Phase Relations, #, *, 4)
[1999Efi] Efimenko, L.P., Petrova, L.P., Sviridov, S.I., “Interactions in TiFe-Ni System at 1200˚C”, Russ. Metall.
(Engl. Transl.), (4), 160–165 (1999) (Experimental, 15)
[1999Lee] Lee, S.M., Perng, T.P., “Correlation of Substitutional Solid Solution with Hydrogenation Properties of
TiFe1–xMx (M = Ni, Co, Al) Alloys”, J. Alloys Compd., 291, 254–261 (1999) (Crys. Structure, Experi-
mental, 18)
[1999Thi] Thiedemann, U., Rösner-Kuhn, M., Drewes, K., Kuppermann, G., Frohberg, M.G., “Temperature
Dependence of the Mixing Enthalpy of Liquid Ti-Ni and Fe-Ti-Ni Alloys”, J. Non-Cryst. Solids,
250–252, 329–335 (1999) (Experimental, Thermodyn., 17)

Fe–Ni–Ti 14 33
[1999Zha] Zhang, J., Ren, X., Otsuka, K., Tanaka, K., Chumlyakov, Yu.I., Asai, M., “Elastic Constants of Ti-48
at.%Ni-2 at.%Fe Single Crystal Prior to B2 → R Transformation”, Mater. Trans., JIM, 40(5), 385–388
(1999) (Crys. Structure, Phys. Prop., Experimental, 21)
[2000Chu] Chu, J.P., Lai, Y.W., Lin, T.N., Wang, S.F., “Deposition and Characterization of TiNi-Base Thin Films
by Sputtering”, Mater. Sci. Eng. A, A277, 11–17 (2000) (Crys. Structure, Experimental, Phys. Prop., 20)
[2000Efi] Efimenko, L.P., Petrova, L.P., Sviridov, S.I., “Interaction of Eutectic Melt Ti2Ni-Ti and Iron Substrate at
1100-1250˚C”, Russ. Metall. (Metally), 3, 42–46 (2000), translated from Izv. Ros. Akad. Nauk, Met., (3),
41–44 (2000) (Experimental, Phase Diagram, Phase Relations, Transport Phenomena, 12)
[2000Jia] Jiang, C., Xu, H., “Effect of Pre-Deformation on Hysteresis in TiNiFe Shape Memory Alloys”, Mater.
Sci. Forum, 327–328, 111–114 (2000) (Experimental, 3)
[2000Lap] Lapshin, V.P., Grishkov, V.N., Lotkov, A.I., “On Certain Anharmonic Characteristics of B2 Phase Ti
(Ni,Fe) Alloys Under Hydrostatic Pressure”, Russ. Phys. J., 43(12), 999–1002 (2000) (Crys. Structure,
Experimental, 21)
[2000Vor] Voronin, V.I., Naish, V.E., Novoselova, T.V., Sagaradze, I.V., “Structures of Monoclinic Phases in
Titanium Nickelide: II. Transformation Cascade B2-R-T”, Phys. Met. Metallogr., 89(1), 19–26 (2000)
[2000Xu] Xu, H., Jiang, C., Gong, S., Feng, G., “Martensitic Transformation of the Ti50Ni48Fe2 Alloy Deformed
at Different Temperatures”, Mater. Sci. Eng. A, A281, 234–238 (2000) (Experimental, 11)
[2001Gup] Gupta, K.P., “The Fe-Ni-Ti System Update (Iron - Nickel - Titanium)”, J. Phase Equilib., 22(2),
171–175 (2001) (Phase Diagram, Review, #, *, 5)
[2001Mur] Murakami, Y., Shindo, D., “Changes in Microstructure Near the R-Phase Transformation in
Ti50Ni48Fe2 Studied by in-situ Electron Microscopy”, Philos. Mag. Lett., 81(9), 631–638 (2001) (Experi-
mental, Morphology, Phase Relations, 25)
[2002Boz] Bozzolo, G.H., Noebe, R.D., Amador, C., “Site Occupancy of Ternary Additions to B2 Alloys”,
Intermetallics, 10, 149–159 (2002) (Crys. Structure, Review, 27)
[2002Ish] Ishida, S., Asano, S., “R-Phase and Electronic Structures of TiNi and TiNi8/9Fe1/9”, Mater. Trans., 43(5),
[2002Kuz] Kuznetsov, A.R., Sagaradze, V.V., “On the Possible Mechanism of Low-temperature Strain-induced
Dissolution of Intermetallic Phases in FCC Fe-Ni-Ti Alloys”, Phys Met Metallogr., 93(5), 404–407
(2002), translated from Fiz Met. Metalloved., 93(5), 13–16 (2002) (Experimental, 22)
[2003Miy] Miyamura, H., Takada, M., Hirose, K., Kikuchi, S., “Metal Hydride Electrodes Using Titanium-Iron-
Based Alloys”, J. Alloys Compd., 356–357, 755–758 (2003) (Electrochemistry, Experimental, Phase
Diagram, 6)
[2003Nis] Nishida, M., Tanaka, K., Li, S., Kohshima, M., Miura, S., Asai, M., “Microstructure Modifications by
Tensile Deformation in Ti-Ni-Fe Alloy”, J. Phys. IV, France, 112(2), 803–806 (2003) (Experimental,
Mechan. Prop., 4)
[2004Jan] Jankowska, E., Jurczyk, M., “Electrochemical Properties of Sealed Ni-MH Batteries Using
Nanocrystalline TiFe type Anodes”, J. Alloys Compd., 372, L9–L12 (2004) (Crys. Structure, Electro-
chemistry, Experimental, 15)
[2005Cho] Choi, M.-S., Fukuda, T., Kakeshita, T., “Anomalies in Resistivity, Magnetic Susceptibility and Specific
Heat in Iron-Doped Ti-Ni Shape Memory Alloys”, Scr. Mater., 53(7), 869–873 (2005) (Crys. Structure,
Electr. Prop., Electronic Structure, Experimental, Phase Relations, Thermodyn., 17)
[2005Jan] Jankowska, E., Makowiecka, M., Jurczyk, M., “Nickel-Metal Hydride Battery Using Nanocrystalline
TiFe-Type Hydrogen Storage Alloys”, J. Alloys Compd., 404–406, 691–693 (2005) (Crys. Structure,
Electrochemistry, Experimental, 11)
[2005Ste] Sitepu, H., Wright, J.P., Hansen, T., Chateigner, D., Brokmeier, H.-G., Ritter, C., Ohba, T., “Combined
Synchrotron and Neutron Structural Refinement of R-Phase in Ti50.75Ni47.75Fe1.50 Shape Memory
Alloy”, Mater. Sci. Forum (Textures of Materials - ICOTOM 14), 495–497, 255–260 (2005) (Crys.
[2005Wan] Wang, J.J., Omori, T., Sutou, Y., Kainuma, R., Ishida, K., “Two-Way Shape Memory Effect Induced by
Cold-Rolling in Ti-Ni and Ti-Ni-Fe Alloys”, Scr. Mater., 52(4), 311–316 (2005) (Experimental,
Kinetics, Phase Relations, Thermodyn., 21)
[2005Yam] Yamada, Y., Nakamura, K., Kitagawa, K., Obara, G., Nakamura, T., “Magnetic Properties of C14 Laves
Phase Ti(Fe1–xTx)2 with T = Mn, Co and Ni (x < 0.6)”, J. Magn. Magn. Mater., 285(1-2), 28–38 (2005)
(Crys. Structure, Experimental, Magn. Prop., Optical Prop., Phase Relations, 10)

34 14 Fe–Ni–Ti
[2006Cac] Cacciamani, G., De Keyzer, J., Ferro, R., Klotz, U.E., Lacaze, J., Wollants, P., “Critical Evaluation of the
Fe-Ni, Fe-Ti and Fe-Ni-Ti Alloy Systems”, Intermetallics, 14, 1312–1325 (2006) (Phase Relations,
Review, #, *, 161)
[2006Cho] Choi, M.S., Ogawa, J., Fukuda, T., Kakeshita, T., “Stability of the B2-Type Structure of Ti-Ni-Fe and Ti-
Ni-Co Shape Memory Alloys”, Mat. Sci. Forum, 512, 233–238 (2006) (Crys. Structure, Experimental,
Morphology, Phase Relations, 17)
[2006Fan] Fan, G., Zhou, Y., Otsuka, K., Ren, X., “Ultrahigh Damping in R-Phase State of Ti-Ni-Fe Alloy”, Appl.
Phys. Lett., 89, 161902–1–3 (2006) (Experimental, Mechan. Prop., 15)
[2006Gho] Ghosh, G., “Iron-Nickel-Titanium”, Landolt- Börnstein: Numerical Data and Functional Relationship in
Science and Technology, New Series, Effenberg, G., Illyenko S., (Eds.), Springer-Verlag, Berlin/Heidel-
berg, Group IV, 11, Subvolume A, Part 4, 299–316 (2005), MSIT Ternary Evaluation Program, in MSIT
ment ID: 10.10608.1.20, (1992) (Crys. Structure, Phase Diagram, Assessment, #, *, 44)
[2006Ria] Riani, P., Cacciamani, G., Thebaut, Y., Lacaze, J., “Phase Equilibria and Phase Transformations in the
Ti-Rich Corner of the Fe-Ni-Ti System”, Intermetallics, 14, 1226–1230 (2006) (Experimental, Mor-
phology, Phase Diagram, Phase Relations, 13)
[2006Yam] Yamamoto, T., Fukuda, T., Kakeshita, T., “Electronic Structure of B2-type Ti-Ni-Fe Alloys Exhibiting
Second-order-like Structural Transformation”, Mater. Trans., 47, 594–598 (2006) (Experimental, Crys.
Structure, 21)
[2007Pro] Prokoshkin, S.D., Belousov, M.N., Abramov, V.Ya., Korotitskii, A.V., Makushev, S.Yu., Khmelevskaya,
I.Yu., Dobatkin, S.V., Stolyarov, V.V., Prokof‘ev, E.A., Zharikov, A.I., Valiev, R.Z., “Creation of
Submicrocrystalline Structure and Improvement of Functional Properties of Shape Memory Alloys of
the Ti-Ni-Fe System with the Help of ECAP”, Met. Sci. Heat Treat., 49(1-2), 51–56 (2007) (Crys.
Structure, Experimental, Morphology, 11)
G. (Ed.), MSI, Materials Science International Services, GmbH, Stuttgart; to be published, (2008)
(Crys. Structure, Phase Diagram, Assessment, 41)
[2008Ted] Tedenac, J.C., Velikanova, T., Turchanin, M., “Ni-Ti (Nickel-Titanium)”, MSIT Binary Evaluation
Program, in MSIT Workplace, Effenberg, G. (Ed.), Materials Science International Services, GmbH,
Stuttgart; to be published (2008) (Crys. Structure, Phase Diagram, Assessment, 37)
(1990)

Fe–Ni–V 15 1
Iron – Nickel – Vanadium

Andy Watson, Lesley Cornish
Introduction
The Fe-Ni-V system is of interest, not only because both Ni and V are components in steels,
but also because Fe and V are important components of Ni-based superalloys for aerospace
applications. The VNi3 phase, which has an ordered tetragonal structure, acts as a strengthen-
ing phase in Ni-based superalloys [1963Zeg, 1977Bra1, 1977Bra2]. However, a major concern
with these materials is the precipitation of the σ phase in alloys during service and much
effort has gone into trying to predict its formation. [1977Bra1, 1977Bra2] attempted to predict
σ phase formation by calculation of density of states and enthalpies of formation using a tight
binding Hamiltonian matrix, but more recently it has been the subject of study by Calphad
techniques [2001Wat]. The other major interest for this system comes from its magnetic
properties, and Fe-Ni-V Permalloys have superior mechanical properties compared to con-
ventional Permalloys. This can give an advantage where abrasion resistance is important, for
example, [1984Tis], but these materials have a reduced saturation magnetization. Neverthe-
less, there is interest in using these materials as films for magnetic and electronic devices
[1990Miy]. Considering the level of industrial interest, it is surprising that there has been
relatively little study of the phase equilibria and thermodynamics of the system. The binary
systems associated with Fe-Ni-V are well known but there have only been a few studies of
the ternary system. The earliest record of the phase equilibria and magnetic properties of the
system were recorded by [1934Kue], and subsequently, the system has been review by [1949Jae,
1983Ray, 1988Ray, 1994Rag1].
Details of experimental studies of the system are summarized in Table 1.
Binary Systems
The three binary systems, Fe-Ni, Fe-V and Ni-V are well known and appear in [Mas2]. There
have been a number of attempts at producing thermodynamic descriptions of the systems. The
earliest thermodynamic description of the Fe-Ni system was produced by [1986Din] and has
been used on many occasions for the study of ternary and higher order systems. More recently,
the liquid phase has been remodeled [1993Lee] in order to improve the level of agreement with
experimental data in the thermodynamic assessment of the Fe-Cr-Ni system. The ordering of
the fcc phase to FeNi3 was modeled by [2000Ans]. The Fe-V system was assessed by
[1991Hua1] but [2006Oka] has reported recent work by [2005Ust] who studied the extent
of the σ phase in the binary Fe-V system using XRD and electron microscopy. They suggest
that the σ phase decomposes below about 650˚C accompanied by phase separation of the bcc
phase. However, in the phase diagram shown by [2006Oka], there would seem to be a narrow
strip of single phase α between the σ phase and the region of phase separation. As pointed out
by [2006Oka], this would seem to be unlikely, the σ phase most probably decomposing

2 15 Fe–Ni–V
eutectoidally to give Fe rich and V rich bcc phases, much like in the Cr-Fe system. As this
remains uncertain, the feature has been ignored in the present work. The Ni-V system was
assessed by [1992Luo] and more recently by [2001Wat], who used a variety of different models
to describe the σ phase. The binary phase diagrams for Fe-V and Ni-V are taken from [Mas2],
the latter being based on [1982Smi], but a recent review of the Fe-Ni system [2008Kuz], as
conducted as part of the MSI binary phase evaluation program, is taken as the source for the
third binary phase diagram.
Solid Phases
No ternary phases have been found in this system. The main feature is the extension of the σ
phase from the Ni-V to the Fe-V binary system. The σ phase field is quite wide (~28 at.% at
900˚C) in the Ni-V binary system and is stable below its peritectic formation temperature of
1280˚C. In the Fe-V system, the congruent transformation temperature of the σ phase field is
given in [Mas2] as 1252˚C, and at it is reasonable to assume that a single phase field extends
right across the phase diagram at temperatures below this. Both the Fe-Ni and Fe-V systems
exhibit large solution phase fields that extend across the binary phase diagrams (γ and α,
respectively) and these extend well into the ternary system with dissolution of the third
element. Both the ordered γ’ (FeNi3) and the θ (VNi3) phases dissolve the third element.
However, it is not known to what level. Both of these phases are different ordered variants of
fcc (L12 and D022, respectively) so complete mutual solubility is not likely.
[1963Zeg] studied the solubility of Fe in the binary V3Ni compound. Alloys were prepared
by arc-melting spectroscopically pure V with commercially pure Fe and Ni (99.9+) and
annealing the cast materials at 800˚C in evacuated quartz ampoules for 3-6 weeks. Optical
microscopy and powder XRD (Cukα radiation) were used to study the alloys. They found that
it was possible to dissolve Fe into the V3Ni binary compound up to a composition of
V3(Fe0.7Ni0.3). Crystallographic details of the phases of the system are given in Table 2.
No invariant equilibria have been detected in this system, but considering the binary invariant
reactions, it is highly likely that a transition type reaction will be present. The information in
Table 3 was taken from the review of [1988Ray].
No determination of the liquidus surface has been carried out as yet, but the likely form it
would take was postulated by [1988Ray] based on the liquidus features of the adjoining binary
systems, Fig. 1. Only three binary invariants are present in the system (Fe-V: peritectic
L+(δFe)Ð(γFe), Ni-V: peritectic L+(V) Ð σ, eutectic LÐσ+(Ni)) and by considering their
respective temperatures, they would most likely extend into the ternary system to meet at a
transition reaction. Thermodynamic calculations conducted by combining the assessed ther-
modynamic descriptions of the binary phases [1986Din, 1991Hua2, 2001Wat] from the
literature would confirm this hypothesis, although the nature of the invariant was found in
this case to be eutectic. This was due to the presence of a minimum in the L+(δFe) Ð (γFe)
Fe–Ni–V 15 3
monovariant extending from the Fe-Ni binary edge, however there is no experimental justifi-
cation for this feature and hence it can be ignored at this time.
Isothermal Sections
Sections at three temperatures have been determined experimentally. [1957Dar] vacuum arc-
melted electrolytic grade materials to produce alloys that were then sealed in He+8% H2 filled
quartz ampoules for ‘long time’ annealing at 1200˚C. Following heat treatment, the ampoules
were broken under water in order to quench the alloys. XRD and microscopic examination
were used to determine the extent of the σ phase in the ternary system at 1200˚C using the
disappearing phase technique. They found that the σ phase extended deep into the ternary
system extending from the Ni-V binary edge, but it stopped short of the Fe-V edge. At that
time, there was some uncertainty as to the temperature range of the σ phase in the Fe-V
system, and the results of [1957Dar] seemed to suggest that the σ phase would not be stable in
the Fe-V binary system at this temperature. Figure 2 shows the isothermal section of the
system at 1200˚C based on the work of [1957Dar]. In the figure, the σ phase field has been
extended to meet the Fe-V binary edge and be consistent with the σ phase in that binary
system. The changes to the phase boundaries are sketched in dashed lines. The extent of the
two-phase regions was not established by [1957Dar], but their locations were estimated, and
hence the σ poor phase boundaries are shown dashed. The isothermal section at 1100˚C
was determined by [1981Zha] using ternary diffusion couples. They were prepared by first
making a series of binary couples from ground and polished metal blocks, which were then
heated at high temperature in sealed quartz tubes. A block of the third component metal was
subsequently welded to the binary couple under flowing argon before heating the assembly at
1100˚C in a sealed quartz tube for 2 weeks. The materials used were electrolytic Fe, carbonyl Ni
and V (purity, 99.7% by weight). After quenching, the samples were studied by EMPA and
hardness measurement in order to determine the phase boundaries of the isothermal section at
1100˚C. The isothermal section is given in Fig. 3, showing the σ phase extending from the Ni-V
to the Fe-V binary edge. Small corrections have been made to ensure consistency with the
accepted binary phase diagrams.
In their work on the creation of a thermodynamic database for steels, [1998Mie] calculated
an isothermal section for 1100˚C, using only thermodynamic descriptions for the binary Fe-Ni
[1987Gab, 1993Lee] and Fe-V [1991Hua2] systems and estimated data for the Ni-V system
based on [1994Rag2]. Despite using no ternary parameters and performing no formal
optimization, the calculated γ and α phase boundaries were in reasonable agreement with
the experimental data from [1981Zha] for Fe rich compositions.
[1988Ray] reports on work conducted by [1960Arm] who used microstructural analyses to
derive an isothermal section for the system at 1000˚C. The pure components were melted in
alumina or zirconia crucibles and chill cast. The alloys were then homogenized at 1300˚C
before annealing under vacuum at 1000˚C for 2 or 3 d. Following quenching, microscopic
examination allowed the phase boundaries in the section to be determined to an accuracy
of ±2 or 3 mass% of any component. Figure 4 shows the isothermal section at 1000˚C, taken
from [1988Ray], based on the work of [1960Arm]. Alterations have been made where
necessary to ensure consistency with the binary phase diagrams. The compositions of the
phases in equilibrium are given in Table 4. These are compared with values for the same
equilibrium for a temperature of 1200˚C estimated by [1988Ray] based on the work
4 15 Fe–Ni–V
of [1957Dar]. As can be seen from the figures and the compositions given in the table, the
size of this three-phase equilibrium increases with decreasing temperature. The only other
phase found in these sections is the θ phase, which is just stable at 1000˚C. The other
intermetallic phases in the Ni-V system (Ni2V and NiV3) are not stable at these temperatures.
Neutron diffraction studies of the long range order parameter in the γ’ and θ phases has been
undertaken by [1970Gom1, 1970Gom2, 1972Gom, 1992Gom] and has suggested that the two
phases exist in equilibrium with each other in the ternary system (see Temperature-Composi-
tion Sections section). However, as pointed out by [1988Ray], it would be expected that the
long range order parameter of the alloys would become constant with varying V content
within the two-phase region, which is contrary to their findings [1972Gom] (Fig. 5). A more
plausible analysis of these results is given by [1988Ray] who suggests that the two intermetallic
phases are in equilibrium with the disordered γ phase at some point along the Ni3V-FeNi3 join.
[1988Ray] produced a room temperature section showing hypothetical phase relationships
based on this premise, Fig. 6.
No formal investigation of a vertical section across the phase diagram has been made, however
of particular interest is how the ordered γ’ phase in the Fe-Ni system and the θ phase in the
Ni-V system extend into the three component system. A number of studies have been made of
the phase relationships along the VNi3 - FeNi3 join and how the ordering of the phases change
with composition. [1970Sar, 1974Sar] used mechanical property studies (Young’s modulus,
UTS, hardness), resistivity measurement and saturation magnetization measurement to in-
vestigate the influence of adding V to FeNi3. Electrolytic Ni, carbonyl Fe and alumothermal V
were melted under vacuum in alundum crucibles. Alloys were either slowly cooled at 2˚C·h–1
following annealing at 850˚C for 4h, or after quenching from 1100˚C. Mechanical property
measurement was carried out during isothermal heat treatments at 440, 500, 550, 610, 670 and
800˚C. Results suggested that the two ordered phases were in fact in equilibrium with the
disordered fcc phase in the plane of this section. This is contrary to work conducted by
[1970Gom1, 1970Gom2, 1972Gom, 1992Gom]. They looked at the influence of substitution
of the third component on the long range order of VNi3 and FeNi3 using neutron diffraction.
They observed a dramatic decrease in the long range order parameter of FeNi3 at around 10
at.% V. Correspondingly, the long range order parameter of the VNi3 structure was found to
increase at about 15 at.% V (Fig. 5). This decrease in the long range order parameter for FeNi3
was explained by the formation of nuclei of the ordered VNi3 phase. It would seem that there is
a two-phase region of FeNi2 and VNi3. However, the interpretation of their results is a little
confusing. As pointed out in [1988Ray], it would be expected that the presence of a two-phase
field comprising these two phases would result in constant long range order parameter for
each of the phases rather than them disappearing completely. This section would clearly
benefit from further investigation.
The most widely studied properties of alloys of this ternary system are the magnetic properties.
[1984Gan1, 1984Gan2, 1984Gan3] used both a standard 4 probe dc method and vibrating
Fe–Ni–V 15 5
sample magnetometer to study ferromagnetism in Ni-rich alloys. Alloys were prepared by

firstly induction melting the component elements and then homogenizing the cast material at
1100˚C for 48 h before annealing at 900˚C prior to a water quench. Magnetization was studied
between 77 and 300 K and it was found that the average number of Bohr magnetons per atom
showed a non-linear variation with V concentration. The magnetization falls with temperature
much faster than with conventional ferromagnets. There is also a sign reversal in the Hall
coefficient for the ternary alloy. [1985Laa] studied the magnetic form factors at room
temperature of alloys of composition (Ni0.6Fe0.4)1–xVx , where x = 0.095-0.159 using polarized
neutron diffraction. It was found that the addition of V as an impurity affected the magnetic
structure of the matrix as a whole and the average magnetic moment decreased. The spatial
distribution, however, remained unaltered. [1986Maj] studied the linear magnetostriction of
Ni-rich alloys from 10-300 K. Induction melted alloys were homogenized at 1150˚C for 48 h
followed by an annealing treatment at 900˚C and water quench to retain the high-temperature
disordered phase. The linear magnetostriction was found to be very small (~4·10–6) and the
minimum Curie temperature of 147 K was found for an alloy of composition 84Ni-5Fe-11V.
A Mössbauer study at 4.2 K of an alloy of composition (Ni0.594Fe0.406)0.841V0.159 was conducted
by [1987Sta], and they found a non-zero magnetic moment for Ni. This suggests that the
electronic structure of this ternary alloy is more complex than the binary Ni-V alloys.
[1990Miy] studied the magnetoresistivity of an Fe-82Ni thin film with V additions. The
films were produced by electron-bean evaporation on to crystallized glass in the presence of
a magnetic field. The saturation magnetization and electrical resistivity of films with a
thickness of 10μm were measured using the Neugebauer method and a 4-probe technique in
a magnetic field of 3980 H, respectively. The addition of V increases the electrical resistivity
only slightly, whereas the anisotropic resistivity decreases.
The effective permeability μe and its stress-sensitivity in high frequency fields (H =
0.4 A·m–1, f = 1-100 kHz) in Fe-Ni-V alloys were investigated by [1984Tak]. Sheets of Fe-
Ni-V alloy were cold rolled to a thickness of 0.025 mm and annealed at 873-1473 K in pure
hydrogen. They were subjected to low temperature heat treatment. The dc magnetic proper-
ties, saturation magnetostriction, Curie point and electrical resistivity were also measured. It
was found that the optimum annealing temperature to achieve maximum μe is shifted to lower
temperatures with increasing frequency. [1991Yao] studied the mechanical properties of
γ’ alloys and concluded that they were ductile at room and high temperature. Elongation
was ~30% at 800˚C.
A brief listing of the experimental studies associated with materials properties is given in
Table 5.
Miscellaneous
The γ phase in the Fe-Ni-V system undergoes a martensitic transformation and has been the
subject of particular study. [1981Geo] melted an alloy of Ni-24Fe with 4.5, 5.0, 5.5 and 6.0
mass% V additions. The alloys were homogenized between 1110 and 1150˚C for 10-21 h. The
alloys were then heat treated at 1150˚C for 1h before quenching and tempering for 2-30 min in
liquid Sn before slow cooling for dilatometry. At a cooling rate of 10˚C/min, the Ms tempera-
ture falls from –20˚C at a V content of 4.5 mass% to –45˚C at 6.0 mass% V. The ageing
of martensite has been studied by [1977Edn, 1978Zai1, 1978Zai2, 1981Zay, 1984Bel]. Hard-
ness and electrical resistance measurements, XRD, nuclear gamma-resonance measurements,
6 15 Fe–Ni–V
and electron microscopy were used by [1977Edn] to investigate the effect of combined
Ni (0-18 mass%) and V (0-10 mass%) additions in Fe-Ni-V alloys. It was found that alloying
Fe-V alloys with Ni promoted the formation of martensite after quenching and strengthening
of the material after heating to 250-550˚C. It was supposed that the strengthening was
associated with the formation during ageing of disperse precipitates of VNi3. Subsequent
work by [1981Zay] indicated that the precipitation of VNi3 is preceded by clustering of
V atoms or possibly microscopic ordering. This was indicated by an increase in the specific
electrical resistance of the material. The early stages of precipitation of VNi3 was studied
by [1984Bel] using the positron annihilation method. It is the precipitation of VNi3 that
was deemed to be responsible for an anomalous increase in the lattice parameter of martensite
on ageing as the matrix progressively becomes denuded of Ni and V [1978Zai2]. The
same authors looked at a combined low-temperature and high-temperature ageing of mar-
tensite and discovered an increase in the degree of hardening over the single heat treatment
[1978Zai1].
[1981Wad] studied nitrogen solubility in Fe-Ni-V alloys with up to 15 mass% V at
temperatures between 1775 and 2040˚C by the Sievert’s method. The solubility followed
Sievert’s law for all compositions studied.
. Table 1
Investigations of the Fe-Ni-V Phase Relations, Structures and Thermodynamics
[1957Dar] XRD, microstructural examination Homogeneity range of σ phase at

1200˚C
[1960Arm] Microstructural examination Isothermal section at 1000˚C
[1963Zeg] XRD, microstructural examination Dissolution of Fe in V3Ni
[1970Sar] Young’s modulus measurement, Compositions along FeNi3-VNi3
XRD, potentiometric method
[1970Gom1, 1970Gom2, Neutron diffraction Ordering and phase relationships
1972Gom, 1992Gom] in the FeNi3-VNi3 section.
[1981Zha] Diffusion couples/EPMA Isothermal section at 1100˚C

Fe–Ni–V 15 7
. Table 2
Crystallographic Data of Solid Phase
Pearson
Symbol/
Phase/ Space
γ, (γFe,Ni) cF4
Fm3m
(Ni) Cu a = 352.4 [V-C2, Mas2]
< 1455
(γFe) a = 364.67 at 915˚C [V-C2, Mas2]
1394 - 912
α, (δαFe,V) cI2
Im3m
(δFe) W a = 293.15 1394˚C [Mas2]
1538 - 1394 dissolves up to 3.8 at.% Ni at 1517˚C
[2008Kuz]
(αFe) a = 286.65 at 25˚C [Mas2]
< 912 dissolves 4.6 at.% Ni at 495˚C [2008Kuz]
(V) a = 302.40 at 25˚C [Mas2]. Dissolves up to 24 at.% Ni at
< 1910 1280˚C.
P63/mmc c = 396.0
Mg
γ’, FeNi3 cP4 a = 355.23 63 to 85 at.% Ni [2008Kuz]
< 517 Pm3m
AuCu3
γ’’, FeNi tP4 a = 357.9 ± 0.1 [V-C2]
metastable P4/mmm c = 357.9 ± 0.1 metastable ordering temperature
AuCu 320˚C at 51.2 at.% Ni [2008Kuz]
σ tP30
P42/mnm
σVNi σCrFe a = 895.4 at 57.5 at.% V [1982Smi]
< 1280 c = 463.5
a = 899.6 at 63.2 at.% V [1982Smi]
c = 465.3 contains 73.5 at.% V at 900˚C and 55 at.% V
at 890˚C [Mas2]
σVFe a = 896.5 at V0.5Fe0.5 [V-C2]
< 1252 c = 463.3 29.6-60.1 at.% V [Mas2].
θ, VNi3 tI8 a = 354.3 at 23.44 at.% V
< 1045 I4/mmm c = 720.2
Ti3Al
a = 354.2 at 24.75 at.% V
c = 721.3
a = 354.1 at 25.60 at.% V [Mas2, 1982Smi]
c = 721.8

8 15 Fe–Ni–V
Pearson
Symbol/
Phase/ Space
VNi2 oI6 a = 255 to 256 at 33.3 at.% V [1982Smi]

< 922 Immm b = 771 to 764
MoPt2 c = 354 to 355
V3Ni cP8
< 900 Pm3n
V3(FexNi1–x) Cr3Si a = 471.15 ± 0.0007 x = 0 [1963Zeg]
a = 469.10 ± 0.0001 x = 0.3 [1963Zeg]
a = 469.45 ± 0.0001 x = 0.5 [1963Zeg]
a = 469.83 ± 0.0001 x = 0.7 [1963Zeg]
VNi8 tI18 a = ~749 [1982Smi]
< 405 - b = ~749
NbNi8 c = 353
. Table 3
Composition (at.%)
Reaction T [˚C] Type Phase Fe Ni V
L+αÐγ+σ ? U - - - -
. Table 4
Three-Phase Equilibria
Composition (at.%)
T [˚C] Phase Fe Ni V
1200 α 45.4 22.6 32

γ 48 20.4 31.6
σ 44 19.5 36.5
1000 α 40 32 28
γ 57 15 28
σ 48 13 39

Fe–Ni–V 15 9
. Table 5
Investigations of the Fe-Ni-V Materials Properties
[1981Geo] Neutron diffraction, Martensitic transformation kinetics

dilatometry
[1984Gan1] 4-probe dc method Hall coefficient
[1984Gan2] Vibrating sample Ferromagnetism in Ni rich Ni-Fe-V alloys
magnetometry
[1985Laa] Polarized neutron Magnetic form factor in (Fe0.4Ni0.6)1–xVx at RT,
diffraction x = 0.095-0.159
[1986Maj] Wheatstone bridge Magnetostriction and TC of Fe-Ni-V alloys
[1987Sta] Mössbauer studies Magnetic moment of Ni in ternary Fe-Ni-V alloys
[1990Miy] 4-probe technique Electrical resistivity and saturation magnetization of
82Ni-Fe+V thin film
[1991Yao] Tensile and fracture test Mechanical properties of alloys with γ’ structure
[1992Gom] Differential magnetic Variation of Tc from FeNi3 to VNi3
susceptibility

10 15 Fe–Ni–V
. Fig. 1
Fe-Ni-V. Liquidus surface projection

Fe–Ni–V 15 11
. Fig. 2
Fe-Ni-V. Isothermal section at 1200˚C

12 15 Fe–Ni–V
. Fig. 3

Fe–Ni–V 15 13
. Fig. 4

14 15 Fe–Ni–V
. Fig. 5
Fe-Ni-V. Long-range-order parameter S plotted against V content for alloys of the series
Ni3Fe1–xVx

Fe–Ni–V 15 15
. Fig. 6
Fe-Ni-V. Hypothetical phase relationships at room temperature

16 15 Fe–Ni–V
References
[1934Kue] Kuehlewein, H., Stoermer, R., “The Characteristics of Ferromagnetic Alloys of the Ternary Iron-
Nickel-Vanadium System” (in German), Z. Anorg. Chem., 218, 65–88 (1934) (Crys. Structure, Kinetics,
Phase Diagram, Thermodyn., 28)
[1949Jae] Jaenecke, E., “Fe-Ni-V” (in German) in “Kurzgefasstes Handbuch aller Legierungen”, Winter Verlag,
[1957Dar] Darby, J.B., Beck, P.A., “σ Phase in Certain Ternary Systems with Vanadium”, Trans. AIME, 209, 69–72
(1957) (Experimental, Phase Diagram, Phase Relations, #, 8)
[1960Arm] Armitage, C. H., “The Fe-Ni-V system”, Thesis, Univ. Wisconsin, U.S.A., 21, 579–580 (1960) as quoted
in [1988Ray]
[1963Zeg] Zegler, S.T., Downey, J.W., “Ternary Cr3O-Type Phases with Vanadium”, Trans. Met. Soc. AIME, 227
[1970Gom1] Goman’kov, V.I., Puzey, I.M., Mal’tsev, E.I., “Effect of Alloying Elements on the Superstructure of
Ni3Fe” (in Russian), Dokl. Akad. Nauk SSSR, 194(2), 309–311 (1970) (Crys. Structure, Experimental,
Magn. Prop., 6)
[1970Gom2] Gomankov, V.I., Puzey, I.M., Maltsev, Ye.I., “Effect of Vanadium, Copper and Germanium on the
Ni3Fe Superstructure”, Phys. Met. Metallogr. (Engl. Transl.), 30, 237–240 (1970), translated from Fiz.
Met. Metalloved., 30(1), 220–222, (1970) (Crys. Structure, Experimental, Phase Diagram, Phase
Relations, 12)
[1970Sar] Sarkisyan, R.S., Selissky, Ya.P., Sorokin, M.N., “Study of the Ternary Solid Solutions Ni3(Fe, V)”, Phys.
Met. Metallogr. (Engl. Transl.), 30(1), 47–53 (1970), translated from Fiz. Met. Metalloved., 30(1), 47–53
(1970) (Crys. Structure, Experimental, Kinetics, 17)
[1972Gom] Gomankov, V.I., Puzey, I.M., Kozis, Ye.V., Maltsev, Ye.I., Sigaev, V.N., “Atomic Ordering in the Ternary
System Ni-Fe-V”, Phys. Met. Metallogr. (Engl. Transl.), 33(3), 191–194 (1972), translated from Fiz. Met.
Metalloved., 33(3), 648–651 (1972) (Crys. Structure, Electronic Structure, Experimental, 6)
[1974Sar] Sarkisyan, R.S., Selisskiy, Ya.P., “Investigation of Ternary Alloys Based on Ni3Fe with Vanadium”, Phys.
Met. Metallogr. (Engl. Transl.), 37(4), 137–141 (1974), translated from Fiz. Met. Metalloved., 37(4),
832–836 (1974) (Crys. Structure, Experimental, Kinetics, 18)
[1977Bra1] Brauwers, M., “Occurrence of the σ Phase Computed from a Cluster Model”, J. Phys. F: Met. Phys.,
7(6), 921–927 (1977) (Calculation, Phase Diagram, Phase Relations, Theory, 17)
[1977Bra2] Brauwers, M., Brouers, F., “On the Occurrence of the σ Phase in Transition-Metal Alloys”, Philos.
Mag., 35, 1105–1109 (1977) (Calculation, Phase Diagram, Phase Relations, Theory, 7)
[1977Edn] Edneral, A.F., Zaitseva, R.D., Perkas, M.D., Rodionov, Yu.L., Sersenbin, O.S., “Ageing of Martensite in
Fe-Ni-V Alloys” (in Russian), Fiz. Met. Metalloved., 44(6), 1245–1253 (1977) (Morphology, Mechan.
[1978Zai1] Zaitseva, R.D., Perkas, M.D., Rodionov, Yu.L., Sarsenbin, O.S., “Influence of Preliminary Low-
Temperature Ageing of Martensite of Fe-Ni-V Alloys on the Variation of Properties during High-
Temperature Ageing” (in Russian), Fiz. Met. Metalloved., 45(1), 78–83 (1978) (Morphology, Mechan.
[1978Zai2] Zaitseva, R.D., Perkas, M.D., “’Anomalous’ Variation in the Lattice Parameter of Martensite during
the Ageing of Fe-Ni-V and Fe-Ni-Co-V Alloys” (in Russian), Fiz. Met. Metalloved., 45(1), 103–109
(1978) (Crys. Structure, Morphology, Mechan. Prop., Experimental, 9)
[1981Wad] Wada,H., Pehlke, R.D., “Nitrogen Solubility in Liquid Fe-V and Fe-Cr-Ni-V Alloys”, Metall. Trans. B,
12(B), 333–339 (1981) (Experimental, Thermodyn., 10)
[1981Geo] Georgiyeva, I.Ya., Matyushenko, L.A., Udovenko, V.A., “Investigation of the Martensitic Transforma-
tion Kinetics and Structural Peculiarities of Ternary Iron-Nickel-Based Alloys”, Phys. Met. Metallogr.
(Engl. Transl.), 52(3), 111–115 (1981), translated from Fiz. Met. Metalloved., 52(3), 580–584 (1981)
(Crys. Structure, Experimental, Kinetics, Phase Relations, 2)
[1981Zay] Zaytseva, R.D., Perkas, M.D., “Investigation of the Maraging Kinetics of Fe-Ni-V and Fe-Ni-Co-V
Alloys”, Russ. Metall., (2), 106–109 (1981) (Morphology, Kinetics, Mechan. Prop., Experimental, 5)
[1981Zha] Zhanpeng, J., “A Study of the Range of Stability of σ Phase in some Ternary Systems”, Scand. J. Metall.,
10, 279–287 (1981) (Electronic Structure, Experimental, Phase Diagram, Phase Relations, #, 14)
[1982Smi] Smith, J.F., Carlson, O.N., Nash, P.G., “The Ni-V (Nickel-Vanadium) System”, Bull. Alloy Phase
Diagrams, 3(3), 342–348 (1982) (Crys. Structure, Phase Diagram, Review, Thermodyn., 35)

Fe–Ni–V 15 17
[1983Ray] Raynor, G.V., Rivlin, V.G., “Phase Equilibria in Iron Ternary Alloys. XI. Critical Evaluation of
Constitution of Chromium-Iron-Vanadium and Iron-Nickel-Vanadium Systems”, Int. Met. Rev.,
28(5), 251–270 (1983) (Crys. Structure, Experimental, Phase Diagram, Phase Relations, Review, 44)
[1984Bel] Belen’kii, A.Ya., Valuev, N.P., Zhikharev, A.N., Zaitseva, R.D., Klimov, A.B., Latyshev, V.K., Moish, Yu.
V., Perkas, M.D., “Investigation of Ageing of Martensite in Fe-Ni-V and Fe-Ni-V-Mo Alloys by the
Positron Annihilation Method” (in Russian), Fiz. Met. Metalloved., 57(6), 1128–32 (1984) (Mechan.
[1984Gan1] Gangopadhyay, A.K., Ray, R.K., Majumdar, A.K., “Sign Reversal of the Extraordinary Hall-Coefficient
in Ni-Fe-Cr and Ni-Fe-V Alloys”, Phys. Rev. B, 30(4), 1801–1810 (1984) (Experimental, Magn. Prop.,
Thermodyn., 48)
[1984Gan2] Gangopadhyay, A.K., Ray, R.K., Majumdar, A.K., “Weak Itinerant-Electron Ferromagnetism in
Ni-Rich Ni-Fe-Cr and Ni-Fe-V Alloys”, Phys. Rev. B, 30(11), 6693–6706 (1984) (Electrical Properties,
Experimental, Kinetics, Magn. Prop., Thermodyn., 52)
[1984Gan3] Gangopadhyay, A.K., Majumder, A.K., Ray, R.K., “The Sign Change of the Extra-Ordinary Hall
Constant Rs in Ni-Fe-V and Ni-Fe-Cr Alloys”, Indian J. Cryogenics, 9(4), 294–301, (1984) (Experimen-
tal, Magn. Prop., Thermodyn., 12)
[1984Tis] Tischer, Z., “Abrasion Resistant Alloy on the Basis of Ni-Fe-V for Magnetic Head Cores” (in Czech),
Slaboproudy Obzor, 45(11), 548–50 (1984) (Mechan. Prop., Experimental, 3)
[1984Tak] Takeyama, T., Sato, Y., “Influence of Heat Treatment and Composition on Effective Permeability and
its Stress-Sensitivity in thin Sheets of Ni-Fe-V Alloys”, J. Jpn. Inst. Met., 48(7), 754–60 (1984) (Magn.
Prop., Mechan. Prop., Experimental, 16)
[1985Laa] van Laar, B., Maniawski, F., Kaprzyk, S., “Neutron Magnetic Form Factors of Ternary Ni-Fe-V Alloys”,
J. Phys. F: Met. Phys., 15(3), 675–680 (1985) (Experimental, Magn. Prop., 17)
[1986Din] Dinsdale, A.T., Chart, T.G., MTDS, National Physical Laboratory, Teddington, UK, unpublished work
(1986) as quoted in [2001Ser]
[1986Maj] Majumdar, A.K., Greenough, R.D., “Linear Magnetostriction in Polycrystalline Ni-Fe-Cr and Ni-Fe-V
Alloys”, J. Magn. Magn. Mater., 59(1–2), 57–61 (1986) (Experimental, Magn. Prop., Phase Relations,
Thermodyn., 10)
[1987Gab] Gabriel, A., Gustafson, P., Ansara, I., “A Thermodynamic Evaluation of the C-Fe-Ni System”, Calphad,
11(3), 203–218 (1987) (Phase Diagram, Phase Relations, Thermodyn., Assessment, 41)
[1987Sta] Stadnik, Z.M., Griesbach, P., Dehe, G., Gutlich, P., Maniawski, F., “Nickel Contribution to the
Magnetism of the Ni-Fe-V Alloy”, J. Magn. Magn. Mater., 70(1–3), 436–438 (1987) (Electronic
[1988Ray] Raynor, G.V., Rivlin, V.G., “Fe-Ni-V” in “Phase Equilibria in Iron Ternary Alloys”, Inst. Metals, London,
433–440 (1988) (Phase Diagram, Phase Relations, Review, 10)
[1990Miy] Miyazaki, T., Ajima, T., Sato, F., “Magnetoresistance of 82Ni-Fe Based Alloy Films”, J. Magn. Magn.
Mater., 83(1–3), 111–112 (1990) (Electrical Properties, Experimental, 13)
[1991Hua1] Huang, W., “A Thermodynamic Evaluation of the Fe-V-C System”, Z. Metallkd., 82(5), 391–401 (1991)
(Phase Diagram, Phase Relations, Thermodyn., Assessment, 54)
[1991Hua2] Huang, W., “Thermodynamic Properties of the Fe-Mn-V-C System”, Metall. Trans. A., 22A(9),
1911–1920 (1991) (Phase Diagram, Phase Relations, Thermodyn., Assessment, 25)
[1991Yao] Yao, X., Chen, N., “Microstructures and Mechanical Properties of (Fe,Co,Ni)3V Alloys”, Mater.
Mechan. Eng., 15(2), 27–31 (1991) (Crys. Structure, Mechan. Prop., Experimental, 10)
[1992Gom] Gomankov, V.I., Gezalyan, A.D., Tretyakov, B.N., Sumin, V.V., “Structural and Magnetic State of
Ni3Fe-Ni3V Alloys” (in Russian), Russ. Metall. (Engl. Transl.), (2), 195–199 (1992), translated from Izv.
Ross. Akad. Nauk, Met., (2), 195–199 (1992) (Experimental, Phase Diagram, Phase Relations, Magn.
Prop., 13)
[1992Luo] Luoma, R., Report TTK-V-B76, Helsinki University of Technology, Laboratory of Materials Processing
and Powder Metallurgy, (1992) (Phase Diagram, Phase Relations, Thermodyn., Assessment, 65)
[1993Lee] Lee, B.-J., “Revision of Thermodynamic Descriptions of the Fe-Cr and Fe-Ni Liquid Phases”, Calphad,
17(3), 251–268, (1993) (Phase Diagram, Phase Relations, Thermodyn., Assessment, 95)
[1994Rag1] Raghavan, V., “Fe-Ni-V (Iron-Nickel-Vanadium)”, J. Phase Equilib., 15(6), 630 (1994) (Phase Diagram,
[1994Rag2] Raghavan, V., Antia, D.P., “The Chromium Equivalents of Selected Elements in Austenitic Stainless
Steels”, Metall. Mater. Trans. A., 25A(12), 2675–2681, (1994) (Phase Relations, Thermodyn., Calcula-
tion, 32)

18 15 Fe–Ni–V
(1998) (Assessment, Calculation, Phase Diagram, Phase Relations, Thermodyn., 98)
[2000Ans] Ansara, I., Private Communication, as quoted in [2001Ser]
[2001Ser] Servant, C., Sundman, B., Lyon, O., “Thermodynamic Assessment of the Cu-Fe-Ni System”, Calphad,
25(1), 79–95, (2001) (Phase Diagram, Thermodyn., Assessment, 44)
[2001Wat] Watson, A., Hayes, F.H., “Some Aspects of Modelling the σ Phase in the Ni-V System”, J. Alloys
Compd, 320(2), 199–206 (2001) (Phase Diagram, Thermodyn., Assessment, 46)
[2005Ust] Ustinovshikov, Y., Pushkarev, B., Sapegina, I., “Phase Transformations in Alloys of the Fe-V System”,
J. Alloys Compd., 398, 133–138 (2005) (Crys. Structure, Phase Diagram, Experimental, 9)
[2006Oka] Okamoto, H., “Fe-V (Iron-Vanadium)”, J. Phase Equilib. Diff., 27(5), 542 (2006) (Review, Phase
Diagram, 3)
(1990)

Fe–Ni–W 16 1
Iron – Nickel – Tungsten

Elena Semenova
Introduction
The Fe-Ni-W system is of great interest in a number of technological fields, such as the
sintering of hard and refractory W-based alloys. The phase diagram of the Fe-Ni-W system has
been studied experimentally since 1932. The first work of [1932Win] focused on compositions
in the region of up to 45 mass% W; eight vertical sections together with the projection of the
liquidus surface were constructed and later reproduced by [1961Eng, 1949Jae]. The investiga-
tion was accompanied by the measurement of some magnetic properties.
Critical assessments of the phase diagram are presented in [1971Win, 1981Ray,
1988Ray, 1994Rag]. The Ni-rich region of the Fe-Ni-W system was studied in detail between
1350-800˚C by [1969Aga], for alloys lying on sections with Fe:Ni ratios from 20:80 to 70:30,
and also isotherms of solubility were constructed. The tungsten solubility in the γ phase was
presented as isotherms is in agreement with [1932Win].
Based mainly on [1932Win] and taking into account the findings of [1969Aga] as well as
information on the binary systems known at that time, [1971Win] proposed isothermal
sections of the Fe-Ni-W phase diagram for temperatures between 800 and 1560˚C. The version
of the liquidus surface projection proposed by [1932Win], as well as the phase diagram at
1400˚C from [1971Win] was supported in the subsequent work of [1986Fer], which
incorporated some suggestions of [1981Hen] regarding the existence of a saddle point on
the surface of the γ primary crystallization field.
There are, however, a number of discrepancies between the different versions of the phase
diagram of this system for the solid state. Equilibrium is hard to attain in this system and
consequently, different phase relations were derived by different researchers depending on
the annealing time used in their experiments. [1982Ban] studied the phase equilibria in the
Fe-rich region of the Fe-Ni-W system as a part of the more complex Co-Fe-Ni-W system.
The latter is of practical interest in relation to the production of martensite-ageing alloys. The
existence of a three-phase (αFe)+γ+μ domain at 1300, 1200 and 800˚C was suggested. But this
is in contradiction with most of the other studies of the ternary phase diagram and also with
the accepted Fe-W binary system [Mas2], where the μ phase decomposes below 1190˚C. The
Fe2W phase was not found by [1982Ban] in the alloys investigated as part of their work.
Moreover, [1972Var] did not see the Laves phase in Fe2W-Ni2W alloys at 950˚C, but equilibria
between the μ and (αFe) phases were observed up to 16.7 at.% Ni in ternary alloys. [1986Zak1,
1986Zak2, 1991Nik, 1992Nik] studied the phase relationships in the ternary Fe-Ni-W alloys in
the W rich corner as a part of their study of the Co-Fe-Ni-W system. Isothermal sections for
1400, 1200, 1050, 950, 800 and 527˚C, as well as vertical sections along 10 and 20 (Fe+Ni)
(mass%) were constructed. [1979Edm], looking for a cause of embrittlement of Fe-Ni-W
alloys, found that furnace cooling resulted in the precipitation of the (Fe,Ni)W phase at the

2 16 Fe–Ni–W
matrix-tungsten interface in (3-5)Fe-(5-7)Ni-W (mass%) alloys. This phase was considered to

be responsible for embrittlement of the alloys. The distribution of the alloy components
between the phase constituents on sintering W rich alloys and their redistribution after
subsequent heat treatment was the subject of investigation by [1965Dzy, 1977Mar, 1980Min,
1982Buk, 1995Dje]. Diffusion of Ni and Fe in W and of W in Ni and Fe was shown to
accompany the sintering process. The W solubility was found to be higher in Ni than in Fe and
to decrease on addition of the latter to an alloy. [1983Du] compared the composition of the γ
and (W) phases in the as sintered state and after heat treatment. [1981Ahn] calculated the
solidus and liquidus curves in the Fe-Ni-W system separating at 1540˚C the (W)/(L+(W)) and
(L+(W))/L regions, respectively. [1986Fer] studied the phase equilibria in the Fe-Ni-W
system. Their own experimental data presented as a series of tie-lines at temperatures of
1000, 1100, 1200, 1300 and 1400˚C, as well as data on liquidus surface [1932Win] were used by
[1986Fer] to evaluate the phase diagram and draw isothermal sections for these respective
temperatures. The liquidus projection and a number of isopleths were also constructed from
the data of [1932Win, 1969Aga, 1982Ban]. [1968Ega, 1969Yeg, 1970Gom, 1972Ive,] studied
the effect of the W substitution for Fe in the FeNi3 phase and on the degree of the long range
ordering. [1982Rom] examined the conditions of heat treatment, cooling and ageing at which
the W phase precipitated from the γ solid solution. The size of W particles was estimated.
[1986Woo] examined the mechanical properties of a composite formed by a low-tungsten (25
mass% W) alloy in a W rich (95 mass% W) matrix.
A number of studies [2000Ryu, 2001Fan, 2001He, 2004Zha1, 2004Zha2, 2006Zha] were
carried out on Fe-Ni-W alloys produced by mechanical alloying. Their thermal stability,
microstructure and phase evolution on heating, grain growth, effect of milling time on
crystallization and mechanical properties were investigated. With a view to using tungsten
heavy alloys in nuclear fusion facilities, [1990Kra] investigated the radiation induced embrit-
tlement of a 1.6Fe-3.4Ni-W (mass%) alloy. With the aim of controlling the formation of the
Ni4W phase, which is detrimental to the mechanical properties of the material, [2003Ron]
examined the ageing mechanism under strain conditions at 800˚C of two Fe-Ni-36W (mass%)
alloys, with compositions Fe:Ni = 1:9 and 3:7. Fine precipitates of Ni4W distributed in the γ
phase were found in the Ni rich sample.
[2005Mar] produced dense and fine grains in tungsten heavy alloys by reaction synthesis
combined with a dynamic consolidation process, and the results obtained were compared with
those observed in conventional material preparation.
[2006Par] applied a ‘master sintering curve’ to analyze both densification and grain growth
data obtained by experiment for three Fe-Ni-W compositions. Activation energies of grain
growth were calculated.
Investigations of the system related to phase relations, structures and thermodynamic are
presented in Table 1.
Binary Systems
The Fe-Ni boundary binary system is accepted from the critical assessment of [2008Kuz]. The
Fe-W system is taken from [Mas2] and Ni-W is from [1991Oka]. It is worth mentioning that
[Mas2] questioned the stability of the Fe2W phase and showed it tentatively as metastable.

Fe–Ni–W 16 3
Solid Phases
The crystallographic data of the solid phases along with their stability ranges are shown in
Table 2. No ternary phases are known in the system. The μ (Fe7W6) phase was found to be
stable by [1932Win, 1972Var, 1981Hen, 1982Ban, 1986Fer, 1991Nik, 1992Nik]. The nickel
solubility of the μ phase was accepted from [1981Hen] (about 10 at.%) as their investigations
involved annealing alloys for prolonged periods of time in order to reach equilibrium at
1000˚C (about 8 months). Data from [1972Var] on the phase relationships in Fe2Ni-Ni2W
alloys at 950˚C indirectly supported this value. In the experimental work of [1932Win,
1981Hen, 1982Ban, 1972Var] (the last work was carried out specifically to find out if the
Fe2W phase exists in the Fe-W binary or Fe-Ni-W ternary systems), the Fe2W phase was not
found. It was, however, observed by [1986Fer, 1987Kar]. In both of these last two cases, the
equilibrium state was evidently not attained in their alloys; by [1986Fer] owing to the nature of
the method used (diffusion couple technique) and by [1987Kar] because of insufficient heat
treatment of the compacted powders (an hour at 1150˚C). [2005Mar] showed the presence of
the phase in a 3Fe-7Ni-W (mass%) alloy that had been consolidated at 1000˚C using a shock
wave treatment, confirming the metastable character of this phase. Here, according to
[1972Var, 1981Hen, 1982Ban], the Fe2W phase is considered to be metastable. [1981Hen]
found substantial mutual solubility of the FeW and NiW equiatomic binary phases (which
were assumed to be isomorphic) taking place at 1000˚C and suggested complete mutual
solubility of them at this temperature and below. The formation of a continuous series of
solid solutions of (Fe,Ni)W at 950˚C and down to 575˚C was reported by [1991Nik, 1992Nik].
[1986Zak1, 1986Zak2] did not observe the FeW phase after annealing at 1200˚C (see Table 1)
in alloys with 80 and 90 mass% W, but they assumed its appearance after more prolonged
annealing. The intermetallic precipitates seen in 5Fe-5Ni-90W (mass%) alloys sintered at
1450˚C were classified as the (Fe,Ni)W phase [1979Edm]. Because of a slowing down of the
diffusion processes in the solid state, the peritectoid reactions by which the FeW, NiW, NiW2
and Ni4W phases are formed remain incomplete following the heat treatment applied in most
of the studies.
Fe-Ni-W powders with 50 and 75 at.% W milled for 40 and 15 h, respectively, and then
heated to 850˚C, contained as the products of crystallization the NiW and Ni4W phases in
addition to the W and γ phases that had crystallized in the sample already at 570˚C [2001He].
The crystallization of the amorphous phase and the precipitation of the (Fe,Ni)W phase were
observed by [2006Zha] after prolonged milling of the 6.1Fe-13.2Ni-80.7W (at.%) powders
(about 60 h) and subsequent annealing. The solubility of W in the γ phase changes slightly
on decreasing the temperature in the 1350-800˚C range for the Fe-Ni-W alloys lying on the
20Fe-80Ni section and is of about 33 mass% [1969Aga]. For the 50Fe:50Ni alloy, the value
of the W solubility at 1350˚C almost coincides with that given by [1932Win] at 1400˚C, at
about 20 mass%. It decreases with increasing iron content in the alloys. The γ phase in the
1.5Fe-3.8Ni-W (mass%) alloy has the composition 21.4Fe-55.3Ni-W (mass%) [1986Woo].
The amount of W found by [1977Mar] in the last portion of the crystallized liquid of a
2.4Fe-Ni-93W (at.%) alloy was almost the same.
[1982Buk] reported the total amounts of Fe and Ni dissolved in the α phase to be about
0.4-1.3 mass%, depending on the heat treatment conditions. [1990Kra] pointed out that the
microstructure of a 1.6Fe-3.4Ni-W (mass%) sample exposed to neutron irradiation contained
two phases, γ+(W). Very small solubility of Fe and Ni in W was also reported by [1977Mar,

4 16 Fe–Ni–W
1980Min, 1982Rom, 1986Woo, 2001Fan]. [1977Mar] reported 0.28 at.% Ni and 0.13 at.% Fe
in W. Mechanical alloying of a W heavy alloy (2.1Fe-4.9Ni-93W (mass%)) followed by
annealing at 1280˚C gives nearly pure W particles embedded in a 63.7W-17.4Ni-19.9Fe
(mass%) matrix [2004Zha2]. The ball milled mixture (for 60 h) has a melting point 220˚C
lower than that of the unmilled powdered. According to [1983Du], the composition of the
phases in the 3Fe-7Ni-W (mass%) alloy changes insignificantly after heat treatment. The
γ phase had the composition 24Fe-51Ni-W and 26Fe-54Ni-W (mass%), and W grains con-
taining less than 0.1 mass% Fe and less than 0.14 mass% Ni were observed after sintering at
1250˚C. A mixture of the same composition manufactured by [2005Mar] using a shock
consolidation process had a matrix of approximately the same make-up of about 22Fe-
53Ni-23W, despite on applying heat, the NiW phase being observed in the specimens
produced at 1000˚C. On ageing a 6.4Fe-Ni-36W (mass%) alloy at 800˚C, a fine dispersed
Ni4W phase precipitates from the γ matrix [2003Ron]. Less than 0.5 mass% Fe dissolves in
NiW2 at 950˚C [1991Nik].
The substitution of W for Fe in the FeNi3 phase leads to a increase in the ordering
temperature, which reaches a maximum at about 555˚C for an alloy with 2 at.% W
[1968Ega]. The long-range ordered crystal structure exists up to 3 at.% W [1968Ega,
1970Gom]. According to [1968Ega, 1969Yeg], the temperature maximum was the result of
the formation of a three component ordered structure. [1972Ive] considered that the long
range order started to decrease at a W concentration of 2.05 at.% and the ordered structure
disappeared in alloys containing about 5 at.% W.
Details of the invariant equilibria involving the liquid phase are given in Table 3, taken from
[1932Win]. Amendments have been made to some of the phase compositions. The phase
labeled as Fe3W2 is actually recognized as μ (Fe7W6). The available information on the
invariant reactions proceeding in the solid state is extremely conflicting due to the difficulties
in obtaining the intermediate phases experimentally, most of which are formed in the solid via
peritectoid reactions. [1991Nik] assumed that the μ Ð α+γ+(Fe,Ni)W eutectoid decomposi-
tion took place in the system at about 1130˚C, while [1992Nik] came to the conclusion that it
should be a peritectoid reaction, μ+α Ð γ+(Fe,Ni)W, taking place in the temperature range
1200-1050˚C. Attempts to derive a sequence of reactions for the solid state, taking into account
either of these reactions and the formation of the (Fe,Ni)W solid solution, were not successful.
Therefore, Fig. 1 gives a partial reaction scheme that reflects only the liquid-solid equilibria in
the system.
Liquidus, Solidus Surfaces
Figure 2 shows the projection of liquidus surface based on that constructed by [1932Win],
with some modifications relating to the locations of the invariant points in the binary system
given by [2008Kuz] and the saddle point and homogeneity range of the μ phase given by
[1981Hen]. Figure 3 gives the solidus surface projection of the system. The solidus tempera-
ture along the boundary of the γ phase decreases in the ternary system and reaches a minimum
at about 49 at.% Ni [1932Win].
Fe–Ni–W 16 5
Isothermal Sections
A series of the isothermal sections at 1560, 1500, 1465, 1455 and 1400˚C were constructed by
[1971Win] on the basis of experimental data from [1932Win]. The section for 1400˚C agrees
with that based on experimental data from [1981Hen] and that computed by [1986Fer]. The
isothermal section at 1400˚C is shown in Fig. 4. On lowering the temperature, the μ phase is
assumed to decompose to give (W)+FeW below 1190˚C. Fragments of the isothermal sections
near the W corner at 1050 and 950˚C proposed by [1992Nik] are shown in Figs. 5 and 6,
respectively. The isothermal section of the whole system at 800˚C according to incomplete
data given by [1981Hen] is presented in Fig. 7. The composition of the (Fe,Ni)W apex of the
(Fe,Ni)W + (W) + NiW2 triangle shown in the partial isothermal section at 950˚C (Fig. 6) is
richer in Fe than that given for 800˚C shown in Fig. 7. On decreasing the temperature down to
575˚C, the phase diagram has a similar appearance to that at 950˚C [1992Nik], since among
the phases taking part in the (W)+NiW2+(Fe,Ni)W equilibrium at 950˚C, the (W) and NiW2
phases do not have any noticeable homogeneity range. The only difference among the sections
at 950, 800 and 575˚C lies in the location of the (Fe,Ni)W apex of the (W)+NiW2 +(Fe,Ni)W
triangle. The latter is displaced towards the FeW phase as the temperature decreases. The
version presented by [1982Ban] for the Fe-rich region at 800˚C can not be used in conjunction
with the data of [1981Hen] because of the appearance of the μ phase that contradicts the latter
work. In the isothermal section at 800˚C calculated by [1986Fer], the invariant equilibrium
(W)+NiW+γ is present while equilibria with NiW2 phase is omitted. This is in contradiction
with the accepted Ni-W binary phase diagram [Mas2] where the NiW2 phase is shown to
exist at 800˚C, and therefore, must take part in equilibria within the ternary system. This
section, as well as all of the others computed by [1986Fer] for the temperatures lower than
1100˚C, are not consistent with the Fe-W binary system either, because both of them show
equilibria including the μ phase, which does not exist at these temperatures, together with a
metastable λ phase.
The first experimental study of the ternary system, by [1932Win], presented 8 vertical sections
located mainly in the Fe rich corner. None of them can be considered as accurate because of
differences in the constitution of the binary systems and in the homogeneity range of the μ
phase. The vertical sections presented by [1986Zak1, 1986Zak2, 1991Nik, 1992Nik] concern
the W rich corner, at 80 and 90 mass% W. They were deduced from XRD measurements made
on a great number of annealed alloys and can be taken as tentative. The section at 90 mass% W
showing an increase in the formation of the (Fe,Ni)W phase and a decrease in the NiW2 phase
with increasing Fe content is presented in Fig. 8. The assessed isopleth at 14.3 at.% W is shown
in Fig. 9.
Thermodynamics
[2004Zha1] calculated a positive excess Gibbs energy of mixing, ΔmixGxs, for both the
amorphous phase and the crystalline solid solution in the Fe-Ni-W system at 300 K. For the
amorphous Fe6.1Ni17.3W76.6 (at.%) phase, ΔmixGxs is 1.77 kJ·mol–1.
6 16 Fe–Ni–W
The apparent activation energy for grain growth in the solid state was estimated by
[2006Par] to be about 241 kJ·mol–1, lower than both that for W diffusion in the solid matrix
(268 to 306 kJ·mol–1) and for densification (367 kJ·mol–1). The activation energy of grain
growth during liquid phase sintering is 106 kJ·mol–1 and is comparable with that of densifica-
tion (101 to 136 kJ·mol–1).
[1986Fer] presented an optimization of the thermodynamic description of the liquid, γ
and μ phases and used it to calculate the phase diagram. The solidus curve separating (W) and
(W)+L regions calculated by [1981Ahn] at 1540˚C was close to that calculated from the data of
[1971Win], while the liquidus curve separating the L and L+(W) regions passed at a higher W
concentration than was shown by experiment.
The activation energy of the atomic redistribution process determined from data on
Young’s modulus and resistivity for FeNi3-Ni3W alloys containing up to 2 at.% W in the
temperature range 350-400˚C, is close to that for the FeNi3 binary alloy and is of about 170
kJ·mol–1. For the alloys containing 2-2.5 at.% W, it falls sharply down to 100 kJ·mol–1
[1968Ega, 1969Yeg].
Since tungsten heavy alloys are manufactured conventionally by sintering powder compacts,
characteristics such as density and hardness are important and are usually reported. The
density of a 1.5Fe-3.5Ni-95W (mass%) alloy, measuring 18.0 g·cm–3 was compared with that
of the matrix at 9.2 g·cm–3 in [1986Woo]. The hardness of the matrix was 1.255 GPa (128 HV),
and was much lower than that of the alloy, which measured 4.609 GPa (470 HV). The strength
of the matrix was found to be less than half that of the specimen. A 3Fe-7Ni-W (mass%) alloy
consolidated at 400˚C by shock synthesis had a density of 18.0 g·cm–3; that of the tungsten
particles themselves being of about 29.4 g·cm–3. The hardness remained consistent throughout
the specimen [2005Mar]. [1977Mar] found the following characteristics for the 2.4Fe-Ni-93W
composition: density of 17.4 g·cm–3, hardness of 3.432 GPa (350 HV), tensile strength of 9
MPa, elongation of 20%. The highest value of microhardness of the γ phase was reported by
[1969Aga] in the alloy 10W-54Fe-36Ni (mass%), after sintering at 1350˚C. The (W) phase
quenched from 800˚C has a hardness of 5.1 GPa [1991Nik]. The hardness of Fe-(5-20)Ni-
(5-50)W (mass%) alloys increases with the W content; an observation explained by the
increase in the amount of μ phase present [1982Ban] and the occurrence of a martensitic
transformation. A maximum hardness, of about 5.384 GPa (540 HV), was found in (W)+γ+μ
ternary alloys at 1200˚C. The variation in hardness with ageing time at 800˚C of a 36W-6.4Fe-
57.6Ni and a 36W-19.2Fe-44.8Ni (mass%) alloy was compared by [2003Ron]. The hardness of
the second alloy decreased monotonically while that of the first one after decreasing to the
same level, increased, so the hardness gap between these two alloys was enlarged as ageing time
increased. Fine Ni4W precipitates strengthened and hardened the first alloy. A 1.4Fe-5.6Ni-
93W (mass%) specimen sintered at 1300˚C after mechanical alloying exhibited fine tungsten
particles of about 3 μm, a density higher than 99% of its theoretical value and a high yield
strength of about 1100 MPa, while its impact energy and elongation characteristics were low
[2000Ryu]. A large W/W contiguity and a low matrix volume fraction were considered as
reasons for poor ductility and impact properties. This alloy, being liquid phase sintered in
addition to being sintered in the solid state, possessed fine tungsten particles of about 6-15 μm
in size; finer than those obtained through a conventional liquid phase sintering process.
Fe–Ni–W 16 7
An alloy of composition 2.1Fe-4.9Ni-93W sintered at 1150˚C for 0.5 h, contains W particles of

an average size of 2 μm distributed homogeneously in the γ phase [2004Zha2]. Sintering at
1280˚C, results in an increase in particle size to 6-8 μm. The density of material sintered at
1150˚C was above 95% of its theoretical value. A theory of liquid phase sintering is presented
in [2007Lee] for Fe-Ni-W alloys.
A number of investigations have been carried out on an alloy of composition 3Fe-7Ni-90W
(mass%). Fe additions to the Ni-90W (mass%) alloys increase the ductility and elongation of
the alloy, which may reach 20% [1965Dzy, 1977Mar]. [2002Ekb] found that the microhard-
ness of the tungsten particles increases from 3.815 GPa (389 HV) for undeformed specimens to
4.992 GPa (509 HV) after 57% deformation at 25˚C. The highest value of microhardness
observed was 5.296 GPa (540±28 HV) following 49% deformation at 800˚C. On increasing
temperature, this value decreases to a value close to that of an undeformed specimen at
1100˚C. The dislocation density of the W particle measured for this composite was observed to
be higher at higher deformation stress. The electrical resistance and hardness increases with
the amount of deformation of the composite [2000Min]. Impact energy tests show that the
toughness of heavy alloys is sensitive to the rate of cooling from the sintering temperature; the
concentration of Ni and Fe in the alloys being a critical factor in the heat treatment process
[1979Edm]. The ultimate tensile strength of a specimen that had been subjected to heat
treatment under vacuum at 1500˚C was shown by [1983Du] to increase, depending on the
applied stress. The ductility of the heat treated specimen increased by about 25 times as
compared to the as-sintered material, the elongation under tension reaching 26.1-27.2%
depending on the applied strain. The maximum crack free reduction by cold rolling was
72% [2000Min]. [1981Hen] showed that the tensile and bending strength of this alloy did not
depend significantly on the exposure time at 900˚C, but it rather did on the furnace atmo-
sphere. On heating a mechanically alloyed specimen, the solubility of W in the γ phase was
found to decrease on increasing the temperature up to about 1480˚C. The size of W particles
increased slowly on heating up to about 600˚C, and on heating up to 1200˚C, crystalline
growth was enhanced [2001Fan].
The Young’s modulus of the (Fe,W)Ni3 ordered phase changes with composition, passing
through a minimum at 2.2 at.% W [1968Ega, 1969Yeg], which was explained by a decrease in
the ferromagnetic interaction and an increase in the metallic bond in the ordered alloys on
substitution of Fe by W atoms. [1969Yeg] found a difference in the Curie point between
annealed and rapidly cooled specimens, which increases linearly from a composition of FeNi3
up to Fe-75Ni-3W (at.%). The Curie temperature of Fe2W-Ni2W alloys decreases on increas-
ing the Ni content up to 10 at.%, after which the temperature passes through a maximum at
about 47 at.% Ni [1972Var].
The recovery and recrystallization of cold worked tungsten specimens depends on the
penetration of the Fe-Ni-W liquid, the penetration rate being dependent on microstructure
and internal stress [2003Ant]. The complete penetration of the Fe-Ni-W melt in deformed
tungsten was observed after 84 s while for specimens recrystallized before penetration, the rate
was moderate.
The experimental techniques used in the investigation of materials properties of Fe-Ni-W
alloys are listed in Table 4.

8 16 Fe–Ni–W
Miscellaneous
The addition of 3 at.% W destroys the long range ordering in FeNi3 owing to the allocation of
Ni atoms to the second coordination sphere [1970Gom].
The fracture surface of an irradiated bend specimen of composition 1.6Fe-3.4Ni-W
(mass%) showed cleavage fracture in the tungsten grains and simple fracture in the Ni based
matrix [1990Kra]. The specimen revealed a strong increase in the ductile-brittle transition
temperature on increasing the neutron flux.
A small decrease in the lattice parameter of the γ phase was observed towards 47 at.% Ni at
950˚C from a = 359.9 to 359.3 pm, by [1972Var].
The W solubility in the γ solution decreases on increasing the Fe content. The most
significant change in the W solubility of the γ phase with temperature was observed for the
alloys lying on the section 50Fe:50Ni [1969Aga]. The solubility of W in the binder phase
decreases as temperature increases for mechanically alloyed specimens, unlike for those
obtained by traditional sintering [2001Fan].
[1965Dzy] studying the distribution of the alloy components in the phases obtained by
liquid sintering showed that introducing Fe in a 10Ni-W (mass%) alloy suppressed the process
of intensive grain boundary diffusion by reducing the Ni solubility in W grains as well as the W
solubility in the Ni based matrix. The solubility of Fe in W exceeds that of Ni; the amount of Fe
in the center of W grain being much greater than that of Ni for alloys with the same
proportion of elements in the matrix. The low melting binder phase of Fe-Ni-W sintered
alloys occupies 21-23% of the surface area.
Depending on cooling conditions, the lattice parameter of the binder phase of a 3Fe-7Ni-
90W (mass%) alloy determined at RT increases from a = 359.25 pm (annealing at 1200˚C)
through a = 359.43 pm (slow cooling) to a = 360.20 pm (quenching); the decrease in the W
content in the binder phase being observed as 2-2.5 mass% on slow cooling and 5 mass% or
more on annealing [1980Min]. The nickel based solid solution can contain from one to several
hundred W phase particles. No texture was observed in a 3Fe-7Ni-W (mass%) composite
quenched from the liquid phase sintering temperature [2000Min].
The study of [1983Du] supported the inference of [1979Edm] that the cracking took place
at the W grain-matrix interface. Hydrogen stored in voids and dissolved in the metals during
the sintering process causes the interfacial embrittlement. Heat treatment under vacuum was
shown by [1983Du] to lead to the removal of the embrittlement and to an improvement in the
tensile properties of the specimens. The different microstructures of two alloys containing the
same amount of W but different ratios of Ni:Fe (9:1 and 7:3) results, according to [2003Ron],
in different mechanism of hardening.
The phase evolution with respect to milling time was determined by [2004Zha2]: the
supersaturated solid solution forms first followed by a partially amorphous phase and then a
mixture of amorphous and nanocrystalline phases. It is an example of mechanically induced
amorphization, the system not having a large negative heat of mixing. During annealing of a
mechanically alloyed specimen, the following stages were observed: stress relaxation, recovery
and grain growth of nanocrystalline phases, phase precipitation and amorphous phase crys-
tallization [2001Fan].
[1995Dje] assumed a statistical distribution of 3 at.% W in the Fe rich alloys of the ternary
system.
The distortion on sintering taking place in alloy compacts with W contents of 83, 88 and
93 (mass%) with Fe:Ni ratio of 3:7, is linked to the underlying microstructure, and for the
Fe–Ni–W 16 9
compositions discussed, the transition from distorting to undistorting compacts occurred at

compositions between Fe-Ni-88W and Fe-Ni-93W. Heating rates of up to 15˚C/min did not
have a significant effect on densification or distortion [2004Bol].
The study by [2001He] of mechanically alloyed (7 to 19.5)Fe-(5.5 to 18)Ni-75W (at.%)
material showed that the precipitation of W particles, followed by crystallization of the γ phase
and formation of the NiW and Ni4W phases in a glassy matrix, took place under heating.
[1984Mud] identified the phase forming at the W-matrix interfaces in Fe-Ni-W
(Fe:Ni=1:1) commercial alloy as (Fe,Ni)6W6C, which seemed to be stabilized by impurities.
According to the model of liquid phase sintering used by [2007Lee] to simulate coarsening
kinetics, the average particle volume increases linearly with time and the size of the particles is
consistent with that obtained experimentally.
It should be emphasized that the information available for the Fe-Ni-W phase diagram
that has been considered here concerns only some aspects of the equilibria and thus can not be
taken as final. The key problem is that it is quite difficult in practice to obtain homogeneous
specimens owing to the great difference both in the melting points of the components and in
their densities. Another challenge is to attain equilibrium in the system, as most reactions
occurring in the solid state are at relatively low temperatures. Similar reservations should be
made concerning the Ni-W binary system used in the calculations. The lack of reliable versions
of the Fe-W and Ni-W phase diagrams limits the possibility of deriving an accurate version of
the Fe-Ni-W phase diagram.
. Table 1
Investigations of the Fe-Ni-W Phase Relations, Structures and Thermodynamics
[1932Win] Melting, thermal and microscopic analysis Fe-Ni(0-45)W (mass%)

[1965Dzy] Sintering at 1450˚C, EPMA, optical 3Fe-7Ni-W, 5Fe-5Ni-W, 7Fe-3Ni-W
microscopy (mass%)
[1968Ega] Induction melting, Young’s modulus, Fe-75Ni-(0-5.1)W (at.%) 400-560˚C
electrical resistivity
[1969Aga] Sintering / melting, microstructure, X-ray Fe-Ni-(0-40)W (mass%) at Fe:Ni =
analysis, microhardness test 20:80, 30:70, 50:50, 60:40, 70:30,
1350-800˚C
[1969Yeg] Young’s modulus, saturation magnetization Fe-75Ni-(0.5-5.1)W
[1970Gom] Neutron diffraction (Ni3Fe)1–xWx, x = 0.01-0.05
[1972Ive] X-ray of alloys after heating at 850, 530, 250˚C (19.9-24.6)Fe-Ni-(0.5-5.05)W (at.%)
down to RT
[1972Var] Sintering then quenching; X-ray analysis, Fe2W-Ni2W, at 950˚C
optical microscopy, EPMA, magnetic
properties
[1977Mar] Sintering at 1470˚C, EPMA 2.4Fe-Ni-93W (at.%)

10 16 Fe–Ni–W
[1979Edm] Sintering, optical microscopy, XRD, TEM, 3Fe-7Ni-W, 5Fe-5Ni-W (mass%)

EPMA, SEM, AES
[1980Min] Sintering, X-ray, microstructure, EPMA, 10(Fe+Ni)-W (mass%), Fe:Ni = 3:7
electron microscopy
[1981Ahn] Thermodynamic calculation incorporating the Fe-Ni-W, 1540˚C
ternary regular solution model
[1981Hen] Metallography, X-ray, DTA, tensile strength, 1400˚C, 1000˚C, 850˚C Fe-Ni-(0-75)W
bending strength tests (mass%)
[1982Ban] Arc melting, optical microscopy, XRD, Fe-(5-20)Ni-(5-50)W (mass%) at 1300,
microhardness, hardness, dilatometry, 1200, 800˚C
thermal analysis
[1982Buk] EPMA (MS-46 “Cameca”) (3-7)Fe-(7-3)Ni-W (mass%),
1550-800˚C
[1982Rom] The two-stage plastic-coal replica extraction Fe-Ni-90W (mass%) Fe:Ni = 3:7 ageing
method, electronic microscopy, XRD, EPMA at 1000-800˚C
[1983Du] EPA, SEM 3Fe-7Ni-W (mass%) sintered and heat
treated in vacuum at 1500˚C
[1984Mud] Sintering, TEM, EDX, scanning Auger 4.5Fe-4.5Ni-W (mass%)
spectrometry
[1986Fer] Diffusion couples, optical microscopy, xFe-(100–x)Ni-(0.1-50)W (mass%) 0.2
microprobe analysis, calculation ≲ x ≲ 98.8, 1000-1400˚C
[1986Woo] Optical microscopy, XRD, EMPA, chemical 1.5Fe-3.5Ni-95W, 21.4Fe-55.3Ni-
analysis 23.4W at 1100˚C
[1986Zak1] Sintering, X-ray, optical microscopy, EPMA, Fe-(0-10)Ni-W (mass%), stepped
Pirani and Alterthum methods, annealing: 1400˚C for 24 h, 1200 for
microhardness test 26 h
[1986Zak2] Sintering, X-ray, optical microscopy, EMPA, 20(Fe+Ni)-W (mass%), stepped
Pirani and Alterthum methods, annealing: 1400˚C for 24 h, 1200˚C
microhardness test for 26 h
[1987Kar] Induction melting, XRD, EPMA, metallography Fe-(0-30)Ni-(17-44)W (mass%)
[1990Kra] Sintering, neutron irradiation, SEM, optical 1.6Fe-3.4Ni-W (mass%) 250˚C
metallography, three point bending test
[1991Nik] Sintering, XRD, optical microscopy, EMPA, 10 and 20 (Fe+Ni)-W (mass%) at 800
Pirani and Alterthum methods, (720 h), 575˚C (1680 h)
microhardness test
[1992Nik] Sintering, XRD, optical microscopy 10 and 20 (Fe+Ni)-W (mass%) at
1050˚C (720 h), 950˚C (1000 h)
[1995Dje] Sintering, EPMA, Mössbauer spectroscopy, Fe-16.3Ni-3W, 450˚C
TEM, calculation

Fe–Ni–W 16 11
[2001Fan] Mechanical alloying, XRD, optical microscopy, 3Fe-7Ni-90W (mass%)

EDX, DTA
[2001He] Mechanical alloying XRD, DSC, SEM, TEM (7.9-12.8)Fe-Ni-50W and (7-19.5)Fe-
Ni-75W (at.%), 570-850˚C
[2003Ron] Sintering, cold rolling, XRD, TEM, hardness Fe-Ni-36W (mass%) Fe:Ni = 9:1; 7:3 at
test 800˚C
[2004Zha1] Mechanical alloying, XRD, TEM 6.1Fe-17.3Ni-76.6W (at.%)
[2004Zha2] Mechanical alloying, XRD, TEM, DSC, EDX, 2.1Fe-4.9Ni-93W (mass%) sintering at
SEM, inert gas fusion infrared analysis 1150 and 1280˚C
[2005Mar] Shock wave synthesis and consolidation, SEM, 10(Fe+Ni)-W (mass%) 300, 400, 800
XRD, BSE, EPMA and 1000˚C
[2006Par] Solid state and liquid phase sintering, SEM, 5.1Fe-11.9Ni-W, 3.6Fe-8.4Ni-W, 2.1Fe-
measuring of grain size 4.9Ni-W (mass%), 1200 to 1500˚C
[2006Zha] Mechanical alloying, XRD, TEM, DSC, EDX, 6.1Fe-13.2Ni-80.7W (at.%) from 200 to
SEM, an inert gas fusion infrared analysis 1400˚C
. Table 2
Pearson
Symbol/
γ, Fe1–x–yNixWy cF4 at x = 0, 0 ≤ y ≤ 0.146

Fm3m at y = 0, 0 ≤ x ≤ 1
Cu at y + x = 1, y ≤ 17.5 at 1495˚C [Mas2]
a = 358 15Fe-3.5Ni-95W (mass%) [1986Woo]
a = 359 at x = 4.6, y = 93 [1977Mar]
(γFe) a = 364.67 at 915˚C [Mas2, V-C2]
1394 - 912
(Ni) a = 352.40 at 25˚C [Mas2]
< 1455
αδ, Fe1–x–yNixWy cI2 at y = 0, 0 ≤ x ≤ 0.046 (αFe)
< 1548 Im3m at y = 0, 0 ≤ x ≤ 0.038 (δFe)
W
(δFe) a = 293.15 [Mas2]
1538 - 1394
(αFe) a = 286.65 at 25˚C [Mas2]
< 912

12 16 Fe–Ni–W
Pearson
Symbol/
(εFe) hP2 P63/ a = 246.8 at 25˚C, 13 GPa [2008Kuz]

mmc c = 396.0
Mg
(W) cI2 a =316.52 at 25˚C [Mas2]
< 3422 Im3m dissolves 2.6 at.% Fe and about
W 0.3 at.% Ni [Mas2, 1991Oka]
a = 316 in a two-phase alloy of 3Fe-10Ni-90W (mass%)
[1982Rom]
γ’, FeNi3 cP4 a = 355.23 63-83 at.% Ni at 347˚C [2008Kuz]
< 517 Pm3m a = 355.9 ± 0.1 24.6Fe-Ni-0.5W
AuCu3 a = 356.9 ± 0.1 19.9Fe-Ni-5.05W (at.%) [1972Ive]
γ’’, FeNi tP4 a = 357.9 Metastable ordering temperature about 320˚C at
51.2 at.% Ni [2008Kuz]
P4/mmm
AuCu
λ, Fe2W hP12 - metastable phase at 33.3 at.% W [Mas2]
≲ 1060 P63/mmc
MgZn2
μ, Fe7W6 hR39 from 40.5 to about 42.1 at.% W [Mas2]
1637 - 1190 R3m a = 475.7 Fe-3.3Ni-33.3W (at.%)
Fe7W6 c = 258.2
δ, (Fex Ni 1–x)W oP* 0 ≤ x ≤ 1 at 950˚C [1992Nik]
P212121
FeW MoNi from 48.5 to about 50.7 at.% W [Mas2]
≲ 1215 dissolves about 8.5 mass% Ni at 1050˚C [1992Nik]
NiW at about 50 at.% W [1991Oka]
< 1068 a = 776 [V-C2]
b = 1248
c = 710
Ni4W tI10 at 19.4 at.% W [1991Oka]
< 1002 I4/m a = 573.0 ± 0.1 [V-C2]
MoNi4 c = 355.3 ± 0.1
NiW2 tI96 at 66.7 at.% W [1991Oka] dissolves ≤0.5 mass% Fe
< 1027 at 950, 800 and 575˚C [1991Nik, 1992Nik]
-
a = 1040 [V-C2]
c = 1090

Fe–Ni–W 16 13
. Table 3
Composition (at.%)
Reaction T [˚C] Type Phase Fe Ni W
L + αδ Ð γ + μ 1465 U1 L 70.7 18.1 11.2

αδ 75.1 12.8 12.09
γ 74.5 16.2 9.3
μ ~48 ~10 ~42
L + μ Ð γ + (W) 1455 U2 L 54.7 33.6 11.7
μ ~48 ~10 ~42
γ 64.1 26.2 9.7
(W) ~0.5 - ~99.5
. Table 4
Investigations of the Fe-Ni-W Materials Properties
[1965Dzy] EPMA Grain growth

[1968Ega] Young’s modulus, electrical resistivity Fe-75Ni-(0-5.1)W (at.%) alloys
[1969Yeg] Young’s modulus, saturation Fe-75Ni-(0.5-5.1)W (at.%) alloys
magnetization
[1969Aga] Microhardness of γ phase measured using 10 and 20 mass% W with Ni:Fe = 40:60;
a PMT-3 instrument 30:70, after sintering at 1350˚C
[1972Var] Curie temperature measured on alloys Change in Curie temperature of Fe2W-
water quenched from 950˚C Ni2W alloy as a function of Ni content
[1977Mar] Mechanical properties of the alloy Ductility, hardness, fracture toughness
sintered at 1470˚C Fe2.4Ni4.6W93 alloy
[1979Edm] Un-notched Charpy test, AES The variations in toughness of the 3(5)Fe-
7(5)Ni-W (mass%) alloys
[1981Hen] Bend test Tensile and bending strength at 900˚C
[1982Ban] Hardness Change in the alloy hardness with respect
to W content at 1200˚C
[1983Du] EPMA, SEM, microhardness tensile test Variation of ultimate tensile and yield
strength with strain rate of 3Fe-7Ni-W
(mass%) alloy
[1986Woo] Sintering, optical microscopy, XRD, EMPA, Density, hardness, stress/strain curves
uniaxial compression test

14 16 Fe–Ni–W
[1990Kra] Neutron irradiation test at 250-300˚C in Ductile-brittle transition temperature of

the reactors FRJ2 and HFR fluxes of up to 1.63Fe-3.52Ni-W (mass%) alloy
56·1024 neutrons μ–2. SEM, metallography
analysis
[1991Nik] Microhardness of (W) phase of the Variation of microhardness of (W) phase
Fe-Ni-W alloys quenched from 800˚C of the alloys along the 90 mass% W
section
[2000Ryu] Density, yield strength, elongation impact of 1.4Fe-5.6Ni-93W (mass%) alloy
energy, size of W particles, matrix volume mechanically alloyed, sintered at 1300˚C
fraction, W/W contiguity. Tensile test and subsequently liquid phase sintered at
1470˚C and water quenched
[2000Min] Tensile test, microhardness, electrical Effect of deformation by rolling on
resistance, SEM, microstructure, X-ray hardness and electrical resistance of the
3Fe-7Ni-90W (mass%) composite slowly
and rapidly cooled
[2001Fan] Mechanical alloying of the 3Fe-7Ni-90W W particle size
(mass%) mixture, XRD, optical Variation of W in γ phase with
microscopy, EDX, DTA temperature
[2002Ekb] Deformation by elongation in a tensile Dislocation density, microhardness
testing machine and by isostatic
extrusion, XRD, microhardness, HVEM,
stereographic photography
[2003Ron] Hardness (Rockwell A) measured at The variation of hardness of the Fe-Ni-
different ageing times at 800˚C 36W (mass%) alloys where Fe:Ni = 1:9
and 3:7
[2003Ant] Melt penetration test, SEM, TEM, hardness Penetration rate, W solid exposed to
measurement 24Fe-43Ni-33W (mass%) melt
[2004Bol] Dilatometry, density, solid volume Distortion, grain size, grain growth rate
fraction and contiguity measured with of (Fe,Ni)1–xWx, x = 83, 88, 93 mass%;
image analysis software Fe:Ni = 3:7
[2004Zha2] Mechanical alloying, XRD, TEM, DSC, EDX, Density, W grain size in 2.1Fe-4.9Ni-93W
SEM, Archimedes water immersion (mass%) composition after sintering at
method 1150 and 1280˚C
[2005Mar] SEM, EDS, X-ray, quantitative image Grain size, density, consolidation of
analysis, microhardness, density, grain compacts by shock synthesis
size

Fe-Ni-W. Reaction scheme
. Fig. 1
Fe–Ni–W 16 15

16 16 Fe–Ni–W
. Fig. 2
Fe-Ni-W. Liquidus surface projection

Fe–Ni–W 16 17
. Fig. 3
Fe-Ni-W. Solidus surface projection

18 16 Fe–Ni–W
. Fig. 4
Fe-Ni-W. Isothermal section at 1400˚C

Fe–Ni–W 16 19
. Fig. 5
Fe-Ni-W. Fragment of the isothermal section at 1050˚C

20 16 Fe–Ni–W
. Fig. 6
Fe-Ni-W. Fragment of the isothermal section at 950˚C

Fe–Ni–W 16 21
. Fig. 7
Fe-Ni-W. Isothermal section at 800˚C

22 16 Fe–Ni–W
. Fig. 8
Fe-Ni-W. Isopleth at 90 mass% W, plotted in at.%

Fe–Ni–W 16 23
. Fig. 9
Fe-Ni-W. Isopleth at 14.3 at.% W

24 16 Fe–Ni–W
References
[1932Win] Winkler, K., Vogel, R., “The Ternary System of the Iron-Nickel-Tungsten” (in German), Arch.
Eisenhuettenwes., 6, 165–172 (1932) (Experimental, Morphology, Phase Diagram, Phase Relations,
Magn. Prop., 6)
[1949Jae] Jaenecke, E., “Fe-Ni-W” (in German) in “Kurzgefasstes Handbuch aller Legierungen”, Winter Verlag,
Heidelberg, 635–636 (1949) (Review, Phase Diagram, Phase Relations, 2)
[1961Eng] English, J.J., “Binary and Ternary Phase Diagrams of Columbium, Molybdenum, Tantalum and Tungsten”,
Defense Metals Information Center, Batelle Memorial Institute, Columbus 1, Ohio, 152, 204–206 (1961)
[1965Dzy] Dzykovich, I.Ya., Makarova, R.V., Teodorovich, O.K., Frantsevich, I.N., “Distribution of Elements
During the Formation of Sintered Alloys of the System W-Ni-Fe”, Sov. Powder Metall. Met. Ceram., 8,
655–660 (1965), translated from Poroshk. Metall., (8), 62–69, (1965) (Experimental, Phase Relations,
Mechan. Prop., 3)
[1968Ega] Eganyan, I.L., Selissky, Y.P., “Investigation of the Effects of Atomic Ordering in Ternary Solid Solutions
on the Basis of Ni3Fe Alloyed by VI Group Elements - Chromium, Molybdenum, Tungsten” (in
Russian), Izv. Akad. Nauk Ukr. SSR, Metallofizika, (20), 100–104 (1968) (Crys. Structure, Experimental,
Phase Relations, Mechan. Prop., Thermodyn., 3)
[1969Aga] Agababova, V.M., Chaporova, I.N., “Boundary of the Monophasic γ-Solid Solution Region in the
Ternary System W-Ni-Fe”, Sov. Powder Metall. Met. Ceram., (7), 571–576 (1969), translated from
Poroshk. Metallurg., (7), 65–72, (1969) (Experimental, Phase Relations, Mechan. Prop., 2)
[1969Yeg] Yeganyan, I.L., Selisskiy, Ya.P., “A Study of the Effects of Atomic Ordering in Ternary Solid So1utions of
Cr, Mo, and W in Ni3Fe.”, Phys. Met. Metallogr., 27(2), 18–25 (1969), translated from Fizika Metallov i
Metalloved., 27(2), 210–218 (1969) (Experimental, Thermodyn., 8)
[1970Gom] Goman’kov, V.I., Puzey, I.M., Mal’tsev, E.I., “Effect of Alloying Elements on the Superstructure of
Ni3Fe” (in Russian), Dokl. Akad. Nauk SSSR, 194(2), 309–311 (1970) (Crys. Structure, Experimental, 6)
[1971Win] Winslow, F.R., “The Iron-Nickel-Tungsten Phase Diagram”, U.S. At. Energy Comm. Pubn, Y-1758 (1971)
(Phase Diagram, Phase Relations, Review) as quoted in [1988Ray]
[1972Ive] Iveronova, V.I., Katsnelson, A.A., Silonov, V.M., “On Atomic Ordering in the System Nickel-Iron-
Tungsten”, Phys. Met. Metallogr., (3), 77–81 (1972), translated from Fiz. Met. Metalloved., (3), 535–539
[1972Var] Varli, K.V., Dyakonova, N.P., Korneva, O.S., Umansky, Ya.S., “Investigation of Some Alloys of the
System Fe-Ni-W” (in Russian), Izv. Vyssh. Ucheb. Zaved., Chern. Met., (1), 120–123 (1972) (Experi-
mental, Phase Relations, Crys. Structure, Morphology, Mechan. Prop., Magn. Prop., 5)
[1977Mar] Margaria, T., Allibert, C., Driole, J., “Structural Characterisation of W-Base Sintered Alloys: W-Ni -Fe,
W-Ni-Co and W-Ni-Cr” (in French), J. Less-Common Met., 53, 85–95 (1977) (Crys. Structure, Experi-
mental, Mechan. Prop., Morphology, Phase Relations, 6)
[1979Edm] Edmonds, D.V., Jones, P.N., “Interfacial Embrittlement in Liquid-Phase Sintered Tungsten Heavy
Alloys”, Metall. Trans. A, 10A, 289–295 (1979) (Crys. Structure, Experimental, Mechan. Prop., Mor-
phology, Phase Relations, 12)
[1980Min] Minakova, R.V., Storchak, N.A., Verkhovodov, P.A., Bazhenova, L.G., Poltoratskaya, V.L., “Some
Structural Characteristics of the Binder Phase of W-Ni-Fe Alloys”, Sov. Powder Metall. Met. Ceram.,
(12), 842–846 (1980), translated from Poroshk. Metall., (12), 45–50 (1980) (Experimental, Crys.
Structure, Morphology, Phase Relations, 16)
[1981Ahn] Ahn, S.T., “Thermodynamic Calculation of W-Ni-Fe Ternary Phase Diagram at 1540˚C”, J. Korean Inst.
Met., 19(11), 947–951 (1981) (Calculation, Phase Diagram, Phase Relations, Thermodyn., 12)
[1981Hen] Henig, E.T., Hofman, H., Petzow, G., “The Constitution of W-Fe-Ni alloys and its Influence on
its Mechanical Properties” (in German) in “Plansee Seminar”, Ortner, H.M., (Ed.), Reutte, Austria,
Metallwerk Plansee, 335–359 (1981) (Experimental, Phase Diagram, Phase Relations, Mechan.
Prop., 63)
[1981Ray] Raynor, G.V., Rivlin, V.G., “Critical Evaluation of Constitutions of Certain Ternary Alloys Containing
Iron, Tungsten and a Third Metal”, Int. Met. Rev., 26, 213–249 (1981) (Crys. Structure, Phase Diagram,
[1982Ban] Bannykh, O.A., Kurbatkina, O., Prokofiev, D.J., “Phase Diagram for Fe-Ni-W System”, Izv. Akad. Nauk
SSSR, Met., (6), 197–203 (1982) (Experimental, Phase Diagram, Phase Relations, Mechan. Prop., 5)

Fe–Ni–W 16 25
[1982Buk] Bukatov, V.G., Romashov, V.M., Gostev, Yu.V., “Effect of Heat Treatment on the Distribution of
Elements in the Phase Components of W-Ni-Fe Alloys” (in Russian), Poroshk. Metall., (10), 38–41
(1982) (Experimental, Crys. Structure, Phase Relations, 6)
[1982Rom] Romashov, V.M., Kurganov, G.V., Vlasov, E.E., “Precipitated Particles in the Binder Phase of W-Ni-Fe
Alloys”, Sov. Powder Metall. Met. Ceram., (12), 952–953 (1982), translated from Poroshk. Metall., (12),
55–56 (1982) (Experimental, Crys. Structure, Morphology, Phase Relations, 5)
[1983Du] Du, J., “Strain and Fracture of Liquid Phase Sintered Alloy 90W-7Ni-3Fe”, Acta Metall. Sin. (China), 19
(4), A354-A358 (1983) (Experimental, Phase Relations, Morphology, Mechan. Prop., 11)
[1984Mud] Muddle, B.C., “Interphase Boundary Precipitation in Liquid Phase Sintered W-Ni-Fe and W-Ni-Cu
Alloys”, Metall. Trans. A, 15A, 1089–1098 (1984) (Crys. Structure, Morphology, Experimental, 34)
[1986Fer] Fernandez-Guillermet, A., Ostlund, L., “Experimental and Theoretical Study of the Phase Equilibria in
the Fe-Ni-W System”, Metall. Trans. A, 17A, 1809–1823 (1986) (Experimental, Calculation, Thermo-
dyn., Phase Diagram, Phase Relations, 32)
[1986Woo] Woodward, R.L., McDonald, I.G., Gunner, A., “Comparative Structure and Physical Properties of
W-Ni-Fe Alloys Containing 95 and 25 wt.% Tungsten”, J. Mater. Sci. Lett., 5(4), 413–414 (1986)
(Experimental, Phase Relations, Morphology, Crys. Structure, Mechan. Prop., 3)
[1986Zak1] Zakharov, A.M., Parshikov, V.G., Vodop’yanova, L.S., Novozhonova, V.A., “Phase Equilibria in Alloys
of the W-Fe-Co-Ni System. I. Alloys Containing 10% (Fe+Co+Ni) at 1400-1200˚C”, Sov. Powder Metall.
Met. Ceram., (4), 313–316 (1986), translated from Poroshk. Metall., (4), 60–64 (1986) (Experimental,
[1986Zak2] Zakharov, A.M., Parshikov, V.G., Vodopyanova, L.S., Godovannaya, E.B., “Phase Equilibria In
Tungsten-Iron-Cobalt-Nickel Alloys Containing 20% Iron + Cobalt + Nickel at 1400-1200˚C” (in
Russian), Izv. Vyss. Uchebn. Zaved., Tsvetn. Metall., (5), 75–79 (1986) (Assessment, Crys. Structure,
Phase Diagram, Mechan. Prop., Experimental, 9)
[1987Kar] Kardonskii, V.M., “Effect of Ni on the Structure and Phase Composition of Fe-W Alloys” (in Russian),
Fiz. Met. Metalloved., 63(1), 133–136 (1987) (Experimental, Crys. Structure, Phase Relations, Morpho-
logy, 4)
[1988Ray] Raynor, G.V., Rivlin, V.G., “Fe-Ni-W” in “Phase Equilibria in Iron Ternary Alloys”, Inst. Metals, London,
4, 441–452 (1988) (Crys. Structure, Phase Diagram, Phase Relations, Review, 7)
[1990Kra] Krautwasser, P., Derz, H., Kny, E., “Influence of Fast Neutron Fluence on the Ductile-Brittle Transition
Temperature of Tungsten, W-10Re, and W-3.4Ni-1.6Fe”, High Temp.-High Pressures, 22(1), 25–32
(1990) (Experimental, Morphology, Mechan. Prop., 8)
[1991Nik] Nikol’skii, A.V., Zakharov, A.M., Parshikov, V.G., Vodop’yanova, L.S., “Phase Equilibria in the
Tungsten-rich Field of the W-Fe-Ni System in the 800-575˚C”, Sov. Powder Metall. Met. Ceram., (8),
675–680 (1991), translated from Poroshk. Metall., (8), 61–67 (1991) (Crys. Structure, Experimental,
Phase Diagram, Phys. Prop., Phase Relations, 11)
[1991Oka] Okamoto, H., “Ni-W (Nickel-Tungsten)”, J. Phase Equilib., 12(6), (1991) (Phase Diagram, Phase
[1992Nik] Nikosky, A.V., Zakharov, A.M., “The W-Fe-Ni Systems at 1050-950˚C and 10-20% (Fe + Ni)”, Russ.
Metall., (5), 213–217 (1992) translated from Izv. Akad. Nauk, Met., (5), 220–223 (1992) (Crys. Structure,
Experimental, Phase Diagram, Phys. Prop., 15)
[1994Rag] Raghavan, V., “Fe-Ni-W (Iron-Nickel-Tungsten)”, J. Phase Equilib., 15(6), 631–632 (1994) (Phase
[1995Dje] Djega-Mariadassou, C., Bessais, L., Servant, C., “Nanocrystalline Precipitates Formed by Aging of BCC
Disordered Fe-Ni-Mo Alloys”, Phys. Rev. B: Condens. Matter, 51(14), 8830–8840 (1995) (Crys. Structure,
Experimental, Phys. Prop., 16)
[2000Min] Minakova, R.V., Pachek, A.P., Kryachko, L.A., Kresanova, A.P., Zatovskii, V.G., “Texture Formation in
the Cold Rolling of Pseudo-Alloys”, Powder Metall., Met. Ceram., 39, 78–84 (2000) (Crys. Structure,
Phase Relations, Electr. Prop., Experimental, Mechan. Prop., 5)
[2000Ryu] Ryu, H.J., Hohg, S.H., “Effects of Sintering Conditions on Mechanical Properties of Mechanically
Alloyed Tungsten Heavy Alloys”, Key Eng. Mater., 183–187, 1291–1296 (2000) (Experimental, Mor-
phology, Kinetics, Mechan. Prop., 15)
[2001Fan] Fan, J., Huang, B., Qu, X., Zou, Zh., “Thermal Stability, Grain Growth and Structure Changes of
Mechanically Alloyed W-Ni-Fe Composite During Annealing”, Inter. J. Ref. Met. Hard Mater., 19(2),
73–77 (2001) (Experimental, Phase Relations, Morphology, 17)

26 16 Fe–Ni–W
[2001He] He, Z., Courtney, T.H., “Crystallization and Thermal Stability of Mechanically Alloyed W-Ni-Fe
Noncrystalline Materials”, Mater. Sci. Eng. A, 315(1-2), 166–173 (2001) (Experimental, Phys. Prop.,
Thermodyn., 18)
[2002Ekb] Ekbom, L., Antonsson, T., “Tungsten Heavy Alloy: Deformation Texture and Recrystallization of
Tungsten Particles”, Inter. J. Refract. Met. Hard Mater., 20, 375–379 (2002) (Experimental, Morphology,
Mechan. Prop., 16)
[2003Ant] Antonsson, T., Ekbom, L., Eliasson, A., Fredriksson, H., “Liquid Ni-Fe Penetration and Recrystallisa-
tion in Tungsten”, Int. J. Refract. Met. Hard Mater., 21, 159–170 (2003) (Experimental, Kinetics,
Transport Phenomena, 30)
[2003Ron] Ronghua, L., Jihua, H., Sheng, Y., Jun, Zh., “Strain Aging Precipitation Behavior of β Phase in W-Ni-Fe
Ternary System”, J. Mater. Sci. Lett., 22(5), 397–398 (2003) (Experimental, Phase Relations, Mechan.
Prop., Morphology, 7)
[2004Bol] Bollina, R., German, R.M., “Heating Rate Effects on Microstructural Properties of Liquid Phase
Sintered Tungsten Heavy Alloys”, Int. J. Refract. Met. Hard Mater., 22, 117–127 (2004) (Experimental,
Morphology, 31)
[2004Zha1] Zhang, Zh-W., Zhou, J.-E., Xi, Sh-Q., Ran, G., Li, P.-L., Zhang, W.-X., “Formation of Crystalline and
Amorphous Solid Solutions of W-Ni-Fe Powder During Mechanical Alloying”, J. Alloys Compd., 370,
186–191 (2004) (Experimental, Morphology, Phase Relations, Calculation, Thermodyn., Kinetics, 35)
[2004Zha2] Zhang, Z.-W., Zhou, J.-E., Xi, S.-Q., Ran, G., Li, P.-L., “Phase Transformation and Thermal Stability of
Mechanically Alloyed W-Ni-Fe Composite Materials”, Mater. Sci. Eng. A, 379A, 148–153 (2004) (Crys.
Structure, Experimental, Kinetics, Morphology, 21)
[2005Mar] Marquis, F.D.S., Mahajan, A., Mamalis, A.G., “Shock Synthesis and Densification of Tungsten Based
Heavy Alloys”, J. Mat. Proc. Tech., 161, 113–120 (2005) (Crys. Structure, Experimental, Mechan. Prop.,
Morphology, Phase Relations, Phys. Prop., 14)
[2006Par] Park, S.J., Martin, J.M., Guo, J.F., Jonson, J.L., German, R.M., “Grain Growth Behaviour of Tungsten
Heavy Alloys Based on the Master Sintering Curve Concept”, Metall. Mater. Trans. A, 37A, 3337–3346
(2006) (Experimental, Calculation, Thermodyn., 63)
[2006Zha] Zhang, Z.W., Chen, G.L., Chen, G., Zhou, J.E., “Amorphization and Thermal Stability of Mechanical
Alloyed W-Ni-Fe”, Mater. Sci. Eng. A, 417A, 34–39 (2006) (Experimental, Phys. Prop., 28)
[2007Lee] Lee, S.-B., Rickman, J.M., Rollett, A.D., “Three-Dimensional Simulation of Isotropic Coarsening in
Liquid Phase Sintering I: A Model”, Acta Mater., 55(2), 615–626 (2007) (Crys. Structure, Experimental,
Kinetics, Mechan. Prop., Thermodyn., 36)
(1990)

Fe–Ni–Zn 17 1
Iron – Nickel – Zinc

Nataliya Bochvar, Lazar Rokhlin
Introduction
The Fe-Ni-Zn phase diagram is of a great importance for galvanizing steels containing Si. The
various alloying elements are added into the molten Zn bath in hot galvanizing. The technol-
ogy of the hot bath galvanizing is widely used for handling most steels. But galvanizing the Si
containing steels remains a technical problem. In general, galvanizing Si in steel gives rise to a
thin, dull grey coating with poor adhesion to the steel substrate. The use of Ni as additive in Zn
bath may decrease the detrimental effects of the silicon. However, the Ni addition to a
galvanizing bath frequently introduces a new type of defect, the entrapment of so-called
“floating dross” particles in the coating. A galvanizing bath is always saturated with Fe, as Fe
constantly dissolves from the galvanized steel articles, and bath essentially becomes a Fe-Ni-Zn
ternary system. Simultaneously, the intermetallic compounds forming in the bath, commonly
referred to as dross particles. Therefore, the study of the Fe-Ni-Zn phase diagram represents a
practical interest.
The Fe-Ni-Zn phase diagram was investigated in a number of works and summarized in
[1987Bha, 2003Rag, 2007Rag] reviews.
A ternary phase of the assumed formula Fe6Ni5Zn89 was reported by [1957Ray].
However, the ternary phase was shown by the later works [1989Per, 1992Reu, 1994Per,
1999Reu] to be an extensive solid solution of the cubic structure closely related to that of
Fe11Zn40.
The nature of phases and phase relations were studied experimentally in the Zn rich part of
the Fe-Ni-Zn system at various temperatures at 700˚C [1940Glu], 370˚C [1957Ray], 450˚C
[1993Che, 1989Per, 1992Reu, 1994Per, 1999Reu, 2000Tan] and 560˚C [2005Pen]. Using the
Calphad method, [2001Tan] calculated the phase boundaries in the Zn rich corner of the
system at 450, 465 and 480˚C, as [1994Per] calculated those at 450 and 480˚C. The experi-
mental studies are summarized in Table 1.
The phase equilibria close to the Zn corner which depict the liquid phase boundary
in equilibrium with solid phases are of importance for galvanizing process. They allow
determining the constitution of floating dross particles at the galvanizing temperatures.
However, there is difference in the description of the equilibria close to the Zn corner
[1994Per, 1995Per, 1995Tan, 1996Tan] which will be debated below in the section “Isothermal
Sections”.
Binary Systems
The Fe-Zn, Fe-Ni and Ni-Zn binary phase diagrams are accepted from [2008Per], [2008Kuz]
and [2008Leb], respectively.

2 17 Fe–Ni–Zn
Solid Phases
A ternary phase of the approximate “formula” of Fe6Ni5Zn89 has been reported by [1957Ray]
to exist in the Zn rich corner of the Fe-Ni-Zn phase diagram. Using microprobe analysis,
[1994Lid] gave an approximate composition as FeNiZn18 and its formula as (Fe,Ni)Zn6.5.
However, no evidence showing conclusively structurally different τ from the Γ2 phase does
exist. On the other hand, [1989Per, 1992Reu, 1994Per, 1999Reu] established the existence of a
continuous series of solid solution between Γ2 phase and Zn89Fe6Ni5 -dross composition at
450˚C. This conclusion was made after examination of the isolated ternary phase annealed
under vacuum at 450˚C by X-ray diffraction method. Its pattern was the same as that of the Γ2
compound and could be indexed into the same fcc crystal lattice system [1989Per]. Comparing
X-ray diffraction results with Mössbauer data, [1999Reu] supposed that Ni atoms occupied Zn
position in the Fe6Ni5Zn89 phase. Also, [1994Lid] proposed that the crystal structure of (Fe,
Ni)Zn6.5 single crystal examined by X-ray analysis is closely related to the Γ2 phase with
the small difference in site occupation. Both structures may be considered as superstructures
of γ-brass. Although [2001Tan, 2005Pen] called it a true ternary phase, all their results show
only that this is an extended solid solution based on the Γ2 phase. Structural investigations of
[2005Pen] did not confirm difference of crystal structures of Γ2 and (Fe,Ni)Zn6.5. The fact that
at 560˚C [2005Pen] observed it only in the ternary system, while it does not exist in the binary
is no evidence for being a true ternary phase. An appearance of a binary phase in the ternary
region at a temperature where the binary phase does not exist itself is quite common case in
ternary systems.
In the present evaluation the “(Fe,Ni)Zn6.5 phase” is accepted to be a part of an extended
solid solution based on the Γ2 phase.
The solubility of Ni in the δ1 and ζ phases of the Fe-Zn system amounts up to 2 and 1 at.%,
respectively, and the Fe solubility in the δ phase of the Ni-Zn system is less than 0.5 at.% at
450˚C [1989Per]. The solid phases of the Fe-Ni-Zn system are listed in Table 2.
The phases Fe3Zn10 and γ of the Ni-Zn system form a continuous solid solution (Γ1).
Based on the metallographic examination of the annealed at 370˚C Zn rich alloys with 0.5Fe-
1.5Ni and 0.75Fe-1.25Ni (mass%), [1957Ray] proposed the ternary compound Fe6Ni5Zn89 (in
fact Γ2) to be formed by a peritectic reaction from the liquid and ζ phases. However, such a
peritectic reaction is not possible because according to [2005Pen] Γ2 is stable at the tempera-
ture of 560˚C that is higher than that of the ζ phase formation. Taking into account the phase
equilibria at 560˚C and a schematic liquidus surface (Fig. 1), an invariant four-phase reaction
of the Γ2 formation L + δ1 + Γ1 Ð Γ2 (560<T<881) seems to be the more likely.
Investigating the structure of the cooled slowly from the liquid state alloys, [1957Ray]
proposed another invariant transition reaction L + τ Ð δ + ζ. [1989Per] reported an invariant
transition reaction: δ + ζ Ð Γ2 + (Zn), later it was confirmed by [1994Per].

Fe–Ni–Zn 17 3
[1957Ray] presented a schematic surface of the primary crystallization fields in the Zn rich
corner up to 3 mass% Fe and 3 mass% Ni with the wide surface of Γ2 and five narrow surfaces
of (Zn), ζ, δ1, δ, γ. The schematic surface of the primary crystallization was presented without
possible directions of the monovariant lines (Fig. 1 is redrawn in at.% and adjusted to the
accepted binary systems).
Isothermal Sections
There are two discrepancies in the description of the liquid phase boundaries and phases in
equilibrium with liquid in the Zn rich alloys at the ordinary temperature of the galvanizing
process 450˚C. [1995Per] believed for the liquid in equilibrium with ζ a constant solubility of
Fe (0.039 mass%) which was independent from the Ni content in the liquid. On the other
hand, [1995Tan, 1996Tan] based on the [1993Che] results and own experiments indicated the
Fe solubility to decrease from 0.029 mass% at 0% Ni to 0.021 mass% at 0.061 mass% Ni for the
equilibrium of the liquid and ζ phases. A further increase in Ni to 0.10 mass% lowered the Fe
solubility limit to 0.016 mass%. These results are confirmed by [2000Tan] and are accepted in
the [2003Rag] review and in this assessment.
The other difference concerns the equilibrium of δ1 with liquid at 450˚C. Interpreting the
[1993Che]’s results, [1995Tan, 1996Tan] proposed an equilibrium of the δ1 phase with the
molten Zn, whereas [1993Che] gave the equilibria only between L and ζ; L, ζ and Γ2; L and Γ2.
On the other hand, [1995Per] indicated that no experimental evidence existed for the
equilibrium of the δ1 phase with the liquid in the Zn rich corner. Only one layer (ζ) or two
layers (ζ + Γ2) were found between the δ1 phase and the Zn rich liquid in the galvanizing bath.
The ζ - Γ2 equilibrium prohibited any tie line between δ and the liquid phase. These data
agreed with the phase equilibria at 370˚C [1957Ray]. New results of [2001Tan] also are in line
with those of [1994Per].
The isothermal sections at 450˚C shown in Figs. 2 and 3 after [2003Rag] who redrawn
them from [1989Per, 1994Per] (Fig. 2) and from [2001Tan] (Fig. 3). Here they are slightly
modified to correspond with the accepted binary systems. The difference between the two
sections is that in Fig. 2 a continuous solid solution Γ2 exists, whereas in Fig. 3 the solution is
broken and Γ2 appears ones again (Γ2’) in the ternary region. [2003Rag] proposes that this
result could be interpreted as a miscibility gap existing at 450˚C rather than the existence of a
true ternary compound. The continuous solid solution is apparently metastable (Fig. 2) and
breaks up into two phases of different compositions (Fig. 3) with the much-longer annealing
times (15 days) used by [2001Tan], as compared with 30 min used by [1989Per, 1995Per].
However, [2001Tan] believes that in the Zn rich corner the ternary phase with a not fixed
stoichiometry exists indeed and has an appreciable homogeneity range. The limits of its
homogeneity range at 450˚C change from 2.1 to 8.7 at.% Ni and from 14.1 to 4.1 at.% Fe,
respectively. The phases being in equilibrium with molten Zn are identical in [1989Per] and
[2001Tan]: ζ, Γ2 (or T) and δ.
Figure 4 shows a partial isothermal section at 560˚C based on [2005Pen] and adjusted to
the accepted binary diagrams. The Γ2 phase has a homogeneity range from 3.2 to 9.1 at.% Ni
and from 10.8 to 4.1 at.% Fe, respectively.

4 17 Fe–Ni–Zn
The Fe solubility in the liquid Zn phase is much higher at 560˚C then at 450˚C, and
decreases substantially with increasing Ni content in the liquid. In contrast, the reduction of
the Fe solubility in the liquid Zn with Ni addition is relatively insignificant at 450˚C.
[2000Tan] constructed experimentally the liquid-phase boundaries of the Fe solubility
at 450, 465 and 480˚C and [1993Che] constructed those at 450˚C. [1993Che] found that for
Ni <0.06 mass% in the bath only the ζ phase was formed. The Ni content of the ζ phase was
relatively constant at ~0.5 mass% for the bath Ni contents of (0.03 to 0.06) mass%. For
Ni >0.06 mass% in the bath a second phase Γ2, containing ~3 mass% Ni, started to appear.
For Ni ≈ (0.06 to 0.09) mass% in the bath the ζ and Γ2 phases could co-exist.
[2001Tan] presented a thermodynamic assessment of the Zn rich corner of the Fe-Ni-Zn
phase diagram, deriving the ternary interaction parameters and calculated isothermal sections
at 450, 465 and 480˚C. They are presented in Fig. 5. The experimental results of [1993Che,
2000Tan] agreed with the calculation very good. The tie triangles (broken lines in Fig. 5) were
added by [2003Rag] approximately and did not take into account the possible presence of the
δ phase in equilibrium with liquid above 450˚C.
Thermodynamics
A thermodynamic description of dross formation in the Ni-Zn bath with galvanizing steel was
made by [1994Per]. The Gibbs energies of the alloy Fe0.06Ni0.89Zn0.05 was ΔfG = –6638 J·mol–1
at 450˚ and ΔfG= –6329 J·mol–1 at 480˚C. The change of the Gibbs energies with the
temperature could be calculated by the equation: ΔfG = –1036 – 8.5407 T J·mol–1.
Using the Mössbauer effect, [1991Doo] studied the microscopic magnetic properties of cubic
microwave ferrite (Zn0.41Ni0.59)Fe2O4.
Miscellaneous
[1997Ana] investigated the stability of the Fe-Ni-Zn coatings during heat treatments up to
400˚C, using microscopic studies. They established the electrocatalytic activity of Fe-Ni-Zn co-
deposits to depend on electrodeposition and surface topography parameters.
Studying the X-ray magnetic circular dichroism, the Fe-ion distribution in crystal lattice of
the spinel ferrite Fe2.01Ni0.48Zn0.51 was established [2002Pat].
[2005Hwa] synthesized the ferrite with the chemical formula of Fe2Ni0.5Zn0.5O4 and
investigated the homogeneity range of the precursor and reproducibility of the as-synthesized
product by elementary analysis and other analyses. The reaction mechanism was also studied
using thermal and escaping gas analyses.

Fe–Ni–Zn 17 5
. Table 1
Investigations of the Fe-Ni-Zn Phase Relations, Structures and Thermodynamics
[1940Glu] Diffusion experiment, Fe-Ni alloys Composition of Fe-Ni alloys changing

dissolved in liquid Zn bath. across 10 mass%. Phase composition of
X-ray and chemical analyses, diffusion layers.
microstructure examination, hardness
measurement
[1957Ray] Annealing of cast alloys at 370˚C for 85 Zn rich alloys with Fe and Ni up to 3 mass%.
days followed by quenching or cooling Isothermal section at 370˚C and surface of
slowly. primary separation.
Metallographic examination, X-ray
diffraction, chemical analysis
[1989Per] Diffusion couples obtained with Fe-Ni Zn rich alloys (Zn>80 at.%). Crystal
alloys at galvanizing in (Zn+0.1 at.% Ni) structure and lattice parameter of the Γ2
bath at 450˚C. phase, isothermal section at 450˚C
Electron microprobe analysis, X-ray
diffraction
[1992Reu] Diffusion layers after Fe galvanized in Ni- Ni content in Ni-Zn bath from 0 to 0.13
Zn bath at 450˚C for 8 min. mass%. Determination of phases in
SEM, determination of the fractal equilibrium with liquid in diffusion layers
dimension in dependence from Ni content
[1993Che] Ni was dissolved in Zn molten in low Ni content from 0.024 to 0.102 mass% and
carbon steel bath at 450˚C for 270 h. Dross Fe content from 0.024 to 0.016 mass%.
was periodically removed from coating of Structure and composition of dross
bath and then remelted in a graphite phases. Isothermal section of the Zn-
crucible in electrical furnace at 450˚C for corner at 450˚C
5 h and quenched in water.
Microstructure examination, XRD and EDS
analyses
[1994Lid] The mixture from Fe and Zn was heated in Crystal structure and lattice parameter of
stainless steel ampoules, sealed under Ar, Zn6.5(FeNi) single crystal
heated to 1300 K in 2 h and cooled to
room temperature at a rate of 30 K/h.
X-ray and electron microprobe analyses
[1994Per] Fe was galvanized in a (Zn-0.1 mass% Ni) Zn rich corner. Determination of phases in
bath at 450 and 480˚C for 30 min. equilibrium with liquid. Calculation of
Electron microprobe analysis, liquidus at 450 and 480˚C
thermodynamic calculation
[1999Reu] δ1(FeZn10) phase was obtained by Crystal structures of δ1(FeZn10) and
mechanical alloying and phase Zn89Fe6Ni5 Fe6Ni5Zn89
was obtained in galvanizing bath. XRD
method, Mössbauer spectra

6 17 Fe–Ni–Zn
[2000Tan] Zn bath with the submerged samples was Liquid phase boundaries in the Zn rich
heated at 600˚C for 3 h, then at 450, 465 region at 450, 465 and 480˚C
and 480˚C for 40h and quenched in water.
Microstructure examination, atomic
absorption spectrophotometry
[2001Tan] The powder of pure Fe, Ni, Zn were sealed Zn rich alloys from 2 to 16 at.% Fe and
in an evacuated quartz tube, heated to from 2 to 11 at.% Ni. Calculation of the
above its estimated liquidus temperature, isothermal sections at 450 and 480˚C and
kept for 2 days and quenched in water. liquidus at 450˚C
Optical and scanning electron
microscopes and SEM-EDS analysis.
Thermodynamic calculation
[2005Pen] The powders of pure Fe, Ni, Zn were Zn rich alloys from 2 to 16 at.% Fe and
sealed in an evacuated quartz tube, from 2 to 11 at.% Ni. Isothermal section at
heated to above its estimated liquidus 560˚C
temperature, kept for 2 days and
quenched in water. Then the annealing at
560˚C for 21 days and quenching in water.
SEM, EDS, X-ray diffraction
. Table 2
Pearson
Symbol/
γ, (γFe,Ni) cF4 continuous solid solution in Fe-Ni.

Fm3m
(Ni) Cu a = 352.4 pure Ni at 25˚C [V-C2, Mas2]
< 1455 Dissolves up to 39.4 at.% Zn at 1040˚C in Ni-Zn
[2008Leb].
(γFe) a = 364.67 pure Fe at 915˚C [V-C2, Mas2]
1394 - 912 Dissolves up to 6 at.% Zn in Fe-Zn [2008Per]

Fe–Ni–Zn 17 7
Pearson
Symbol/
α, (αδFe) cI2
Im3m
(δFe) W a = 293.15 pure Fe at 1390˚C [V-C2, Mas2].
1538 - 1394 Dissolves up to 42 at.% Zn at 782˚C in Fe-Zn,
[2008Per]
Dissolves up to 3.8 at.% Ni at 1517˚C in Fe-Ni
[2008Kuz].
(αFe) a = 286.65 pure Fe at 25˚C [Mas2]. Dissolves 4.6 at.% Ni at
< 912 495˚C [2008Kuz]
(Zn) hP2 a = 266.50 pure Zn at 25˚C [Mas2]
< 419.58 P63/mmc c = 494.70
Mg
γ’, FeNi cP4 63 to 85 at.% Ni [2008Kuz]
< 517 Pm3m a = 355.23
AuCu3
Γ1 cI52 continuous solid solution.
Im3m
Fe3Zn10 Cu5Zn8 a = 899 ~75.5 to 79 at.% Zn [2008Per]
< 782
γ, Ni-Zn a = 893.57 70 to 77 at.% Zn [2008Leb]
< 881
Γ2, Fe1–xNixZny cF408 at 450˚C [1994Per]:
F43m at y ≈ 0.93 0.023 < x ≈ 0.045
Fe11Zn40 at x ≈ 0.103 y ≈ 0.87
at 560˚C [2005Pen]:
at x ≈ 0.09 y ≈ 0.87
at x ≈ 0.036 y ≈ 0.906
at x ≈ 0.03 y ≈ 0.863
a = 1808.38 [1994Lid]
a = 1800 [1989Per]
a = 1801.7 [1999Reu]
Fe11Zn40 a = 1796.3 at x = 0 ~0.658 < y < 0.81 [2008Per]
< 550 a = 1798.6
δ1, FeZn10 hP550 86 to 92.5 at.% Zn, [2008Per]
< 672 P63mc a = 1283
FeZn10 c = 5770
ζ, FeZn13 mC28 a = 1342.4 ~93 to 94 at.% Zn, [2008Per]
< 530 C2/m b = 760.8
CoZn13 c = 506.1
β = 127.3˚

8 17 Fe–Ni–Zn
Pearson
Symbol/
β, NiZn cP2 47.3 to 58.3 at.% Zn

1040 - 675 Pm3m a = 290.83 [2008Leb]
CsCl
β1, NiZn tP4 a = 389.5 45.3 to 58.3 at.% Zn
< 818 P4/mmm c = 321.4 [2008Leb]
AuCu
δ, Ni-Zn mC28 a = 1337.6 89 to 90 at.% Zn
< 490 C2/m b = 751.1 [2008Leb]
CoZn13 c = 762.7

Fe–Ni–Zn 17 9
. Fig. 1
Fe-Ni-Zn. Schematic partial surface of the primary phase separation in the Zn corner

10 17 Fe–Ni–Zn
. Fig. 2
Fe-Ni-Zn. Partial isothermal section at 450˚C

Fe–Ni–Zn 17 11
. Fig. 3

12 17 Fe–Ni–Zn
. Fig. 4

Fe–Ni–Zn 17 13
. Fig. 5
Fe-Ni-Zn. Calculated liquid phase boundaries at 450, 465, 480˚C

14 17 Fe–Ni–Zn
References
[1940Glu] Gluskin, D.Ya., “Phases, Formed by Interaction of Refractory Metals with Light-Melts Metals”, Zh. Tekh.
Fiz., 10(18), 1486–1501 (1940) (Crys. Structure, Experimental, 15)
[1957Ray] Raynor, G.V., Noden, J.D., “A Note on the Zn-Rich Alloys of the System Zn-Fe-Ni”, J. Inst. Met., 86,
269–271 (1957) (Experimental, Crys. Structure, 5)
[1987Bha] Bhan, S., Jain, K.C., Singh, M., “The Iron-Nickel-Zinc System”, J. Alloy Phase Diagrams, 3(1), 31–37
(1987) (Review, Phase Diagram, Crys. Structure, 39)
[1989Per] Perrot, P., In-Wha, C., Reumont, G., Dauphin, J.-Y., “Phase Equilibria in the Zinc Rich Corner of the
Iron-Nickel- Zinc Ternary System”(in French), Compt. Rend. Acad. Sci. Paris, Ser. II, 308, 1413–1417
(1989) (Phase Diagram, Phase Relations, Crys. Structure, 7)
[1991Doo] Dooling, T.A., Cook, D.C., “Magnetic-Field Distributions in Zinc-Nickel Ferrite”, J. Appl. Phys., 69(8),
5352–5354 (1991) (Experimental, Magn. Prop., 4)
[1992Reu] Reumont, G., Perrot, P., Foct, J., “Fractal Evaluation of Liquidus in the Fe-Zn-Ni System at 450˚C”,
J. Mater. Sci. Lett., 11, 1611–1613 (1992) (Experimental, Morphology, Phase Diagram, Phase Rela-
tions, 9)
[1993Che] Chen, Z.W., See, J.B., “Dross Phases Formed in Galvanizing Baths Containing (0-0,1) wt% Nickel
at 450˚C”, ISIJ Int., 33(2), 307–312 (1993) (Experimental, Phase Diagram, Phase Relations, Crys.
Structure, 10)
[1994Lid] Lidin, S., Jacob, M., Larsson A.-K., “(Fe, Ni)Zn6.5, a Superstructure of γ-Brass”, Acta Crys., Sect. C: Cryst.
Struct. Commun., 50C(3), 340–342 (1994) (Crys. Structure, Experimental, 7)
[1994Per] Perrot, P., Reumont, G., “Thermodynamic Description of Dross Formation When Galvanizing Silicon
Steels in Zinc-Nickel Baths”, J. Phase Equilib., 15(5), 479–482 (1994) (Phase Diagram, Phase Relations,
Morphology, Thermodyn., 15)
[1995Per] Perrot, P., Reumont, G., “Authors Reply to- An Alternative Description of Dross Formation When
Galvanizing Silicon Steels in Zinc-Nickel Baths”, J. Phase Equilib., 16(3), 207 (1995) (Abstract, Phase
Relations, 6)
[1995Tan] Tang, N.-Y., “An Alternative Description of Dross Formation When Galvanizing Silicon Steels in Zinc-
Nickel Baths”, J. Phase Equilib., 16(2), 110–112 (1995) (Review, Phase Diagram, Phase Relations, 14)
[1996Tan] Tang, N.-Y., “Accurate Description of Liquid Boundary -A Reply to the Reply by Professors Perrot and
Reumont”, J. Phase Equilib., 17(2), 89–91 (1996) (Review, Phase Relations, 20)
[1997Ana] Ananth, M.V., Parthasaradhy, N.V., “Hydrogen Evolution Characteristics of Electrodeposited Ni-Zn-Fe
Coatings in Alkaline Solutions”, Int. J. Hydrogen Energy, 22(8), 747–751 (1997) (Experimental, Mor-
phology, Thermodyn., 25)
[1999Reu] Reumont, G., de Figueiredo, R.S., Fost, J., “Structural Comparison between the γ2-FeZn4 Compound
Obtained by Mechanical Alloying and the γ2-Fe6Ni5Zn89 Galvanizing Dross”, J. Mater. Sci. Lett., 18,
1879–1882 (1999) (Crys. Structure, Experimental, Phase Relations, 15)
[2000Tan] Tang, N-Y., “Determination of Liquid-Phase Boundaries in Zn-Fe-Mx Systems”, J. Phase Equilib., 21(1),
[2001Tan] Tang, N.Y., Su, X., Toguri, J.M., “Experimental Study and Thermodynamic Assessment of the Zn-Fe-Ni
System”, Calphad, 25(2), 267–277 (2001) (Assessment, Experimental, Phase Relations, Thermodyn., 16)
[2002Pat] Pattrick, R.A.D., van der Laan, G., Henderson, C.M.D., Kuiper, P., Dudzik, E., Vaughan, D.J., “Cation
Site Occupancy in Spinel Ferrites Studied ba X-Ray Magnetic Circular Dichroism: Developing a
Method for Mineralogists”, Eur. J. Mineral, 14(6), 1095–1102 (2002) (Crys. Structure, Experimental, 34)
[2003Rag] Raghavan, V., “Fe-Ni-Zn (Iron-Nickel-Zinc)”, J. Phase Equilib., 24(6), 558–560 (2003) (Review, Phase
[2005Hwa] Hwang, C.-C., Tsai, J.-S., Huang, T.-H., “Combustion Synthesis of Ni-Zn Ferrite by Using Glycine and
Metal Nitrates-Investigations of Precursor Homogeneity, Product Reproducibility, and Reaction
Mechanism”, Mater. Chem. Phys., 93, 330–336 (2005) (Experimental, 28)
[2005Pen] Peng, F., Yin, F., Su, X., Zhi, L., Zhao, M., “560˚C Isothermal Section of Zn-Fe-Ni System at the Zn-rich
Corner”, J. Alloys Compd., 402(1-2), 124–129 (2005) (Experimental, Morphology, Phase Diagram, Phase
Relations, 11)
[2007Rag] Raghavan, V., “Fe-Ni-Zn (Iron-Nickel-Zinc)”, J. Phase Equilib. Diffus., 28(4), 394–394 (2007) (Review,
Phase Diagram, 5)

Fe–Ni–Zn 17 15
[2008Kuz] Kuznetsov, V., “Fe-Ni (Iron-Nickel)”, MSIT Binary Evaluation Program, in MSIT Workplace,
Effenberg, G. (Ed.), MSI, Materials Science International Services, GmbH, Stuttgart; to be published
(2008) (Crys. Structure, Phase Diagram, Phase Realtions, Assessment, #, 41)
[2008Leb] Lebrun, N., “Ni-Zn (Nickel-Zinc)”, MSIT Binary Evaluation Program, in MSIT Workplace, Effenberg, G.
(Ed.), MSI, Materials Science International Services, GmbH, Stuttgart; to be published (2008) (Crys.
Structure, Phase Diagram, Phase Realtions, Assessment, 9)
[2008Per] Perrot, P., “Fe-Zn (Iron-Zinc)”, MSIT Binary Evaluation Program, in MSIT Workplace, Effenberg, G.
(Ed.), MSI, Materials Science International Services, GmbH, Stuttgart; to be published (2008) (Crys.
Structure, Phase Diagram, Phase Realtions, Assessment, 5)
(1990)

Fe–Ni–Zr 18 1
Iron – Nickel – Zirconium

Viktor Kuznetsov
Introduction
The system itself had not attracted much attention, and proper phase equilibria are known
rather poorly. [1968Tar1, 1973Tar] studied phase equilibria in the Zr corner; unfortunately,
these results seem to suffer from oxygen contamination. The review [1992Rag] contains
virtually only three hypothetical sections and data for the solubility of Fe and Ni in Zr.
Recently [1999Vju] has constructed a partial isothermal section at 1000˚C for the Fe-ZrFe2-
Zr2Ni7-Ni region, combining diffusion couple technique and study of equilibrated alloys by
EPMA, XRD and scanning electron microscopy.
On the other hand, the amorphous alloys of the system, which are formed moderately
easily, are considered promising as high-permeability and resistive alloys [1990Sid]. So there
exist a number of studies of their properties [1983Shi, 1983Ino, 1984Shi, 1984Kri, 1987Puz,
1987Sta, 1988Vio1, 1988Vio2, 1993Noh, 1994Zat, 1999Dik, 2005Ham].
Thermodynamic data exist only for the enthalpies of formation of the liquid phase. Those
were measured by [1989Sid, 1993Wan, 1999Thi] along three composition sections. Calcula-
tions of the enthalpy of formation, based on the extrapolation of descriptions of bounding
binaries, were performed by [1990Sid, 1995Tom, 1996Tom] with generally good results.
[1993Wan] tested systematically a number of extrapolation models which all also gave nearly
equally good results. [1985Col] suggested a simple electronic model for the enthalpies of
formation of liquid alloys of transition metals.
The studies of phase equilibria, crystal structures and thermodynamic properties are
summarized in Table 1.
Binary Systems
The Fe-Ni system is accepted from the MSIT evaluation [2008Kuz]. The accepted version of
the Fe-Zr edge, taken from the recent experimental revision of the system [2002Ste], is
presented in Fig. 1. The phase diagram of the Ni-Zr binary is given in Fig. 2. It is based on
[2007Oka], but the temperature of the eutectic L Ð ZrNi + Zr2Ni was changed to 1022˚C,
measured by [2007Wan].
Solid Phases
No ternary compounds were reported. The absence of a mutual solubility of Zr2Fe and Zr2Ni,
claimed by [1968Tar1, 1973Tar], is most probably due to the contamination of their samples
by O and/or N, which leads to the appearance of a phase with the Fe3W3C (cF112) structure
instead of the binary Zr2Fe phase [1972Hav, 1992Rag]. Under oxygen free conditions at 850˚C,
where both Zr2Fe and Zr2Ni are stable, those do form a continuous solid solution [1972Hav].
2 18 Fe–Ni–Zr
The solid solubility of Ni in ZrFe2 at 800 and 1200˚C is about 80 mol% “ZrNi2” [1958Ell].
The smaller value, presented by [1999Vju] in their figure 1a, seems to be inferred by analogy
with the investigated simultaneously Hf-Fe-Ni system, as no experimental data for that region
are provided. Some physical properties of Zr(Fe1–xNix)2 were studied by [1977Mur] (lattice
spaces, Curie temperatures, Mössbauer data) and [1982Osi] (Curie temperature), both for 0 ≤
x ≲ 0.4. Contrary to the statement of [1992Rag], neither [1977Mur] nor [1982Osi] measured
the solubility limit; both found their samples to retain the Laves phase structure for the whole
concentration range studied.
The solubility of Ni and Fe in Zr at 700 and 600˚C is below 0.1 at.% [1973Tar].
The metastable icosahedral quasicrystalline phase was found as a primary precipitation
phase from the supercooled liquid, obtained by heating of an amorphous phase of the
Zr70Fe20Ni10 composition above the glass transition temperature [2000Sai]. At the heating
rate of 0.67 K·s–1 a clear crystallization temperature of 400˚C was observed. It decomposes at
further heating at about 627˚C, giving a mixture of Zr2Fe and Zr2Ni.
Crystallographic data for the stable phases are presented in Table 2.
All the invariant equilibria suggested by [1973Tar] include the “Fe2Zr” phase, which nearly
definitely is oxygen-stabilized [1972Hav, 1992Rag]. Therefore they cannot be accepted here.
Isothermal Sections
A partial isothermal section (solubility of Fe and Ni in the (βZr) phase) at 1100˚C is given in
Fig. 3, based on the results of [1968Tar1]. The authors claim that partial sections obtained for
1200, 1100 and 1000˚C proved to be identical.
Figure 4 presents a partial isothermal section at 1000˚C, based on the results of [1999Vju]
with slight modifications necessary to bring it into agreement with the accepted versions of the
binary systems. In particular, the uncertain equilibria with the Fe3Zr phase, which is not stable
at this temperature, were removed. The solubility of Ni in the ZrFe2(h1) Laves phase is
accepted from [1958Ell].
Figure 5 presents a partial isothermal section (solubility of Fe and Ni in the (βZr) phase)
at 900˚C. It is based on the results of [1973Tar] with the following modifications. Though
EPMA of all their two-phase samples gave only Zr2(Fe,Ni) as the second phase, which
indeed is in agreement with [1972Hav], they arbitrarily inserted a three-phase field (βZr)+
Zr2(Ni,Fe)+Zr2(Fe,Ni). This field, as well as the corresponding kink on the solubility line, were
removed here.
A partial section at 820˚C, presented by [1973Tar], can not be accepted, as it contradicts to
the accepted versions of both Fe-Zr and Ni-Zr binary systems.
The vertical sections presented in [1968Tar1] and [1973Tar] include equilibria with the
“Fe2Zr” phase (different from the Laves phase), which in agreement with [1992Rag] are
considered to be oxygen stabilized. Therefore these sections are not accepted here.

Fe–Ni–Zr 18 3
Thermodynamics
The measured values of the enthalpies of formation of liquid are summarized in Table 3. For
[1989Sid] the approximating equation is given (the table provided in the original work is
indeed calculated from that). For [1993Wan] data from their table 2 are reproduced, and data
of [1999Thi] are presented in Fig. 6, as no tabular data are provided in the original work. There
are several attempts to generalize these fragmentary data and obtain a description for the
whole concentration range using both the polynomial description [1995Tom, 1996Tom] and
the regular associate model [1999Thi], but those seem to be too model-dependent.
[1968Tar2] studied the influence of small (up to ~2 mass%) additions of Fe and Ni on

mechanical and corrosion (in superheated water, CO2 and air) properties of Zr. Corrosivity
in water and CO2 remained essentially the same, whereas the influence on the oxidation
behavior as well as on the strength at room temperature and at 400˚C was favorable.
[1983Ino] and [1992Zhi] studied mechanical properties of partially crystallized amor-
phous alloys.
[1993Pec] investigated stability of precipitates of Zr2(Fe,Ni) in the commercial alloy
Zircaloy-2 under irradiation.
[2005Ham] found nonlinear I-V characteristics of a nanocrystalline mixture of Zr2Ni and
Zr2Fe obtained by annealing of an initially amorphous alloy Fe0.27Ni0.11Zr0.62 at 973K.
Miscellaneous
The concentration dependence of the lattice spaces of the Zr2(Fe,Ni) phase is presented in
Fig. 7 [1972Hav, 1992Rag].
As was noted in the Introduction, amorphous alloys of the system attracted rather much
attention, and a number of their physical properties was measured. [1983Shi, 1984Shi]
measured resistivity in a wide interval of temperatures and pressures. Various magnetic
properties were studied by [1984Kri, 1987Puz, 1987Sta, 1994Zat]. [1988Vio1, 1988Vio2]
studied the relaxation of magnetic properties after irradiation. [1993Noh] investigated relaxa-
tion of the structure during cyclic heat treatment within a stability range of amorphous
alloys (“enthalpy relaxation”). [1999Dik] searched for a correlation between the local structure
of amorphous alloys as determined from Mössbauer data and the products of their crystalli-
zation.
[2001Abr] studied alloys of Zr with stainless steel. They determined phase composition
and stability of alloys during annealing.
[2004Bio] measured structural and magnetic properties of Ni81Fe19/Zr multilayers.

4 18 Fe–Ni–Zr
. Table 1
Investigations of the Fe-Ni-Zr Phase Relations, Structures and Thermodynamics
Temperature / Composition /
Reference Method / Experimental Technique Phase Range Studied
[1958Ell] XRD Section ZrFe2-“ZrNi2”, 800 and

1200˚C
[1968Tar1] Metallography, hardness and microhardness 0.25 to 25 mass% (Fe + Ni), 1200
measurement to 700˚C
[1973Tar] Metallography, XRD, DTA, EPMA, hardness and Zr-Zr2Ni-ZrFe2, 900 to 600˚C
microhardness measurement
[1977Mur] XRD, Curie temperature and magnetization Zr(Fe1–xNix)2, 0 ≤ x ≲ 0.4
measurements, Mössbauer study
[1982Osi] XRD, Curie temperature measurement Zr(Fe1–xNix)2, 0 ≤ x ≲ 0.44
[1989Sid] High-temperature isoperibolic calorimetry Ni1–x(Fe0.67Zr0.33)x, 0 ≤ x ≲ 0.15,
1600˚C, liquid
[1993Wan] High-temperature calorimetry (Fe0.86Ni0.14)-Zr (0 to 0.14 Zr),
1600˚C, liquid
[1999Thi] Levitation alloying calorimetry (NiZr)-Fe, 0 to 0.35Fe, 1619˚C,
liquid
[2000Sai] DSC, TEM, electron microdiffraction, XRD Fe20Ni10Zr70 (initially amorphous),
327˚C to 727˚C
. Table 2
Pearson
Symbol/

1538 - 1394 Im3m
W
< 912 Im3m
W

Fe–Ni–Zr 18 5
Pearson
Symbol/
γ, (γFe,Ni) cF4
(γFe) Fm3m a = 364.67 pure Fe at 915˚C [V-C2, Mas2]
< 1517 Cu
< 1455
(βZr) cI2 a = 360.90 pure Zr at T > 863˚C [Mas2, V-C2]
1855 - 863 Im3m
W
(αZr) hP2 a = 323.16 pure Zr at 25˚C [Mas2]
< 863 P63/mmc c = 514.75
Mg
λ1, Zr cF24 0 < x < 0.8 [1958Ell]
(Fe1–xNix)2 Fd3m C15 structure
MgCu2 a = 705.4 x = 0.1 [1977Mur]
a = 704.2 x = 0.2 [1977Mur]
a = 702.3 x = 0.3 [1977Mur]
a = 700.9 x = 0.4 [1977Mur]
ZrFe2(h1) at x = 0
< 1673 a = 702 to 709 ~27.5 to 34.4 at.% Zr [2002Ste]
a = 701.67 ± 0.06 x = 0; 27.6 at.% Zr [2002Ste]
a = 705.24 ± 0.05 x = 0; 30.8 at.% Zr [2002Ste]
a = 708.75 ± 0.05 x = 0; 34.6 at.% Zr [2002Ste]
λ2, ZrFe2(h2) hP24 26.5 to ~27 at.% Zr [2002Ste]
1345 - ~1240 P63/mmc C36 structure
MgNi2 a = 495.34 ± 0.07 in the alloy Zr25Fe75 (at.%) annealed at 1290˚C for
c = 1614.3 ± 0.3 7.5 h, together with (αFe) and Zr6Fe23 phases
[2002Ste]
a = 498.8 at 1100˚C [V-C2]
c = 1632
Zr3Fe oC16 74.8 to 75.4 at.% Zr
< 851 Cmcm a = 332 [2002Ste]
Re3B b = 1100 in the alloy Zr60Fe40 (at.%) annealed at 700˚C for
c = 882 1000 h, together with the λ1 phase and traces of
the Zr2Fe phase
a = 333 [2002Ste]
b = 1095 at 75 at.% Zr [1991Ard]
c = 882
ZrNi5 < 1300 cF24 a = 670.64 ± 0.06 at 14.85 at.% Zr [1991Nas]
F4m
AuBe5 a = 670.72 ± 0.06 at 18.40 at.% Zr

6 18 Fe–Ni–Zr
Pearson
Symbol/
Zr2Ni7 mC36 a = 469.8 ± 0.9 [1991Nas]

< 1440 C2/m b = 823.5 ± 1.3 dissolves Fe up to gross composition
Ni7Zr2 c = 1219.3 ± 1.6 Zr0.219Fe0.423Ni0.358 [1999Vju]
β = 95.83˚
ZrNi3 hP8 a = 530.9 [1991Nas]
< 920 P63/mmc c = 430.3
Ni3Sn
Zr8Ni21 aP29 a = 647.21 [1991Nas]
< 1180 P1 b = 806.45
Ni21Hf8 c = 858.75
α = 75.18˚
β = 68.00˚
γ = 75.20˚
Zr7Ni10 oC68 a = 1238.6 ± 0.6 at 41.07 at.% Zr [1991Nas]
< 1160 Aba2 b = 915.6 ± 0.5
Ni10Zr7 c = 921.1 ± 0.5
a = 1249.7 ± 0.4 at 43.54 at.% Zr [1991Nas]
b = 921.0 ± 0.5
c = 932.5 ± 0.2
Zr9Ni11 tI40 a = 988.0 ± 0.1 [1991Nas]
1170 - 978 I4/m c = 661 ± 1
Pt11Zr9
Zr oC8 a = 326.8 [1991Nas]
Ni Cmcm b = 993.7
< 1280 CrB c = 410.2
Zr2(Fe1–xNix) tI12,
I4/mmc complete solid solution at 850˚C [1972Hav] C16
CuAl2 structure
Zr2Fe a = 637.3 ± 0.1 at x = 0 in the alloy Zr40Fe60 (at.%) annealed at 800˚
951 - 780 c = 560.4 ± 0.1 C for 500 h, together with the λ2 and Zr3Fe phases
[2002Ste]
Zr2Ni a = 648.3 at x = 1 [1991Nas]

< 1120 c = 526.7 see Fig. 7 for dependence on x

Fe–Ni–Zr 18 7
Pearson
Symbol/
Zr6Fe23 cF116 20.6 to 21.6 at.% Zr; metastable;

(metastable) Fm3m an oxygen-stabilized phase [2002Ste]
Th6Mn23 a = 1172 in the alloy Zr30Fe70 (at.%) annealed at 1000˚C for
200 h, together with the ZrFe2(h2) phase [2002Ste]
a = 1169 [V-C2]
. Table 3
Quantity, per
Temperature mole of atoms
Reaction or Transformation [˚C] [kJ, mol, K] Comments
(1–x) Ni(L) + 0.67x Fe(L) + 0.33x 1600 ΔH = x(1–x) 0 ≤ x ≤ 0.15 high-temperature

Zr(L) = Ni1–xFe0.67xZr0.33x(L) (–96.17–52.86x isoperibolic calorimetry
+233.42x2) [1989Sid]
0.67(1–x) Fe(L) + 0.14(1–x) 1600 ΔH = 1.521 x=0
Ni(L) + x Zr(L) =
Fe0.67(1–x)Ni0.14(1–x)Zrx(L)
ΔH = 2.716 x = 0.013
ΔH = 4.975 x = 0.037
ΔH = 7.252 x = 0.061
ΔH = 9.937 x = 0.092
ΔH = 12.46 x = 0.122
ΔH = 14.60 x = 0.151
ΔH = 16.52 x = 0.178
ΔH = 17.87 x = 0.194
ΔH ± 5% high-temperature calorimetry
[1993Wan]

8 18 Fe–Ni–Zr
. Fig. 1
Fe-Ni-Zr. The Fe-Zr system

Fe–Ni–Zr 18 9
. Fig. 2
Fe-Ni-Zr. The Ni-Zr system

10 18 Fe–Ni–Zr
. Fig. 3
Fe-Ni-Zr. Solubility of Fe and Ni in (βZr) at 1100˚C

Fe–Ni–Zr 18 11
. Fig. 4
Fe-Ni-Zr. Partial isothermal section at 1000˚C. Dashed lines in two-phase regions are tie lines
determined by EPMA

12 18 Fe–Ni–Zr
. Fig. 5
Fe-Ni-Zr. Solubility of Fe and Ni in (βZr) at 900˚C

Fe–Ni–Zr 18 13
. Fig. 6
Fe-Ni-Zr. Enthalpies of formation of the liquid phase from liquid components at 1600˚C on the
section ZrNi-Fe
1 - experimental points,
2 - calculated using regular associated model,
3 - point from [1993Wan] falling to the section

14 18 Fe–Ni–Zr
. Fig. 7
Fe-Ni-Zr. Lattice parameters of the Zr2(Fe1–xNix) solid solution (metastable at room temperature)

Fe–Ni–Zr 18 15
References
[1958Ell] Elliott, R.P., Rostoker, W., “The Occurrence of Laves-Type Phase Among Transition Elements”, Trans.
Am. Soc. Met., 50, 617–632 (1958) (Crys. Structure, Experimental, 27)
[1968Tar1] Tararaeva, E.M., Grigor’ev, A.T., “The Zr corner of the Zr-Fe-Ni System” (in Russian), Fiz.-Khim.
Splavov Tsirkoniya, 107–113 (1968) (Phase Diagram, Experimental, *, #, 7)
[1968Tar2] Tararaeva, E.M., Grigor’ev, A.T., “Corrosional and Mechanical Properties of the Alloys Zirconium-
Iron-Nickel” (in Russian), Fiz.-Khim. Splavov Tsirkoniya, 113–117 (1968) (Experimental, Interface
Phenomena, Mechan. Prop., 7)
[1972Hav] Havinga, E.E., Damsma, H., Hokkeling, P., “Compounds and Pseudo-Binary Alloys with the CuAl2
(C16)-Type Structure”, J. Less-Common Met., 27, 169–186 (1972) (Crys. Structure, Phase Relations,
Experimental, *, 19)
[1973Tar] Tararaeva, E.M., Ivanov, O.S., “The Zr-Fe-Ni Diagram” (in Russian), Stroenie i Svoistva Splavov dlya
Atom. Energ., 131–138 (1973) (Phase Diagram, Phase Relations, Phase Relations, Experimental, *, #, 3)
[1977Mur] Muraoka, Y., Shiga, M., Nakamura, Y., “Magnetic Properties and Mössbauer Effects of A(Fe1–xBx)2
(A = Y or Zr, B = Al or Ni) Laves Phase Inter-Metallic Compounds”, Phys. Status Solidi, 42A, 369–374
(1977) (Crys. Structure, Experimental, Magn. Prop., 15)
[1982Osi] Osipova, L.V., Panteleymonov, L.A., “Magnetic Properties of Fe-Ni-Zr and Fe-Ni-Nb Alloys”, Russ.
Metall., (3), 183–185 (1982), translated from Izv. Akad. Nauk, Met., (3), 205–207 (1982) (Experimental,
Magn. Prop., 8)
[1983Ino] Inoue, A., Tomioka, H., Masumoto, T., “Mechanical Properties of Ductile Fe-Ni-Zr and Fe-Ni-Zr (Nb
or Ta) Amorphous Alloys Containing Fine Crystalline Particles”, J. Mater. Sci., 18, 153–160 (1983)
(Crys. Structure, Experimental, Mechan. Prop., Morphology, 5)
[1983Shi] Shirakawa, K., Fukamichi, K., Kaneko, T., Masumoto, T., “Electrical Resistance of Fe-Zr and Fe-Ni-Zr
Amorphous Alloys Under Hydrostatic Pressure”, Phys. Lett. A, 97, 213–216 (1983) (Experimental,
Electr. Prop., 28)
[1984Kri] Krishnan, R., Rao, K.V., Liebermann, H.H., “Magnetization and FMR Studies in Amorphous Fe90Zr10
and Fe70Ni20Zr10 Ribbons”, J. Appl. Phys., 55, 1823–1825 (1984) (Experimental, Magn. Prop., 16)
[1984Shi] Shirakawa, K., Fukamichi, K., Kaneko, T., Masumoto, T., “Electrical Resistivity Minima of Fe-(Ni, Co)-
Zr Amorphous Alloys”, J. Phys. F: Met. Phys., 14, 1491–1499 (1984) (Electr. Prop., Experimental, 36)
[1985Col] Colinet, C., Pasturel, A., Hicter, P., “A d Band Bonding Model of the Enthalpy of Formation of Ternary
Transition Metal Alloys”, Z. Metallkd., 76, 542–545 (1985) (Calculation, Thermodyn., 33)
[1987Puz] Puzniak, R., Rao, K.V., “Anomalous Temperature Dependence of the Effective Susceptibility Exponent
in Amorphous Fe-Ni-Zr Alloys (Abstract)”, J. Appl. Phys., 61, 4428–4428 (1987) (Abstract, Magn.
Prop., 1)
[1987Sta] Stadnik, Z., Griesbach, P., Dehe, G., Guetlich, P., Miyazaki, T., “Nickel Contribution to the Magnetism
of Fe-Ni-Zr Metallic Glasses”, Phys. Rev. B, 35, 430–432 (1987) (Electr. Prop., Experimental, Magn.
Prop., 27)
[1988Vio1] Violet, C.E., Borg, R.J., Rao, K.V., Noques, J., Taylor, R.D., Batra, A.P., “Temperature Hysteresis and
Relaxation Effects in Amorphous Fe-Ni-Zr Alloys (Abstract)”, J. Appl. Phys., 63, 3398–3398 (1988)
(Abstract, Magn. Prop., 0)
[1988Vio2] Violet, C.E., Borg, R.J., May, L., Rao, K.V., Nogues, J., Taylor, R.D., Batra, A.P., “Magnetic Behavior of
Amorphous Fe-Ni-Zr Alloys and Their Response to Radiation Damage”, Hyperfine Interact., 42,
963–966 (1988) (Electrical Prop., Experimental, 4)
[1989Sid] Sidorov, O.Yu., Esin, Yu.O., Geld, P.V., “Enthalpies of Formation of Zirconium Alloys with Iron,
Cobalt, Nickel, and Copper” (in Russian), Rasplavy, (3), 28–33 (1989) (Calculation, Experimental,
Thermodyn., *, 22)
[1990Sid] Sidorov, O.Yu., Valishev, M.G., Pletneva, E.D., Esin, Yu.D., Geld, P.V., “Enthalpies of Formation of
Nickel-based Ternary Liquid Alloys”, J. Appl. Chem. USSR, 63, 1497–1501 (1990), transl. from Zh. Prikl.
Khim., 63, 1371–1374, (1990) (Experimental, Calculation, Thermodyn., 27)
[1991Ard] Ardisson, J.D., Mansur, R.A., da Silva, E.G., “A Study of Structural and Electronic Properties of the
Alloy Systems (Zr1–xTix)2Fe and (Zr1–xTix)3Fe in the Range 0 ≤ x ≤ 0.2”, Scr. Met. Mater., 25(6),
1327–1331 (1991) (Crys. Structure, Experimental, Electronic Structure, Magn. Prop., 6) cited from
abstract

16 18 Fe–Ni–Zr
[1991Nas] Nash, P., Zayanth C.S., “Ni-Zr (Nickel-Zirconium)” in “Phase Diagrams of Binary Nickel Alloys”,
Nash, P., (Ed.), ASM Intl., Materials Park, OH, 390–394 (1991) (Phase Relations, Crys. Structure,
Assessment, 38)
[1992Rag] Raghavan, V., “The Fe-Ni-Zr (Iron-Nickel-Zirconium) System” in “Phase Diagrams of Ternary Iron
Alloys”, Indian Institut of Metals, Calcutta, 6B, 1094–1098 (1992) (Crys. Structure, Phase Diagram,
[1992Zhi] Zhigalina, O.M., Sosnin, V.V., Glezer, A.M., “Structure and Mechanical Properties of Microcrystalline
Alloys of the System Ni-Fe-Zr”, Met. Sci. Heat Treat., 34, 263–268 (1992), translated from Metallov.
Termich. Obrab. Met., 34, 25–28 (1992) (Crys. Structure, Experimental, Mechan. Prop., Morphology, 7)
[1993Noh] Noh, T.-H., Inoue, A., Fujimori, H., Masumoto, T., “Enthalpy Relaxation and Curie Temperature
Behavior in Fe-(Ni,Co)-Zr Amorphous Alloys”, J. Non-Cryst. Solids, 152, 212–218 (1993) (Experimen-
tal, Phase Relations, 16)
[1993Pec] Pecheur, D., Lefebvre, F., Motta, A.T., Lemaignan, C., Charquet, D., “Effect of Irradiation on
the Precipitate Stability in Zr Alloys”, J. Non-Cryst. Solids, 205, 445–451 (1993) (Experimental,
Morphology, 14)
[1993Wan] Wang, H., Lueck, R., Predel, B., “Thermodynamic Investigation on Liquid Iron-Nickel-Zirconium
Alloys”, J. Phase Equilib., 14, 48–53 (1993) (Experimental, Calculation, Thermodyn., *, 15)
[1994Zat] Zatroch, M., Kovac, J., Rohr, L., Aubertin, F., Gonser, U., “Moessbauer and Magnetic Investigations of
Iron-rich Fe-Ni-Zr Amorphous Alloys”, Phys. Status Solidi B, 184, 499–508 (1994) (Electr. Prop.,
Experimental, Magn. Prop., Thermodyn., 23)
[1995Tom] Tomiska, J., Wang, H., “On the Algebraic Evaluation of the Ternary Molar Heat of Mixing HE from
Calorimetric Investigations”, Ber. Bunsen-Ges. Phys. Chem., 99, 633–640 (1995) (Calculation, Thermo-
dyn., 27)
[1996Tom] Tomiska, J., Neckel, A., “The Margules Concept: The Basis of Modern Algebraic Representations of
Thermodynamic Excess Properties”, J. Phase Equilib., 17, 11–20 (1996) (Calculation, Thermodyn., 23)
[1999Dik] Dikeakos, M., Altounian, Z., Ryan, D.H., Kwon, S.J., “Local Structure in Amorphous Fe-TM-Zr (TM =
Co, Ni, Cu) Studied by Moessbauer Spectroscopy”, J. Non-Cryst. Solids, 250–252, 637–641 (1999) (Crys.
Structure, Electr. Prop., Experimental, 17)
[1999Thi] Thiedemann, U., Roesner-Kuhn, M., Drewes, K., Kuppermann, G., Frohberg, M.G., “Mixing Enthalpy
Measurements of Liquid Ti-Zr, Fe-Ti-Zr and Fe-Ni-Zr Alloys”, Steel Res., 70, 3–8 (1999) (Experimental,
Calculation, Thermodyn., *, 20)
[1999Vju] Vjunitsky, I.V., Abramycheva, N.L., Kalmykov, K.B., Dunayev, S.F., “II. Solid Phase Interaction of
Elements in the Fe-Ni-Zr and Fe-Ni-Nb Systems at 1273 K” (in Russian), Vestn. Mosk. Univ., Ser. 2,
Khim., 40, 179–182 (1999) (Experimental, Phase Relations, *, #, 4)
[2000Sai] Saida, J., Li, Ch., Matsushita, M., Inoue, A., “Nano-Icosahedral Quasicrystalline Phase Formation from
a Supercooled Liquid State in Zr-Fe-Ni Ternary Metallic Glass”, Appl. Phys. Lett., 76, 3037–3039 (2000)
(Crys. Structure, Experimental, Phase Relations, 12)
[2001Abr] Abraham, D.P., Richardson, J.W., McDeavitt, S.M., “Microscopy and Neutron Diffraction Study of a
Zirconium-8 mass% Stainless Steel Alloy”, J. Mater. Sci., 36, 5143–5154 (2001) (Crys. Structure,
Experimental, Morphology, Phase Diagram, Phase Relations, 32)
(2002) (Crys. Structure, Experimental, Phase Diagram, Phase Relations, 88)
[2004Bio] Biondo, A., Nascimento, V.P., Lassri, H., Passamani, E.C., Morales, M.A., Mello, A., Biasi, R.S., Baggio-
Saitovitch, E., “Structural and Magnetic Properties of Ni81Fe19/Zr Multilayers”, J. Magn. Magn. Mater.,
277, 144–152 (2004) (Crys. Structure, Experimental, Magn. Prop., Morphology, 22)
[2005Ham] Hamed, F., “Nonlinear I-V Characteristics Observed in Annealed Ni-Fe-Zr Metallic Glass”, Physica B,
[2007Oka] Okamoto, H., “Ni-Zr (Nickel-Zirconium)”, J. Phase Equilib. Diff., 28, 409 (2007) (Phase Relations,
Phase Diagram, Review, *, #, 3)
[2007Wan] Wang, N., Li, Ch., Du, Z., Wang, F., “Experimental Study and Thermodynamic Re-assessment of the
Ni-Zr System”, Calphad, 31, 413–421 (2007) (Experimental, Assessment, Calculation, Phase Relations,
Phase Diagram, Thermodyn., *, 30)
Structure, Phase Diagram, Phase Realtions, Assessment, #, 41)

Fe–Ni–Zr 18 17
(1990)

Fe–O–Pb 19 1
Iron – Oxygen – Lead

Introduction
Ferrites, non-metallic solid magnetic materials, are the complex compounds of the iron oxide
Fe2O3 with oxides of other metals by their chemical compositions. By their magnetic proper-
ties the ferrites are the analogues of ferromagnetics but they possess lower densities and lesser
losses on the eddy currents. That’s why ferrites are widely used in radio engineering, electron-
ics and super high frequent technology productions. With a view to optimization of alloys
compositions selection for preparation of ferrites information about phase relations in the
corresponding ternary and multicomponent systems is of a great importance. Among these
systems the Fe-O-Pb system plays a considerable role, but information concerning phase
relations is quite scanty. It is presented in literature by a partial isobaric section in air
[1984Sha], the solubility of lead in liquid iron in the presence of oxygen [1995Li] and the
constitution of the PbO-Fe2O3 temperature-composition section [1955Coc, 1957Ber,
1960Mar, 1962Mou, 1978Mex, 1984Sha, 1986Nev]. Phase contents of the alloys and crystal
structures of the identified intermediate phases were studied by [1928Joh, 1938Ade, 1955Coc,
1957Ber, 1960Mar, 1962Mou, 1978Mex, 1984Sha, 1986Nev, 1988Ara, 1997Dor, 1998Cla,
1998Hua, 2000Dia, 2001Dia, 2002Car, 2002Mar, 2003Cas, 2004Dia, 2005Pal]. Data on ther-
modynamic properties were experimentally obtained by [1986Nev] and [1995Li]. The applied
experimental methods as well as the studied temperature and composition ranges are pre-
sented in Table 1. Literature information concerning the Fe-O-Pb system was reviewed in
[1989Rag]. Further determination of the phase equilibria character is necessary, in particular,
on the constitution of the temperature-composition sections formed by Fe2O3 with lead
oxides Pb3O4, Pb12O17, Pb12O19 and PbO2.
Binary Systems
Phase diagrams of the Fe-O and Fe-Pb systems are accepted from [Mas2]. The constitution of
the O-Pb system is accepted on the basis of [1998Ris] assessment (Fig. 1).
Solid Phases
Crystallographic data about known unary, binary and ternary phases are compiled in Table 2.
Compositions of the all reported ternary phases lie along the PbO-Fe2O3 section. Existence
of the τ1, τ2 and τ3 phases was established certainly during both crystal structures and
phase relations studies. In particular, data about the τ1 phase were reported by [1955Coc,
1957Ber, 1962Mou, 1978Mex, 1984Sha, 1986Nev], about the τ2 phase - by [1928Joh, 1957Ber,
1960Mar, 1962Mou, 1984Sha, 1986Nev], as well as concerned the τ3 phase - by [1938Ade,

2 19 Fe–O–Pb
1957Ber, 1960Mar, 1962Mou, 1978Mex, 1984Sha, 1986Nev, 1997Dor, 1998Cla, 2000Dia,

2001Dia, 2002Mar, 2003Cas, 2004Dia, 2005Pal]. Also information about the τ4 and τ5 exis-
tence was presented by [1955Coc], but later it was shown by [1962Mou] that the τ2 and τ3
phases possess homogeneity ranges covering the compositions of the τ4 and τ5 phases.
Data about the existence of the τ6 and τ7 phases ([1960Mar] and [1978Mex, 1999Hsu],
respectively) were not confirmed by investigations of phase relations along the PbO-Fe2O3
temperature-composition section [1984Sha, 1986Nev].
On the basis of a dissociation process studies it was established by [1984Sha] that equilibria
with the participation of the following phases take place: L + τ2 + τ3 + β at 1315˚C,
L + βPb3O4 + αPbO + τ1 at 455˚C, L + βPb3O4 + τ1 + τ2 at 430˚C and L + βPb3O4 + τ3 + β
at 410˚C. Also equilibria with the participation of the PbOx-based phase with inexact stoichi-
ometry were reported. The character of all the respective invariant reactions is not established.
Phase relations at subsolidus temperatures in the range of compositions adjacent to the PbO-
Fe2O3 section were schematically shown by [1984Sha]. It was established that the βPb3O4
phase takes part in equilibria with the τ1, τ2 and τ3 phases and with the β phase.
Isothermal Sections
The solubility of lead in the liquid iron in the presence of oxygen was studied by [1995Li] at the
temperatures of 1550, 1600 and 1650˚C and various oxygen contents. The obtained depen-
dences are shown in Fig. 2. A rise in lead solubility with increasing oxygen content and
temperature was observed. Using the method of linear regression, the following functions
lg(at.%){Pb} were evaluated as –0.51 + 0.50·{at.% O} ± 0.025 at 1550˚C, –0.43 + 0.67·{at.% O}
± 0.089 at 1600˚C and –0.36 + 0.76· {at.% O} ± 0.038 at 1650˚C.
The PbO-Fe2O3 temperature - composition section being named as quasibinary in many

publications, does not possess quasibinary character on the Fe2O3 side because this phase
melts incongruently in the boundary binary Fe-O system. The section shown in Fig. 3 after
[1989Rag] is based on the data of [1986Nev] in the PbO rich part and [1962Mou] in the Fe2O3
rich side. Another version of the PbO-Fe2O3 phase diagram was constructed by [1984Sha]
on the basis of dissociation curves projections. The character of the phase relations at
low temperatures needs further verification using different physico-chemical experimen-
tal techniques.

Fe–O–Pb 19 3
Thermodynamics
Enthalpies of melting ΔHSmelt of the τ1, τ2 and τ3 phases were calculated by [1986Nev] using
the solution of equations following from the equilibrium conditions of coexisting phases.
These values were obtained as 22.24 kJ·mol–1, 49.92 kJ·mol–1 and 61.67 kJ·mol–1, respectively.
The enthalpies of formation of the τ3 phase from oxides (ΔfH) or from simple substances
(ΔfH298) were calculated by [1992Rez] by approximate methods using the enthalpies of the
change of cation coordination in the formation of the compounds from simple oxides. The
reported values are 37 kJ·mol–1 and –5115 kJ·mol–1, respectively. In the study of lead solubility
in liquid iron, [1995Li] have calculated the activity coefficient f oPb and the interaction
parameter eoPb at the temperatures of 1550, 1600 and 1650˚C (Table 3).
In case Pb is used as heat exchanger liquid in steel tubes of a nuclear reactor, the system is
interesting in case of oxygen contamination of the cooling system producing oxide com-
pounds which are radioactive and may be deposited in cool parts of the tubing system causing
unwanted levels of radiation in the outer parts of the reactor system.
Because of their particular magnetic properties, ferrites, in particular, lead-containing,
find many industrial applications, in the first instance as magneto-electric materials. Informa-
tion concerning investigations of the Fe-O-Pb materials properties is collected in Table 4.
[1957Ber] studied dependence of magnetic energy on the temperature of sintering for alloys
with different PbO:Fe2O3 ratios [1957Ber] and observed a maximum energy values at the
composition PbO-4Fe2O3. The corresponding dependences of the residual magnetic induc-
tion and the coercive force were also constructed by [1957Ber]. Magnetic measurements on
the epitaxial films with the composition Fe12.9PbO22.9 were carried out by [1997Dor]. These
objects exhibit magnetically isotropic behavior in the film plane with magnetic remanence to
saturation magnetization divided by 4π ratio M(r)/M(s) = 88 ± 2.9% and coercive field Hc =
198.94 ± 7.72 kA·m–1. However, the films were anisotropic with respect to the film normal
such that the c crystallographic axis is a magnetically hard direction and all directions
normal to the c axis are magnetically easy. The saturation magnetization (4πM (s)) value for
the films is 0.063 T at room temperature. Magnetic properties of thin films with the com-
position of Fe12PbO19 prepared by deposition on Si\SiO2 and sapphire substrates were
studied by [2000Dia] and [2001Dia], respectively. The influence of the substrate temperature
(550-775˚C) and the oxygen pressure (1-3 mbar) on the magnetic properties during the
deposition was reported by [2000Dia]. The χ type lead hexaferrite films with high saturation
magnetization and high coercive field (302.39 kA·m–1) were grown using a substrate tempera-
ture of 700˚C and a pressure of 3.0 mbar of oxygen, while moderate value of coercive field of
the thin films deposited on sapphire substrate at 700˚C under 3.0 mbar partial pressure of high
purity oxygen was 198,94 kA·m–1 [2001Dia]. The optimum value of coercive field of the
Fe12PbO19 powder obtained by [2004Dia] using modifications to the traditional ceramic route
was 318.31 kA·m–1 at 900˚C. It was concluded that at temperatures higher than 900˚C
the magnetic properties are drastically affected as a consequence of the volatility of PbO.
Phase formation during self-propagating high-temperature synthesis of ferrites was studied
by [2002Mar]. The combustion temperature was 1267˚C, the average front velocity was
9·10–4 m·s–1, the obtained intermediate phases were FeO, Fe3O4 and Fe4PbO7. The value
4 19 Fe–O–Pb
of coercivity was 48 kA·m–1. Results of tunneling magnetoresistance effect studies in the Fe-O-
Pb granular films were presented by [1998Cla, 1999Hsu, 2000Hsu]. The dynamics of the 2b
site in the Fe12PbO19 compound was investigated by [1998Cla] on polycrystalline and oriented
single-crystal samples above the Curie temperature.
. Table 1
Investigations of the Fe-O-Pb Phase Relations, Structures and Thermodynamics
Temperature/
Composition/Phase
[1928Joh] as quoted X-ray diffraction Fe4PbO7

by [1962Mou]
[1938Ade] X-ray Laue and rotation techniques Fe12PbO19
[1955Coc] as quoted optical microscopy The PbO-Fe2O3 section
by [1960Mar] and
[1989Rag]
[1957Ber] X-ray Debye-Scherrer studies, thermal analysis, 875-1275˚C, the PbO-
magnetic steel tester measurements Fe2O3 section
[1960Mar] Thermal analysis, metallography, powder X-ray The PbO-Fe2O3 section
diffraction
[1962Mou] X-ray diffraction (Norelco diffractometer), DTA 600-1400˚C, the PbO-
Fe2O3 section
[1978Mex] Solid state reactions studying, The PbO-Fe2O3 section
thermogravimetry, X-ray diffraction
[1984Sha] Thermobalance, X-ray diffraction The PbO-Fe2O3 section
[1986Nev] DTA, X-ray diffraction, crystal growth studying The PbO-Fe2O3 section
[1995Li] Gas-light Tammann furnace measurements of 1550, 1600, 1650˚C, the
solubility Fe rich corner
[1997Dor] X-ray diffraction (standard and grazing 600˚C, room
incidence), Rutherford back-scattering temperature, the
spectrometry Fe12.9PbO22.9 thin films
[1998Cla] Comparative Fe-57 Mössbauer spectroscopy 477-707˚C, Fe12PbO19
(polycrystalline and oriented single-crystal
samples)
[1998Hua] Method of manufacturing granular films whole range of
compositions
[2000Dia] Pulsed laser ablation deposition 550-775˚C, Fe12PbO19
[2001Dia] Pulsed laser ablation deposition, X-ray 700˚C, Fe12PbO19
diffraction

Fe–O–Pb 19 5
Temperature/
Composition/Phase
[2002Car] Optical microscopy, scanning electron 476˚C, Fe-O-Pb thin

microscopy, electron probe microanalysis, X- layers
ray diffraction, Mössbauer spectroscopy
[2002Mar] Self-propagating high-temperature synthesis, Fe12PbO19
X-ray diffraction, thermal analysis, chemical
analysis, magnetic properties determination,
density measurements, arrested front method
[2003Cas] Laser ablation deposition 700˚C, Fe12PbO19 thin
films
[2004Dia] Mössbauer spectroscopy, X-ray diffraction > 800˚C, Fe12PbO19
[2005Pal] Ceramic method, Rietveld refinement X-ray Fe12PbO19
diffraction
. Table 2
Pearson
Symbol/
(δFe) (h2) cI2 a = 293.15 [Mas2]

1538 - 1394 Im3m
Fe1–x–yPbxOy W x = 0, 0 < y ≤ 2.9·10–4, T = 1528˚C [Mas2]
(γFe) (h1) cF a = 364.67 [Mas2]
1394 - 912 4
Fm3m
Fe1–x–yPbxOy Cu x = 0, 0 < y ≤ 9.4·10–5, T = 1371˚C [Mas2]
(αFe) (r) cI2 a = 286.65 at 25˚C [Mas2]
< 912 Im3m
Fe1–x–yPbxOy W x = 0, 0 < y ≤ 8·10–6, T ≈ 912˚C [Mas2]
(εFe) hP2 a = 246.8 at 25˚C [Mas2]
> 1.3·105 bar P63/mmc c = 396
Mg
(βPb) cF4 a = 495.02 at 25˚C [Mas2]
< 327.502 Im3m
FexPb1–x–yOy Cu x = 0, 0 < y · 10–6, T ≈ 327˚C [Mas2]
y = 0, 0 < x · 2.5·10–4, T ≈ 910˚C [E]

6 19 Fe–O–Pb
Pearson
Symbol/
(αPb) hP2 a = 326.5 at 25˚C [Mas2]

> 1.03·105 bar P63/mmc c = 538.7
Mg
α, Fe1–xOx cF8 x = 0.5126 to 0.5457 [Mas2]
(wüstite) Fm3m
1424 - 570 NaCl a = 430.88 in the alloy Fe48.5O51.5, T = 20˚C [E]
a = 428.00 in the alloy Fe47.2O52.8, T = 20˚C [E]
γFe3O4 (h) cF56 57.1 to 58.02 at.% O [Mas2]
1596 - 580 Fd3m
MgAl2O4 a = 840 [E]
βFe3O4 (r) mC224 - ~57.1 at.% O [Mas2]
< 580 Cc
βFe3O4
αFe3O4 (hp) m*14 - ~57.1 at.% O [Mas2]
> 2.5·10–5 bar
β, Fe2O3 hR30 59.82 to ~60 at.% O [Mas2]
< 1457 R3c a = 503.42 at 600˚C [Mas2, V-C2]
Al2O3 c = 1374.83
ε (Fe-O) c** - metastable; ~51.3 to ~53.5 at.% O [Mas2]; labelled as
“P’ (wüstite)” [Mas2]
η (Fe-O) mP500? - metastable; ~52 to ~54 at.% O [Mas2]; labelled as “P”
P21/m (wüstite)” [Mas2]
κ (Fe-O) hR6 - metastable; 51.3 to 53.2 at.% O [Mas2]; labelled as
R3 “wüstite (low-tempe-rature)” [Mas2]
NiO (l)
λ (Fe-O) cI80 - metastable; ~60 at.% O; labelled as “βFe2O3” [Mas2]
Ia3
Mn2O3
μ (Fe-O) tP60 - metastable; ~60 at.% O; labelled as “γFe2O3” [Mas2]
P43212
ν (Fe-O) m*100 metastable; ~60 at.% O; labelled as “εFe2O3”
a = 1299 [Mas2] [S]
b = 1021
c = 844
β = 95.33˚

Fe–O–Pb 19 7
Pearson
Symbol/
βPbO (h) oP8 50 at.% O, labelled as “PbO-M” [Mas2, 1998Ris]

~887 - ~489 Pbma
or a = 547.6 [1961Lec1]
Pbcm b = 474.3
βPbO c = 587.6
a = 548.9 at T = 27˚C [H]
b = 475.5
c = 589.1
αPbO (r) tP4 50 at.% O, labelled as “PbO-L” [Mas2, 1998Ris]
≲ 489 P4/nmm
αPbO a = 396 [1961Lec2]
c = 501
a = 397.59 at T = 27˚C [H]
c = 502.3
a = 397.2 [1989Rag]
c = 501.8
βPb3O4 (r) tP28 57.1 at.% O, labelled as “Pb3O4-T” [Mas2, 1998Ris]
595 - (–103) P42/mbc
βPb3O4 (r) a = 881.5 at T = 25˚C [S]
c = 656.5
a = 880.6 [1989Rag]
c = 656.4
αPb3O4 (l) oP28 57.1 at.% O, labelled as “Pb3O4-R”
< –103 Pbam [Mas2]
a = 912.4 at T = – 268˚C [1988Wri, 2001Guz]
b = 846.7
c = 656.7
a = 881.89 [1989Rag]
b = 880.68
c = 656.36
γ, Pb12O17 oP28 58.6 at.% O [Mas2, 1998Ris]
361 - < 0 Pmc21? a = 778 [1988Wri, 2001Guz]
b = 1098
c = 1148

8 19 Fe–O–Pb
Pearson
Symbol/
δ, Pb12O19 mP62 61.3 at.% O [Mas2, 1998Ris]

335 - 54 Pc? or P21/c a = 773 in the alloy PbO1.57 [E]
b = 1083
c = 1147
β = 88.77˚
a = 775.3 [S]
b = 1084.8
c = 1150.2
β = 88.93˚
a = 1150 [1988Wri, 2001Guz]
b = 1084.3
c = 777.3
β = 91.08˚
βPbO2 tP6 66.1 to 66.7 at.% O, with a small amount of hydrogen;
251 - < 0 P42/mnm labelled as “PbO2-I” [Mas2, 1998Ris]
TiO2 (rutile)
a = 491 [E]
c = 336
a = 495.5 [S]
c = 338.3
a = 495.56 1988Wri, 2001Guz]
c = 338.67
a = 495.78 [1989Rag]
c = 338.78
αPbO2 (hp) cF12 - metastable;
Fm3m about 66.7 at.% O; contains a small amount of
CaF2 hydrogen; labelled as “PbO2-III” [Mas2]
θ (Pb-O) m** - metastable;
P21 or 21/m 50 at.% O [Mas2]
ρ (Pb-O) o** - metastable;
50 at.% O; labelled as “PbOα” [Mas2]
σ (Pb-O) o** - metastable;
57.1 at.% O [Mas2]
ξ (Pb-O) o** - metastable;
57.1 to 61.1 at.% O; labelled as “PbOn” [Mas2]
ζ (Pb-O) pseudocubic - metastable;
58.6 at.% O [Mas2]

Fe–O–Pb 19 9
Pearson
Symbol/
Δ, Pb2O3, mP20 metastable;

1 bar P21/a 60 at.% O [1961Whi]
hydrostatic a = 781.4 [1988Wri, 2001Guz]
pressure b = 562.5
c = 846.6
R (Pb-O) pseudocubic - metastable;
61.3 at.% O [Mas2]
R’ (Pb-O) m** - metastable;
61.3 at.% O [Mas2]
f (Pb-O) oP12 - metastable;
Pbcn about 66.7 at.% O; contains a small amount of
Nb2FeO6 hydrogen; labelled as “PbO2-II” [Mas2]
* τ1, Fe2Pb2O5 t** a = 779 [1957Ber, 1962Mou]
870 - ~650 c = 1585
a = 780 [1978Mex]
c = 1582
labelled as “δ” [1962Mou]
* τ2, Fe4PbO7 h** a = 1186 [1928Joh, 1962Mou]
880 - 750 c = 4714
labelled as “γ” [1962Mou]
* τ3, Fe12PbO19 hP64 [1938Ade]
~1315 - ~760 P63/mmc a = 588 in the Fe12.9PbO22.9 epitaxial films
c = 2302
a = 512 deposited at T = 600˚C [1997Dor]
c = 2367
a = 588.5 in the Fe12PbO19 thin films deposited at T = 700˚C
c = 2306.6 [2001Dia]
a = 592 [2002Mar]
c = 2322
a = 587 [2002Mar]
c = 2312
labelled as “β” [1962Mou]
* τ4, - - [1955Coc]
Fe10Pb2O17

10 19 Fe–O–Pb
Pearson
Symbol/
* τ5, Fe10PbO16 - - [1955Coc]

* τ6, Fe8PbO13 h** a = 662 [1960Mar]
c = 1019
* τ7, Fe6PbO10 h** a = 591 [1978Mex]
c = 2352
. Table 3
Values of Activity Coefficient and Interaction Parameters Referring to O [1995Li]
T [˚C] % {Pb}Fe-Pb f ˚Pb e˚Pb
1550 0.31 3.23 – 0.50

1600 0.38 2.66 – 0.67
1650 0.43 2.31 – 0.76
. Table 4
Investigations of the Fe-O-Pb Materials Properties
[1957Ber] Magnet steel tester measurements Residual magnetic induction, coercive

force, magnetic energy
[1997Dor] Vibrating sample magnetometer, SQUID Magnetic anisotropy, magnetic
magnetometer static magnetic remanence, coercive field, saturation
techniques magnetization
[1998Cla] Comparative Fe-57 Mössbauer Dynamics of the 2b site
spectroscopy
[1998Hua] Magnetic resistivity measurements Magnetic resistivity
[1999Hsu] Magnetic resistivity measurements Magnetic resistivity
[2000Dia] Saturation magnetization and coercive Saturation magnetization, coercive field
field measurements
[2000Hsu] Tunneling magnetoresistance Tunneling magnetoresistance
measurements

Fe–O–Pb 19 11

field measurements
[2002Mar] Coercive field measurements Coercive field
field measurements

12 19 Fe–O–Pb
. Fig. 1
Fe-O-Pb. The O-Pb phase diagram

Fe–O–Pb 19 13
. Fig. 2
Fe-O-Pb. Lead solubility as a function of oxygen content in liquid iron at 1550, 1600 and 1650˚C

14 19 Fe–O–Pb
. Fig. 3
Fe-O-Pb. Temperature - composition section PbO-Fe2O3

Fe–O–Pb 19 15
References
[1928Joh] Johansson, K., “Mineralogical Communications” (in German), Z. Kristallogr., 68, 87–118 (1928) (Crys.
Structure, Experimental) as quoted by [1962Mou]
[1938Ade] Adelskoeld, V., “X-Ray Studies on Magnetoplumbite, Pb0.6Fe2O3 and other Substances Resembling
“β-Alumina”, Na2O·11Al2O3”, Arkiv Kemi, Mineral. Geol., 12A(29), 1–9 (1938) (Crys. Structure, Experi-
mental, 12)
[1955Coc] Cocco, A., “The Binary System PbO-Fe2O3” (in Italian), Ann. Chim. (Rome), 45, 737–753 (1955) (Crys.
Structure, Phase Relations, Experimental, 4) as quoted by [1960Mar] and [1989Rag]
[1957Ber] Berger, W., Pawlek, F., “Crystallographic and Magnetic Studies of the PbO-Fe2O3 System” (in German),
Arch. Eisenhuettenwes., 28(2), 101–108 (1957) (Crys. Structure, Phase Diagram, Experimental, Magn.
Prop., 10)
[1960Mar] Margulis, E.V., Kopylov, N.I., “The Lead Monoxide-Ferric Oxide System”, Russ. J. Inorg. Chem. (Engl.
Transl.), 5(11), 1196–1199 (1960), translated from Zh. Neorg. Khim., 5(11), 2474–2479 (Crys. Structure,
Morphology, Phase Diagram, Experimental, *, 11)
[1961Lec1] Leciejewicz, J., “Neutron-Diffraction Study of Orthorhombic Lead Monoxide”, Acta Crystallogr., 14(1),
[1961Lec2] Leciejewicz, J., “On the Crystal Structure of Tetragonal (Red) PbO”, Acta Crystallogr., 14(12), 1304
[1961Whi] White, W.B., Dachille, F., Roy, R., “High-Pressure-High Temperature Polymorphism of the Oxides of
Lead”, J. Am. Ceram. Soc., 44(4), 170–174 (1961) (Crys. Structure, Phase Relations, Experimental, 16)
[1962Mou] Mountvala, A.J., Ravitz, S.F., “Phase Relations and Structures in the System PbO-Fe2O3”, J. Am. Ceram.
Soc., 45(6), 285–288 (1962) (Crys. Structure, Phase Diagram, Experimental, #, 11)
[1978Mex] Mexmain, J., Hivert, S.L., “Preparation and Characterization of Lead Ferrites” (in French), Ann. Chim.
(Paris), 3(2), 91–97 (1978) (Crys. Structure, Experimental, Phase Diagram, *, 5)
[1984Sha] Shaaban, S.A., Abadir, M.F., Mahdy, A.N., “The System Pb-Fe-O in Air”, British Ceram. Transact. J.,
83(4), 102–105 (1984) (Crys. Structure, Phase Diagram, Phase Relations, Experimental, *, 7)
[1986Nev] Neviva, M., Fischer, K., “Contribution to the Binary Phase Diagram of the System PbO-Fe2O3”, Mater.
Res. Bull., 21(11), 1285–1290 (1986) (Crys. Structure, Phase Diagram, Thermodyn., Calculation,
Experimental, #, 11)
[1988Ara] Arakcheeva, A.V., Karpinskii, O.G., “Polytypic Relations in the Structures of the Group of Hexagonal
Ferrites. II. Ferrites of Ba, Pb, Sr, K”, Sov. Phys.-Crystallogr. (Engl. Transl.), 33, 381–383 (1988),
translated from Kristallografiya, 33, 646–649 (1988) (Crys. Structure, Theory, 7)
[1988Wri] Wriedt, H.A., “O-Pb (Oxygen-Lead)”, Bull. Alloy Phase Diagrams, 9(2), 106–127 (1988) (Crys. Struc-
ture, Phase Diagram, Review, 174) as quoted by [2001Guz]
[1989Rag] Raghavan, V., “The Fe-O-Pb System”, Ternary Systems Containing Iron and Oxygen, 5, 242–244 (1989)
(Phase Diagram, Review, #, 9)
[1992Rez] Reznitskii, L.A., “Estimate of the Enthalpies of Formation of Compounds with the Magnetoplumbite
Structure MFe12O19 (M = Pb, Sr, Ba) and of Barium Ferrites”, Russ. J. Phys. Chem. (Engl. Transl.), 66(7),
1027–1028 (1992), translated from Zh. Fiz. Khim., 66, 1931–1932 (1992) (Thermodyn., Calculation, 8)
[1995Li] Li, L., Weyl, A., Janke, D., “Solubility of Zn and Pb in Liquid Iron and their Partition Between Liquid
Iron and Selected Steelmaking Slag Systems”, Steel Research, 66(4), 154–160 (1995) (Phase Diagram,
Phase Relations, Thermodyn., Experimental, Kinetics, 19)
[1997Dor] Dorsey, P.C., Qadri, S.B., Grabowski, K.S., Knies, D.L., Lubitz, P., Chrisey, D.B., Horwitz, J.S., “Epitaxial
Pb-Fe-O Film with Large Planar Magnetic Anisotropy on (0 0 0 1) Sapphire”, Appl. Phys. Lett., 70(9),
1173–1175 (1997) (Crys. Structure, Experimental, Magn. Prop.) cited from abstract
[1998Cla] Clark, T.M., Evans, B.J., “Mössbauer Investigation of M-Type Hexaferrites Above Their Curie
Temperatures”, J. Magn. Magn. Mater., 177, 237–238 (1998) (Crys. Structure, Experimental, Magn.
Prop, 5)
[1998Hua] Huang, Y.H., Hsu, J.H., Chen, J.W., Chang, C.R., “Granular Fe-Pb-O Films with Large Tunneling
Magnetoresistance”, Appl. Phys. Lett., 72(17), 2171–2173 (1998) (Crys. Structure, Experimental, Magn.
[1998Ris] Risold, D., Nagata, J.-I., Suzuki, R.O., “Thermodynamic Description of the Pb-O System”, J. Phase
Equilib., 19(3), 213–233 (1998) (Crys. Structure, Phase Relations, Thermodyn., Experimental, 19)

16 19 Fe–O–Pb
[1999Hsu] Hsu, J.H., Huang, Y.H., “Tunneling Magnetoresistance Effect in Fe-Pb-O and Fe-PbO Granular Films: a
Comparison”, J. Magn. Magn. Mater., 203, 94–96 (1999) (Morphology, Experimental, Magn. Prop.)
cited from abstract
[2000Dia] Diaz-Castanon, S., Leccabue, F., Watts, B.E., Yapp, R., “PbFe12O19 Thin Films Prepared by Pulsed Laser
Deposition on Si/SiO2 Substrates”, J. Magn. Magn. Mater., 220(1), 79–84 (2000) (Crys. Structure,
Experimental, Magn. Prop.) cited from abstract
[2000Hsu] Hsu, J.H., Chang, C.R., Huang, Y.H., “Enhancement of Tunneling Magnetoresistance through a
Magnetic Barrier of Granular Fe-Pb-O System”, IEEE Trans. Magn., 36(5), 2815–2817 (2000) (Mor-
phology, Experimental, Magn. Prop.) cited from abstract
[2001Dia] Diaz-Castanon, S., Leccabue, F., Watts, B.E., Yapp, R., Asenjo, A., Vasquez, M., “Oriented PbFe12O19
Thin Films Prepared by Pulsed Laser Deposition on Sapphire Substrate”, Mater. Lett., 47(6), 356–361
(2001) (Crys. Structure, Experimental, Magn. Prop.) cited from abstract
[2001Guz] Guzei, L.S., “O-Pb. Oxygen-Lead” in “Phase Diagrams of Binary Metallic Systems” (in Russian), Lya-
kishev, N.P. (Ed.), Vol. 3, Chapter 1, Mashinostroenie, Moscow, 768–769 (2001) (Crys. Structure, Phase
Diagram, Review, 1)
[2002Car] Carbucicchio, M., Rateo, M., Martini, C., Palombarini, G., Benamati, G., Fazio, C., “Phase
Composition of the Oxidised Layers Grown on Steel Exposed to Liquid Lead at 749 K”, Hyperfine
Interactions, 141(1-4), 403–408 (2002) (Crys. Structure, Phase Relations, Experimental, Transport
Phenomena) cited from abstract
[2002Mar] Martirosyan, K.S., Avakyan, P.B., Nersesyan, M.D., “Phase Formation during Self-Propagation High-
Tempetature Synthesis of Ferrites”, Inorg. Mater. (Engl. Trans.), 38, 400–403 (2002) (Crys. Structure,
Magn. Prop., Phys. Prop., Experimental, 11)
[2003Cas] Castro-Rodriguez, R., Palomares-Sanchez, S., Leccabue, F., Arisi, E., Watts, B.E., “Optimal Target-
Substrate Distance in the Growth of Oxides Thin Films by Pulsed Laser Deposition”, Mater. Lett., 57
(22-23), 3320–3324 (2003) (Crys Structure, Phase Relations, Experimental, Theory, Transport Phenom-
ena) cited from abstract
[2004Dia] Dias-Castanon, S., Faloh-Gandarilla, J.C., Leccabue, F., Albanese, G., “The Optimum Synthesis of High
Coercivity Pb-M Hexaferrite Powders Using Modifications to the Traditional Ceramic Route”, J. Magn.
Magn. Mater., 272, 2221–2223 (2004) (Crys. Structure, Experimental, Magn. Prop.) cited from abstract
[2005Pal] Palomares-Sanchez, S.A., Diaz-Castanon, S., Ponce-Castaneda, S., Mirabal-Garcia, M., Leccabue, F.,
Watts, B.E., “Use of the Rietveld Refinement Method for the Preparation of Pure Lead Hexaferrite”,
Mater. Lett., 59(5), 591–594 (2005) (Crys. Structure, Experimental, 17)
[H] Hansen, M. and Anderko, K., Constitution of Binary Alloys, McGraw-Hill, New York (1958)
[Mas2] Massalski, T.B. (Ed.), Binary Alloy Phase Diagrams, 2nd edition, ASM International, Metals Park,
Ohio (1990)
[V-C2] Villars, P. and Calvert, L.D., Pearson’s Handbook of Crystallographic Data for Intermetallic Phases,
2nd edition, ASM, Metals Park, Ohio (1991)

Fe–O–Si 20 1
Iron – Oxygen – Silicon

Olga Fabrichnaya
Introduction
The Fe-O-Si system has several applications in materials sciences and geology. Silicon is most
commonly used as deoxidizer for molten steel [1952Gok, 1957Fit]. Silicon is also an important
residual alloying element in steels. The extensively studied FeO-Fe2O3-SiO2 system is part of a
slag system [1943Whi] and it is important in silica-brick technology [1989Rag]. Iron silicates
are end members of solid solutions important for understanding of mantle mineralogy and
seismic structure of the Earth. Therefore, elastic properties, thermal expansion and seismic
wave velocities of these minerals were extensively studied by different techniques [2004Fab].
The phase transformations in the FeO-SiO2 system were experimentally studied at high
pressures and temperatures [1967Lin, 1967Aki, 1977Aki, 1980Boh, 1987Yag]. Si, S and O
are possible light elements, which dissolve in Fe-Ni alloys composing the outer core of the
Earth [1989And, 1989Sve, 1991Ito]. Iron alloys and silicates were studied under extreme
pressure and temperature conditions to understand the processes in the mantle and core of
the Earth [1991Ito, 1996Boe]. Experiments in diamond anvil cells and shock-wave studies
enable to study materials at the p, T conditions of the Earth interior and to interpret results of
seismic studies [1989And, 1989Sve, 1991Ito, 2002Che].
In the experimental study of the iron saturated FeO-SiO2 system by [1932Bow, 1939Cro,
1951Sch, 1952Mic, 1955All] the phase diagram was constructed and liquid compositions
(content of FeO, Fe2O3, SiO2) were determined. The silica rich part of this diagram is
characterized by the presence of a miscibility gap in liquid. The invariant equilibrium between
two liquids of different composition and silica was investigated by [1927Gre1, 1927Gre2].
[1939Cro] experimentally studied melting in the FeO-SiO2 system in presence of Fe as well as
in SiO2 crucibles without Fe and demonstrated that in the later case melt consists mainly of
Fe3O4 and SiO2 forming a different series than in presence of Fe. The temperature dependence
of solid phase buffers (univariant equilibria providing constant activity of O) was measured
by different techniques. An electrochemical method (emf) was used by [1981Jac, 1981Sch,
1985Jac, 1987One, 1988One, 1989Jac]. Equilibration with CO/CO2 gas mixtures was per-
formed by [1932Sch, 1946Cir, 1966Sch2], a H2 membrane method was applied by [1978Hew]
and a thermogravimetric method by [1965Val, 1983Mye]. [1948Dar] investigated SiO2 +
Fe3O4+slag and SiO2+Fe2SiO4+slag equilibria at different CO2/CO gas mixtures to deter-
mine melting temperatures. Using data from an earlier study [1932Sch] the phase diagram
log10(pCO2/pCO) vs temperature was constructed by [1948Dar]. An investigation of [1952Mic]
provides information on SiO2+slag and SiO2+Fe3O4+slag equilibria at different oxygen par-
tial pressures and temperatures. Schühmann and Esio [1951Sch] determined the oxygen
partial pressure by recording the CO2/CO ratio in gas phase bubbled through slag in Fe
crucibles. The composition of slag was also analyzed. Distin et al. [1971Dis] carried out oxygen
content measurements in liquid Fe for calculation of the FeO activity in FeO-SiO2 liquid

2 20 Fe–O–Si
equilibrated with liquid iron. Bodsworth [1959Bod] used Fe crucibles and H2/H2O mixtures
to determine the oxygen partial pressure of FeO-SiO2 liquid in equilibrium with metallic Fe.
Schühmann et al. [1953Sch] used a quenching technique to study the liquidus surface in
the FeO-Fe2O3-SiO2 region between 1250 and 1450˚C. Muan [1955Mua] presented liquidus
data at oxygen partial pressures ranging from 10–11 to 1 bar. Turkogan and Bill [1957Tur]
equilibrated melt with CO2/CO gas mixtures at 1550˚C. Their values were used by [1962Tur]
to calculate SiO2, FeO and Fe2O3 activities in melt. Oishi et al. [1982Ois] performed electro-
motive force measurements of slag at 1300˚C. Their data for SiO2+Fe+slag equilibria deviate
from [1951Sch, 1952Mic].
Silicon is the most commonly used deoxidizer for steel. Therefore the equilibrium between
silicon and oxygen in molten iron was studied in many works [1950Hil, 1952Gok, 1961Hsi,
1967Buz, 1969Nov, 1970For, 1974Ark, 1977She, 1981Ave, 2005Shi]. Solubility of oxygen in
Fe-Si melt was recently studied by [2005Shi] in inert atmosphere at 1600˚C. A minimum of the
oxygen solubility at 20 mass% Si was indicated by [2005Shi]. At the same temperature of
1600˚C, [1961Hsi], [1967Buz], [1969Nov] and [1977She] indicated minima at 5-6, 6.8, 3.6 or
3.89 mass% Si, respectively, while [1950Hil, 1952Gok] studied compositions up to 10 and
15 mass% Si, respectively and in both works no minimum was found. [1974Ark] indicated the
presence of a minimum in the solubility curves at 1600-1700˚C. A maximum of the oxygen
solubility at 85 mass% Si mentioned by [2005Shi] is based on thermodynamic calculations.
There is no experimental confirmation of this maximum. An isothermal section at 1600˚C
showing details of the Si and O solubility in the Fe rich corner was constructed in the works
[1952Gok, 1970For]. An assessment of interaction parameters is presented by [1966Sch1,
1974Sig].
The equilibrium between silicon and oxygen in (δFe) in contact with liquid iron has been
studied by [1970Nis] and [1981Fuj]. [1981Fuj] calculated a first-order interaction coefficient
in the δ phase for compositions up to 0.1 mass% Si.
The activities of Si and O in liquid iron alloys were studied by [1967Sch, 1973Vla,
1986Zin] using the emf technique. [1964Tay, 1981Lev] applied the emf method to derive
the Gibbs energy of the Fe2SiO4 (fayalite) phase. Activity of FeO in the FeO-SiO2 system was
measured by a gas equilibration technique [2004Fre]. Ban-ya et al. measured the activity of
FeO at 1400˚C [1980Ban] and the enthalpy of mixing of FeO-SiO2 melts at 1420˚C in Fe
crucibles [1982Ban].
A review of thermodynamic data (enthalpy of formation, entropy and Cp) of the phases in
the FeO-Fe2O3-SiO2 system is presented by [2004Fab]. There are calorimetric data available
for fayalite [1952Kin, 1953Orr, 1982Wat, 1982Rob] and for the high-pressure phases γ-spinel
Fe2SiO4 [1982Wat, 1979Nav, 1989Aka, 2007Yon] and FeSiO3 [1982Wat, 1979Nav]. Thermo-
dynamic data for high-pressure phases were also calculated from phase equilibria for ferrosilite
[1980Boh] and for γFe2SiO4 [1965Aki, 1977Aki, 1979Oht, 1987Yag].
Reviews of experimental data available for the Fe-O-Si system were presented by
[1937Wen, 1943Whi, 1957Fit, 1965Mua, 1989Rag, 2004Fab].
There are several thermodynamic assessments of the Fe-O-Si system [1979Kau, 1980Goe,
1985Bjo, 1993Wu, 1996Sax, 1997Fab, 1997Sel, 1999Rom, 2004Jun1, 2007Jak]. [1979Kau] used
the substitutional solution model for the liquid phase and calculated phase diagrams.
[1997Sel] and [1997Fab] used the ionic liquid model to describe the liquid phase and obtained
very similar results. The difference between these two assessments is in the thermodynamic
parameters selected for the phases and in the additional consideration of high pressure
phases by [1997Fab]. [1980Goe] used the associate model to describe the liquid phase.
Fe–O–Si 20 3
[1985Bjo] described liquid as an ideal solution of three silicate complexes. [1985Sas] used the
model of central atom to calculate activity, enthalpy of mixing and enthalpy of formation of
fayalite. [2002Dav] also assessed this system using the associate model. [1993Wu, 1999Rom]
assessed the FeO-SiO2 system using the quasichemical model. The modified quasichemical
model was also used by [2004Jun1, 2007Jak] to assess thermodynamic parameters in the FeO-
Fe2O3-SiO2 system and to calculate phase diagrams. Jung et al. [2004Jun2] used a modified
Wagner model to calculate deoxidation equilibria in liquid iron for 15 elements including Si.
Experimental and theoretical studies of the Fe-O-Si system are summarized in Table 1.
Binary Systems
The Fe-Si binary system is accepted from [1982Kub]. Si-O is accepted from [1992Hal] based
on an evaluation of [1990Wri]. Polymorphic transformations in SiO2 at high pressures
and temperatures are accepted from [2004Fab]. The phase diagram of the Fe-O system is
accepted from [1991Sun]. The thermodynamic assessment of [1991Sun] gives results very
close to [Mas2].
Solid Phases
The crystallographic data for solid phases are listed in Table 2. Fe and Si have very low
solubility for oxygen, Si has practically no solubility for Fe, while Fe can dissolve up to 25
at.% of Si. The SiO2 binary compound undergoes polymorphic transformations, the order
with increasing temperature is α-quartz, β-quartz, tridymite, crystobalite. Two high pressure
modifications of SiO2 were found experimentally with coesite and stishovite structure. Coesite
forms at a pressure of 3-4 GPa. With the pressure increasing above 9 GPa it transforms to the
more dense stishovite phase with rutile structure. At atmospheric pressure only one ternary
phase Fe2SiO4 (fayalite) is stable, having the olivine structure. However, at pressures of
5-8 GPa fayalite transforms to the spinel structure (γ-spinel), which decomposes to a mixture
of FexO (wüstite) and SiO2 (stishovite) at pressures of about 18 GPa. A crystal structure
investigation of spinel Fe2SiO4, performed by [1990Din], indicates that it has mixed normal-
inverse structure - 37.9% of Si occupy octahedral sites and 18.9% of Fe occupy tetrahedral
sites. A FeSiO3 ferrosilite ternary phase with pyroxene structure forms at 1-3 GPa from
fayalite and SiO2 (β-quartz) [1980Boh]. At high pressures and temperatures an ortho modifi-
cation and two clino modifications of pyroxene were found [1984Sue, 1997Hug, 1997Woo]
(see Fig. 1). According to the phase diagram presented by [1994Hug] a triple point for
ferrosilite composition is placed at 4.6 GPa and a temperature of about 800˚C. [1997Woo]
studied the equilibrium between ortho- and high-clinoferrosilite at 800-1300˚C. [1983Web]
reported high-temperature pyroxenoid FeSiO3 with triclinic structure, synthesized at 2 GPa
and 1250˚C. Ferrosilite decomposes in the range 8-10 GPa to a mixture of γ spinel Fe2SiO4 and
SiO2 (Stishovite). Calculated p-T phase diagrams of SiO2 and FeO-SiO2 systems at high
pressures are presented in [2004Fab] (see Fig. 2 and 3). Transformations between the ortho
and clino modifications of FeSiO3 are not shown in Fig 3, because these two phases were
described as a single phase by [2004Fab] due to lack of thermodynamic data. Several experi-
mental studies [1992Ros, 1997Oht, 1998Ang, 1998Woo, 2000Haz] indicated stability of
spinelloid solid solutions of composition Fe3–xSixO4 (x = 0.28-0.75), which form in the
4 20 Fe–O–Si
Fe3O4-Fe2SiO4 system at pressures of 3-8 GPa. A complete solid solution with γ-spinel
structure is stable in this system above 9 GPa. In this work γ-spinel and Fe3O4 are presented
as different phases because at normal pressure Fe3O4 does not dissolve any Fe2SiO4. According
to [2000Woo] there are three spinelloid polytypes II, III and V (spd II, spd III, spd V) which
differ in the b unit cell parameter. The phase diagram of [2000Woo] at 1100˚C is presented in
Fig. 4. It was also shown by [2000Woo] that a phase Fe7SiO10, previously reported as
metastable [1985Mod], appears in phase assemblages at 5-6 GPa and therefore it is a stable
phase at moderate pressures. The crystal structure of Fe7SiO10 was investigated by [2005Ake]
using TEM and, combining the obtained results with XRD data of [1985Mod], a space group
different from that given by [1985Mod] was determined for this compound.
Quasibinary Systems
The isobaric section of the FeO-Fe2O3-SiO2 system at the oxygen partial pressure of air
approximately is a quasibinary system Fe3O4-SiO2 [1965Mua], because magnetite is stable
phase at this condition. Strictly speaking this diagram is not exactly quasibinary, because the
Fe+2/Fe+3 ratio of Fe3O4 in air slightly changes with temperature. Experimentally this system
was studied by [1927Gre2, 1955Mua]. The results of these experimental studies are summar-
ized in [1959Phi, 1965Mua]. The calculated diagram at oxygen partial pressure of air agrees
well with data of [1965Mua], it is presented in Fig. 5.
A calculated phase diagram of the Fe2O3-SiO2 system [1997Sel] is presented in Fig. 6. In
this calculation the gas phase is suppressed and thus it is hypothetical, as at elevated tempera-
tures all Fe-containing phases decompose into O2 gas and phases with lower O-content.
The miscibility gap in the iron-saturated FeO-SiO2 system was studied by [1927Gre1]. The
phase diagram of the FeO-SiO2 system at iron saturation was experimentally studied by
[1932Bow]. The corresponding calculated phase diagram from [1997Fab] is presented in
Fig. 7a. The Fe2O3 content in the liquid phase is presented in Fig. 7b. Strictly speaking this
diagram is not exactly quasibinary, because metallic Fe is present at some amount.
Kato et al. [1984Kat] investigated melting relations in the Fe2SiO4-FeSiO3 quasibinary part
of the FeO-SiO2 system at pressures of 5, 6 and 9 GPa. Between the fayalite and ferrosilite
compositions a eutectic melting occurs. Ferrosilite was observed to melt incongruently form-
ing liquid and coesite. Phase diagrams at 6 and 9 GPa from [1984Kat] are presented in Figs. 8a
and 8b.
A reaction scheme of the Fe-Fe2O3-SiO2-Si partial system is presented in Figs. 9a to 9c. It is

based on the review of [1989Rag] with some corrections according to [1997Fab]. This scheme
does not include equilibria with the gas phase. Details (temperatures and phase compositions)
of the invariant reactions in the FeO-Fe2O3-SiO2 system calculated by [1997Fab] are presented
in Table 3.
Invariant equilibria at high pressures were determined by [1984Kat]. A eutectic point
LFe Ð Fe2SiO4+FeSiO3 was indicated at an Fe2SiO4 content of 74 mol% and a temperature of
1335˚C at 6 GPa. A eutectic point L Ð γFe2SiO4+FeSiO3 was indicated at 55 mol% Fe2SiO4,
1530˚C and 9 GPa. A peritectic formation of FeSiO3 from liquid and SiO2(Coes) was
Fe–O–Si 20 5
determined at 35 mol% of Fe2SiO4 at 1435˚C at 6 GPa and 15 mol% Fe2SiO4 at 1610˚C and
9 GPa. According to [1967Aki] an invariant point αFe2SiO4-γFe2SiO4-liquid was indicated at
1520˚C and 6.2 GPa, while [1979Oht] placed this point at the same temperature but at a
pressure of 7 GPa.

The liquidus surface projection of the FeO-Fe2O3-SiO2 partial system, calculated by
[1997Fab], is presented in Fig. 10. It agrees well with the experimental data of [1953Sch,
1955Mua]. A schematic liquidus surface of the larger region Fe-Fe3O4-SiO2-Si from [1989Rag]
is presented in Fig. 11 based on calculations performed by [1973Iye].
The Tr = Cr transformation in SiO2 was not taken into account by [1989Rag] and the
corresponding degenerated reactions D1 and D2 at 1471˚C are not shown in the reac-
tion scheme.
Liquidus phase relations at high pressures were established in the works of Lindsley
[1964Lin, 1967Lin], Alimoto et al. [1967Aki], Ohtani [1979Oht] and Kato et al. [1984Kat].
The schematic liquidus relations of the FeO-SiO2 system at high pressures are presented in
Fig. 12, taken from [1984Kat]. [1967Aki] found that both αFe2SiO4 and γFe2SiO4 melt
congruently at pressures up to ~7 GPa. [1979Oht] confirmed congruent melting of
γFe2SiO4 up to 13 GPa, while at pressures above 13 GPa it melts incongruently decomposing
to liquid and stishovite. The phase diagram from [1979Oht] is presented in Fig. 13.
Isothermal Sections
In the work of Schuhmann et al. [1953Sch] isothermal sections of the FeO-Fe2O3-SiO2 partial
system were constructed based on experimental phase equilibrium studies at 1250, 1300, 1350,
1400, 1450˚C. Isothermal sections at lower temperatures (1000˚C and 25˚C) are constructed by
extrapolations. [1982Ois] constructed a partial isothermal section at 1300˚C from emf mea-
surements. [1997Sel] and [1997Fab] calculated isothermal sections at 1300 and 1450˚C, which
are in reasonable agreement with data of [1953Sch, 1982Ois], although the experimental
solubilities of FeO and Fe2O3 in liquid at 1300˚C are slightly higher than the calculated
ones. The isothermal sections at 1300 and 1450˚C from [1997Fab] are presented in Figs. 14a
and 14b.
The isothermal section of the iron rich corner of the Fe-O-Si system at 1600˚C showing
details of solubilities at SiO2 saturation is shown in Fig. 15 according to [1989Rag].
Potential Diagrams
The potential diagram log10(pCO2/pCO) vs temperature was constructed by Darken [1948Dar]
including his own experimental results and results from other studies. The value of log10(pCO2/
pCO) is directly related to the partial pressure of oxygen at the temperature given. Figure 16
presents a diagram of this type, log10(pCO2/pCO) vs T, of the FeO-SiO2-O2 partial system,
calculated by [1997Fab]. It agrees very well with the diagram of [1948Dar] and with results of
[1932Sch, 1946Cir, 1952Mic, 1951Sch, 1927Gre2, 1966Sch2]. The potential diagram for
6 20 Fe–O–Si
equilibrium between liquid and silica, calculated at 1250, 1300 and 1350˚C is presented in
Fig. 17. This diagram demonstrates that the content of Fe2O3 in slag equilibrated with SiO2 at
fixed partial pressure of oxygen does not depend on the temperature in the calculated
temperature region. The calculated diagrams agree well with the experimental data of
[1952Mic, 1982Ois].
Thermodynamics
The reaction of dissolution of silicon and oxygen in liquid iron was studied in many works
[1950Hil, 1952Gok, 1961Hsi, 1967Buz, 1969Nov, 1970For, 1974Ark, 1977She, 1981Ave,
2005Shi]. The thermodynamic treatment of experimental results is based on the following
reaction: SiO2(s)=[Si]+2[O], where symbols in square brackets are concentrations of compo-
nents in liquid Fe expressed in mass%. This equilibrium was thermodynamically treated by the
mass action law expressing the product of activities of O and Si in Fe melt by an equilibrium
constant [1952Gok] (corrected in [1953Chi]), 1967Buz, 1969Nov, 1973Iye, 1974Sig, 1977She,
1981Ave, 1986Zin, 1999Ma, 2005Mik, 2005Shi]. The first-order interaction parameters at
1600˚C recommended by [1974Sig] are eSiO= – 0.131, eOSi= – 0.23, eOO= – 0.20, eSiSi= 0.11.
A modified Wagner formalism taking into account the formation of SiO associates was used by
[2004Jun2] to calculate deoxidation equilibria in liquid iron at 1550-1650˚C. [1998Lee] used
the ionic liquid model to describe deoxidation equilibria in liquid iron at 1600˚C. Calculated
solubilities of O and Si in liquid Fe at 1545, 1600 and 1650˚C from [1997Sel] are presented in
Fig. 18. The results are in good agreement with [1952Gok].
The activities of Si and O in liquid iron alloys were studied by [1967Sch, 1973Vla,
1986Zin] using the emf technique. The emf method was used to derive the Gibbs energy of
formation of Fe2SiO4 (fayalite) in the works of [1964Tay, 1981Lev]. The activity of FeO in the
FeO-SiO2 system was measured by gas equilibration technique [1951Sch, 1959Bod, 1980Ban,
2004Fre]. Vapor pressure measurements were performed by [1971Dis] to determine FeO
activities at high temperatures. Calculated FeO activities at 1263, 1315, 1364, 1407˚C from
[1997Fab] are presented in Fig.19a. They agree well with [1951Sch, 1959Bod]. Calculated FeO
activities at 1785, 1880 and 1960˚C are presented in Fig. 19b. They reproduce the experimental
data of [1971Dis] within the uncertainty limits. Calculations of FeO activities in liquid,
performed in the present evaluation using the thermodynamic database of [1997Fab] show
reasonable agreement with data of [2004Fre] at 1550 and 1600˚C.
Ban-ya et al. [1982Ban] measured enthalpies of mixing of FeO-SiO2 melts in Fe crucibles
at 1420˚C. The calculated enthalpy of mixing of FeO-SiO2 melts in equilibrium with metallic
Fe from [1997Fab] is presented in Fig. 20.
A review of experimental data for thermodynamic values H, S and Cp for phases in the
FeO-Fe2O3-SiO2 system is presented by [2004Fab]. There are calorimetric data available
for the enthalpy of formation of fayalite [1952Kin], entropy derived from adiabatic calori-
metry measurements [1982Rob], enthalpy of fusion obtained by drop calorimetry [1953Orr,
1984Ste], enthalpy increment obtained by drop calorimetry [1953Orr] and heat capacity
measurements by differential scanning calorimetry [1982Wat]. For the high-pressure
phases γ-spinel Fe2SiO4 the enthalpy of transformation was obtained by solution calori-
metry [1979Nav] and drop calorimetry [1989Aka], entropy was derived from adiabatic
calorimetry data [2007Yon] and heat capacity was obtained by differential scanning calori-
metry [1982Wat]. Enthalpy of formation of ferrosilite FeSiO3 was obtained by solution
Fe–O–Si 20 7
calorimetry [1979Nav] and heat capacity was measured by differential solution calorimetry
[1982Wat]. The thermodynamic data for high-pressure phases were also calculated [1997Fab]
using available phase equilibria and calorimetric data along with equations of state to take into
account pressure contribution to Gibbs energy. In calculations, phase equilibrium data of
[1980Boh] were used for ferrosilite and data of [1965Aki, 1977Aki, 1979Oht, 1987Yag] for
γFe2SiO4.
There are several thermodynamic assessments of the whole Fe-O-Si system [1979Kau,
1980Goe, 1985Bjo, 1993Wu, 1997Fab, 1997Sel, 1999Rom, 2004Jun1, 2007Jak] using different
models for the liquid phase. [1979Kau] used the substitutional solution model, [1997Sel] used
the ionic liquid model and [1980Goe, 1985Bjo, 2002Dav] used the associate model. [1993Wu,
1999Rom] assessed the FeO-SiO2 partial system using the quasichemical model. The quasi-
chemical model was also used by [2004Jun1, 2007Jak] to assess thermodynamic parameters in
the FeO-Fe2O3-SiO2 system.
The thermodynamic description of [1997Fab] using the ionic liquid model is recom-
mended in the present work, because it reproduces well experimental data at 1 bar and at high
pressures. Thermodynamic values calculated by [1997Fab] are presented in Tables 4 and 5.
For geophysical applications data like compressibilities, thermal expansions and seismic wave
velocities of Fe-containing silicates are important, measured for example by static compres-
sion, ultrasonic and Brillouin scattering. The bulk elastic modulus and its pressure derivative
are usually derived from static compression experiments. Sound velocities are derived from
Brillouin spectroscopic data. Thermal expansion is usually studied by in-situ XRD measure-
ments. Review papers are devoted to thermal expansion of spinels [1985Tay] and to thermo-
elastic properties of phases in the FeO-Fe2O3-SiO2 system including high-pressure phases
[2004Fab].
Magnetic properties of orthoferrosilite FeSiO3 were determined by susceptibility and
magnetization measurements as well as by Mössbauer spectroscopy [1986Reg]. From these
data the temperature of magnetic ordering was obtained as 40 K. The electric field gradient for
Fe2SiO4 (fayalite) was determined by Mössbauer spectroscopy of a single crystal [2002Lot].
Magnetic properties of spinel and spinelloid structure in the Fe2SiO4-Fe3O4 system were
measured by [2001Yam1, 2004Kon]. Electric properties of spinel solid solutions in the
Fe2SiO4-Fe3O4 system were measured by [2001Yam2]. Magnetic properties of the mineral
iscorite Fe7SiO10 was measured by [1985Mod]. Paramagnetic behavior was found at tempera-
tures above –23˚C, weak ferromagnetism was found at temperatures below –23˚C.
Hardness of oxide scales on Fe-Si alloys is important to determine hot-rolling conditions
for production of outstanding steels. Microhardness measurements on Fe-Si alloys (up to
3 mass% Si) at room temperature and high temperatures were performed by [2006Ama] after
oxidation at 800 and 1000˚C.
Recently attention was focused on synthesis and properties of nanocomposite materials in
the Fe-O-Si system for potential applications in electronics and optics [2006Kim]. The
alternating current electrical conductivity of gel-derived glass of composition 55Fe2O3-
45SiO2 (mol%) was measured by [2006Bas] after reduction at 650˚C and further heat-
treatment in air at 500˚C to grow Fe-core Fe3O4 shell nanostructure, which forms a percolate

8 20 Fe–O–Si
network within silica gel. Magnetic properties of nanocomposite Fe-SiO2 powders were
studied by [2006Kim].
[2003Kap] studied the contact angle of liquid Fe on a SiO2 substrate under Ar and CO-
CO2-Ar atmospheres in the temperature range 1550-1560˚C using X-rays and the sessile-drop
method. The angle was found to be around 135˚. Fayalite slag formed due to reaction between
substrate and Fe was found to accumulate around the drop. The results are of relevance to
explain the mechanism of corrosion of SiO2 containing refractory materials by liquid Fe.
Experimental studies of material properties are presented in Table 6.
Miscellaneous
Conditions for nucleation of oxide particles during deoxidation are reviewed and recent
experimental studies of the nucleation of SiO2 are described by [1972Sig]. The critical
supersaturation is discussed and influence of the rate of mixing of deoxidant addition on
the number of particles of deoxidation products is considered. Several studies are devoted to
internal oxidation of Fe-Si alloys [1960Sch, 1984Tak, 1986Wie1, 1986Wie2, 1986Tak,
2006Tak]. Diffusion coefficients of oxygen in Fe-Si alloys were derived from experimental
data in [1960Sch, 1984Tak, 1986Tak]. [1987Lee] studied initial oxidation of Fe-Si alloys at
25˚C by different kinds of surface spectroscopies. [1976Mor] studied transition from external
to internal oxidation in Fe-Si alloys as function of oxygen partial pressure. [1971Log] studied
morphology and structure of wustite-fayalite scale formed on Fe-Si alloys during oxidation by
CO2/CO gas mixtures at 1000˚C. [1982Rol] studied oxidation and creep of Fe-Si alloys.
[1998Won] reported precipitation kinetics of Fe contamination at a Si-SiO2 interface during
dry oxidation at 900˚C based on TEM and atomic force microscopy.
[1967Eib] investigated crystal structure of fayalite Fe2SiO4 by Mössbauer spectroscopy as
function of temperature. Splitting of lines, which became more pronounced at high tempera-
tures, confirms that Fe+3 occupies both non-equivalent octahedral sites of the fayalite struc-
ture. [1992Bec] investigated fayalite Fe2SiO4 at elevated temperatures by Mössbauer
spectroscopy, also. The pO2 dependent broadening of Mössbauer lines was discussed in context
of fayalite crystal structure. Kinetics of fayalite formation from FeO and SiO2 were investigated
in [1992Bec].
Ross et al. [1999Ros1, 1999Ros2] obtained Raman spectra and electronic absorption
spectra for clinoferrosilite at high pressures. Transformation of low-clinoferrosilite to high-
clinoferrosilite with pressure increase and back with pressure decrease was observed in-situ
[1999Ros1]. [1999Ros2] showed that high FeSiO3 (space group C2/c) gained additional
stabilization energy at high pressure due to crystal field effect of Fe+2 in octahedral sites.
Results of Ito [1991Ito] on interaction between molten iron and silicate at high pressure
and temperature indicate that certain amount of SiO2 dissolves into liquid iron from silicate
melt. These results confirm that Si and O may be important alloying light elements of Earth’s
core if core segregation proceeds in magmatic ocean of the proto-Earth.
[2001Bel] constructed a molecular dynamic model of the FeO-SiO2 system using Born-
Mayer pair potential. The potential includes effective dipole-dipole interaction for Fe-Si pairs
obtained from experimental data for the Gibbs energy of solution.

Fe–O–Si 20 9
. Table 1
Investigations of the Fe-O-Si Phase Relations, Structures and Thermodynamics
[1927Gre1] Phase equilibria in gas furnace, 1700˚C, FeO-SiO2, liquid miscibility gap
temperature control by optical
pyrometry, quenching, microscopic study
[1927Gre2] Melting in electric furnace in air, 1660˚C, FeO-Fe2O3-SiO2, liquid miscibility
temperature measurement by optical gap
pyrometry, chemical analysis
[1932Bow] Phase equilibria in presence of Fe, 1100-1800˚C, Fe-FeO-SiO2
chemical analysis, microscopic study
[1932Sch] Equilibration with CO/CO2 gas mixtures 900˚C, Fe2O3-10SiO2, Fe2O3-SiO2, 3Fe2O3-
SiO2
[1939Cro] Phase equilibria in Fe- and siliceous 1200-1600˚C, Fe-FeO-Fe2O3-SiO2
crucibles, microscopic study, chemical
analysis
[1948Dar] Equilibration with CO/CO2 gas mixtures 900-1600˚C Fe-O-Si log10(PCO2/PCO) in the
range between –2 and 4
[1950Hil] Phase equilibria in SiO2, MgO, Al2O3 1550, 1600, 1650˚C, Fe-Si alloys
crucibles in Ar atmosphere 0.001-10 mass% Si
[1951Sch] Equilibration with CO/CO2 gas mixtures in 1263, 1315, 1364, 1407, FeO-SiO2 (up to
Fe-crucibles, chemical analysis 50 mass% SiO2) in presence of Fe
[1952Gok] Equilibration Fe-O-Si alloys in SiO2 1545-1650˚C, up to 15 at.% Si, H2O/H2 in
crucibles with H2O/H2 gas mixture, the range 0.002-0.326
quenching and chemical analysis
[1952Kin] HF solution calorimetry 25˚C, Fe2SiO4 (fayalite) enthalpy of
formation
[1952Mic] Equilibration with CO/CO2 gas mixtures, 1250, 1300, 1350˚C, FeO-Fe2O3-SiO2
SiO2 crucibles
[1953Orr] Drop-calorimetry 25-1451˚C, Fe2SiO4 (heat content,
enthalpy of fusion)
[1953Sch] Equilibration in Pt-crucibles in nitrogen 1250-1450˚C, FeO-Fe2O3-SiO2
atmosphere, quenching, optical
microscopy
[1955All] Equilibration in Fe crucibles in CO/CO2 1150-1400˚C; FeO-Fe2SiO4 in presence of
gas mixtures, quenching, XRD, optical Fe
microscopy
[1955Mua] Equilibration with CO2/H2, quenching, 1200-1473˚C, p(O2) in the range
XRD, optical microscopy 10–10.9-1 atm, FeO-Fe2O3-SiO2
[1955Sch] Thermodynamic calculations of isoactivity 1350˚C, FeO-Fe2O3-SiO2 (FeO from 40 to
lines 100 mass%, Fe2O3 from 0 to 60 mass%)

10 20 Fe–O–Si
[1957Tur] Equilibration with CO/CO2 gas mixtures, 1550˚C, FeO-Fe2O3-SiO2

chemical analysis after quenching
[1959Bod] Equilibration with H2O/H2 gas mixtures, 1265, 1305, 1365˚C, FeO-SiO2 in presence
chemical analysis after quenching of Fe
[1960Sch] Heat treatment in H2O/H2 and CO/CO2 820-1056˚C, Fe-Si alloys 0.24-1.6 mass% Si
atmosphere
[1962Tur] Calculations of activities of SiO2, FeO, 1550˚C, FeO-Fe2O3-SiO2
Fe2O3 from phase equilibrium data
[1964Lin] Piston-cylinder high-pressure apparatus, 1150˚C, 1.8 GPa; 1400˚C, 4.5 GPa;
XRD Fe2SiO4+SiO2
[1964Tay] EMF 750-1200˚C, Fe2SiO4, Gibbs energy of
formation
[1965Aki] Tetahedral-anvil high-pressure apparatus, 700-1200˚C, 4-7 GPa; Fe2SiO4
XRD
[1966Sch2] Equilibration with CO/CO2 gas mixtures, 1000-1200˚C, solid phase oxygen buffers
XRD, optical microscopy in Fe-O, Fe-SiO2-Fe2SiO4, Fe2SiO4-Fe3O4-
SiO2 systems
[1967Aki] Tetahedral-anvil high-pressure apparatus, 800-1700˚C, 2-7.6 GPa; Fe2SiO4 (α = γ
XRD transition, melting)
[1967Buz] Phase equilibria in SiO2 crucibles in Ar 1600˚C, Fe-Si alloys 0.01-15.5 mass% Si
atmosphere, XRD
[1967Eib] XRD, Mössbauer spectroscopy –193-727˚C, Fe2SiO4
[1967Sch] EMF 1600˚C, Fe-Si alloys equilibrated with SiO2
1.39-3.13 mass% Si
[1969Kul] Thermodynamic calculations of partial 1600˚C, FexO-SiO2
pressures of species in gas phase
[1969Nov] Phase equilibria in SiO2 crucibles, 1600˚C, Fe-Si alloys 0.008-50 mass% Si
chemical analysis
[1970Nis] Equilibrium in Ar atmosphere, chemical 1550˚C, up to 0.07 at.% Si
analysis
[1971Dis] Equilibration of levitated Fe beads with 1785-1960˚C, FeO-SiO2 (in equilibrium
molten FeO-SiO2 slag with Fe) activity of FeO
[1971Log] Heat treatment with CO/CO2 mixture, 1000˚C, Fe-Si alloy, 1.5 mass% Si
optical, electron microscopy, microprobe,
metallography, chemical analysis
[1972Sig] Polarography 1550˚C, Fe-Si (0.48 and 1.17 mass% Si)
[1973Iye] Calculations based on phase equilibria 1200-1730˚C, Fe-Si-O
[1973Vla] EMF 1550-1650˚C, Fe-Si-O melt Si
0.01-2 mass%

Fe–O–Si 20 11
[1974Ark] Equilibration in Ar atmosphere, chemical 1600˚C, Fe-Si alloys 0.008-100 mass% Si

analysis
[1976Mor] Heat treatment in gas mixture H2O/H2, 850˚C, Fe-3 mass% Si
Chemical analysis, IR-spectroscopy
[1977Aki] Cubic-anvil high pressure apparatus, 600-1100˚C, p(GPa) = 3.64+0.0025T(˚C)
in-situ XRD Fe2SiO4 (α = γ transformation)
[1977She] Equilibration in Ar atmosphere, chemical 1600, 1650˚C, Fe-Si alloys 0.01-40 mass%
analysis Si
[1978Hew] Hydrothermal system using hydrogen 650-850˚C, 0.1 GPa, Fe2SiO4+Fe3O4+SiO2
diffusion membrane (QFM) buffer
[1979Kau] Calphad 25-2127˚C, Fe2O3-SiO2, Fe3O4-SiO2,
FeO-SiO2
[1979Nav] Solution calorimetry (2PbO·B2O3 melt), 713˚C, αFe2SiO4, γFe2SiO4, FeSiO3
high pressure synthesis, XRD, microprobe, Enthalpy of transformation and reactions
microscopy, calculations
[1979Oht] Multianvil high pressure apparatus, XRD, 1000-2700˚C, 5-20 GPa, αFe2SiO4,
optical microscopy γFe2SiO4 melting
[1980Ban] Equilibration with H2O/H2 gas mixture in 1400˚C, FexO-SiO2, activity of FexO
iron crucibles
[1980Boh] Piston-cylinder high pressure apparatus, 700-1050˚C, 1-1.6 GPa, FeSiO3
XRD, electron microprobe
[1980Goe] Thermodynamic calculations based on 1100-1400˚C, Fe-FeO-Fe2O3-SiO2
associate model for liquid
[1981Ave] Equilibrium in H2O-H2-Ar mixture in SiO2 1600, 1650, 1700˚C, Fe-Si alloys with
crucibles 0.005-2.32 mass% Si
[1981Fuj] Zone melting technique 1530-1535˚C, δFe-Si alloy up to 0.1 mass
% Si
[1981Lev] EMF 1100-1300˚C, Gibbs energy of formation
of Fe2SiO4
[1982Ban] High-temperature isoperibolic 1420˚C, FexO-SiO2 x(SiO2) from 0 to
calorimetry 20 mol%
[1982Ois] EMF 1200, 1300˚C, SiO2 saturated iron silicate
slag in the range from Fe to Fe3O4
saturation
[1982Rob] Adiabatic calorimetry –268-108˚C, Fe2SiO4 (fayalite)
[1982Rol] XRD, optical and electron metallography 700-800˚C, pO2 = 2·103-1.013·105 Pa, 16 N/
mm2 tensil stress, Fe-Si (1 and 4 mass% Si)
[1982Wat] Differential scanning calorimetry 77-427˚C, α- and γFe2SiO4, FeSiO3
clinopyroxene (heat capacity)

12 20 Fe–O–Si
[1983Kuh] XRD, SEM, IR-spectroscopy, X-ray 850˚C, Fe-Si alloys 10-40 mass% Si
photoelectron spectroscopy
[1983Mye] Thermogravimetric gas mixing furnace, 800-1300˚C, solid phase oxygen buffers
CO2/H2 gas mixtures, oxygen partial in Fe-O, Fe-SiO2-Fe2SiO4, Fe2SiO4-Fe3O4-
pressure measurement with ZrO2 SiO2 systems
electrode, equilibrium control
[1983Web] Piston-cylinder, XRD 1250˚C, 2 GPa, FeSiO3 triclinic structure
[1984Kat] Multianvil high-pressure apparatus, XRD, 1250-1550˚C, 5-9 GPa, Fe2SiO4-FeSiO3
electron microprobe
[1984Ste] Drop calorimetry 712-1432˚C, Fe2SiO4 (fayalite)
[1984Sue] High-temperature XRD, FeSiO3 1050˚C, FeSiO3
hydrothermal synthesis at 800˚C and
2 GPa
[1984Tak] XRD, electron microprobe analysis 950-1050˚C, γ-Fe-Si alloys with 0.07-0.92
mass% Si
[1985Bjo] Calphad, associate model 1100-1900˚C, Fe-FeO-Fe2O3-SiO2
[1985Mod] XRD, electron microprobe analysis 900˚C, Fe7(Si0.94Fe0.06)O10
[1985Sas] Thermodynamic calculations, central 1315-1600˚C, FeO-SiO2
atom model
[1986Tak] XRD, microprobe analysis 800-900˚C, Fe-Si alloys (0.07-0.4 mass%
Si)
[1986Wie1] Light microscopy, SEM, microprobe 1450˚C, Fe-Si alloys (up to 3 mass% Si)
analysis
[1986Wie2] TGA, XRD, microprobe analysis, SEM, IR 850˚C, Fe-Si alloys (0.5-3 mass% Si)
[1986Zin] EMF 1600-1670˚C, 0.043-0.391 mass% Si
(activity Si and O in liquid Fe)
[1987Lee] Surface spectroscopies: Auger Electron 25˚C, Fe-8.75 at.% Si at initial stage of
(AES), Electron Energy Loss (EELS), X-ray oxidation at very low PO2
photoelectron (XPS)
[1987One] EMF 627-1147˚C, Fe+Fe2SiO4+SiO2
627-1147˚C, Fe3O4+Fe2SiO4+SiO2
[1987Yag] Multianvil high-pressure apparatus, in situ 800-1200˚C, 4-6 GPa, Fe2SiO4 α = γ
XRD combined with synchrotron transition
radiation
[1989Aka] H-T solution calorimetry, XRD 702˚C, Fe2SiO4, enthalpy of α = γ
transformation
[1989Jac] EMF 623-1127˚C, Fe+Fe2SiO4+SiO2
807-1067˚C, Fe3O4+Fe2SiO4+SiO2

Fe–O–Si 20 13
[1990Din] XRD 900˚C, 7 GPa (synthesis) of Fe2SiO4

(γ-spinel), crystal structure
[1992Bec] High-temperature Mössbauer 500-1130˚C, pO2 = 5·10–14, αFe2SiO4
spectroscopy
[1992Ros] Multi-anvil high pressure apparatus, 1200˚C, 7 GPa, Fe2SiO4-Fe3O4
microprobe, XRD
[1993Tyu] Thermodynamic calculations 1300˚C, FeO-SiO2 (in presence of Fe), FeO
activity
[1994Hug] Single-crystal X-ray in diamond-anvil cell T = 800-1200˚C, p = 1-8 GPa, FeSiO3
[1994Mat] Thermodynamic calculations 1250˚C, FeO-SiO2 (in presence of Fe), O2
activity
[1996Hug] Piston-cylinder high-pressure apparatus, Synthesis at 1100˚C, 3 GPa; FeSiO3, up to
single crystal XRD in diamond anvil cell, 4.6 GPa
TEM
[1997Fab] CALPHAD assessment, ionic liquid model pressure up to p = 20 GPa and
temperature up to 2000˚C, Fe-FeO-Fe2O3-
SiO2
[1997Hug] Piston-cylinder high-pressure apparatus, 950˚C, 2 GPa, ortho FeSiO3, 1100˚C,
multianvil high-pressure apparatus, XRD 9 GPa, clino FeSiO3, 20-821˚C, unit-cell
parameters
[1997Li] EMF 1550˚C, Fe-2.5 mass% Si under CO2
blowing (activity of O and Si)
[1997Oht] Multi-anvil high pressure apparatus 1200˚C, 4-10 GPa, Fe2SiO4-Fe3O4
[1997Sel] CALPHAD assessment, ionic liquid model p = 105 Pa, temperature up to 2000˚C,
Fe-FeO-Fe2O3-SiO2
[1997Woo] Multi-anvil high pressure apparatus, XRD 800-1300˚C, 5-8 GPa, ortho=high-clino
of quenched samples, TEM FeSiO3 transition
[1998Ang] Belt high-pressure apparatus, single 1200˚C, 4 GPa (synthesis) of Fe2.57Si0.43O4,
crystal XRD, electron microprobe XRD spectra at 25˚C
[1998Lee] Calculation with ionic liquid model 1600˚C, Fe-O-Si alloys with content of Si
(up to 10 mass%) and O (up to 0.1 mass%)
[1998Won] TEM, atomic force microscopy 900˚C, Fe contamination of Si-SiO2
interface
[1998Woo] Piston-cylinder high-pressure apparatus, 1100˚C, 5.6 GPa, Fe2.45Si0.55O4
XRD
[1999Ma] Thermodynamic calculations 1600˚C, Fe-O-Si alloys with content of Si
(up to 0.01 mass%) and O (up to 0.25
mass%)

14 20 Fe–O–Si
[1999Rom] CALPHAD assessment, quasichemical 1000-1800˚C, FeO-SiO2 in presence of Fe.

model
[1999Ros1] Synthesis in multianvil high-pressure 1100˚C, 9 GPa (synthesis), 1.57-175 GPa:
apparatus, XRD, Raman spectra at high low-high clinoferrosilite (FeSiO3)
pressure (diamond anvil cell) transition
[1999Ros2] Synthesis in multianvil high-pressure 1200˚C, 8 GPa (synthesis) FeSiO3, spectra
apparatus, XRD, Mössbauer spectra, measurements from 1 atm to 5 GPa
electronic absorbtion spectra at high
pressure (diamond anvil cell)
[2000Haz] Multi-anvil high pressure apparatus, Synthesis at 6 GPa, 1200˚C, crystal
single crystal X-ray in diamond anvil cell structure study up to 8.95 GPa, Fe2SiO4-
Fe3O4
[2000Woo] Multi-anvil high-pressure apparatus 900-1200˚C, 2-9 GPa, Fe2SiO4-Fe3O4
[2001Fri] Compound energy formalism 1130˚C, Fe2SiO4 nonstoichiometry, mole
fraction of Fe+3 and vacancies at pO2 in
the range 10–14-10–8 atm
[2001Ott] Polymeric model of liquid 1600˚C, activity of FeO in FeO-SiO2 in
presence of Fe
[2001Zha] Thermodynamic calculation 1600˚C, activity of FeO in FeO-SiO2 in
presence of Fe
[2004Fre] Equilibration with gas mixtures, 1550-1600˚C, FeO-SiO2-O2
thermodynamic calculations
[2004Jun1] CALPHAD assessment, modified 400-2000˚C, Fe-FeO-SiO2-O2
quasichemical model
[2004Jun2] Assessment, modified Wagner’s 1550-1650˚C, 10–3-100 mass% Si
formalism equilibrium between liquid Fe and solid
SiO2
[2004Tyu] Thermodynamic calculation 25˚C, Fe-Si-O
[2005Ake] TEM, energy dispersive X-ray 1200˚C, 6 GPa (synthesis), Fe7SiO10
microanalysis (EDX), electron energy loss
spectroscopy (EELS)
[2005Mik] Numerical analysis on Si deoxidation of 1550-1650˚C, up to 2.1 mass% Si and
molten Fe using Darken formalism 0.036 mass% O
[2005Shi] Equilibrium study in inert atmosphere, 1600˚C, Fe-Si (0.1-70 mass% Si) in
chemical analysis, gravimetry equilibrium with SiO2
[2006Ama] XRD, microprobe, SEM Fe-Si (0-3 mass% Si) after oxidation at
800, 1000˚C

Fe–O–Si 20 15
[2006Bas] TEM, Mössbauer spectroscopy 500-650˚C, 55Fe2O3-45SiO2 (mol%) glass

after reduction and heat treatment to
produce Fe-core Fe3O4 shell
nanostructure
[2006Kim] Chemical vapor condensation, XRD, TEM 700-1100˚C, Fe/SiO2 nanocomposite
[2006Tak] Hot-compression test at 1000˚C, Raman 1100, 1200˚C, Fe-Si (up to 3 mass% Si) in
spectroscopy, X-ray absorption analysis, gas 74%N2-17%H2O-8%CO2-1%O2
in-situ XRD up to 900˚C
[2007Jak] CALPHAD assessment, modified 1000-2000˚C, Fe-FeO-Fe2O3-O2
quasichemical model
[2007Yon] Adiabatic calorimetry –268-30˚C, γFe2SiO4 (heat capacity,
standard entropy)
. Table 2
Pearson
(αδFe) cI2
Im3m a = 293.15 pure Fe at 1390˚C [Mas2]
(δFe) W
1538 - 1394 a = 286.65 pure Fe at 25˚C [Mas2]
(αFe) dissolves 4.6 at.% Ni at 495˚C
< 912
1394 - 912 Fm3m
Cu
P63/mmc c = 396.0
Mg
(Si) cF8 a = 543.06 at 25˚C [Mas2]
< 1414 Fd3m
C (diamond)
α1, Fe3Si cF16 ordered D03 modification of Fe with 11
to 30 at.% Si [1982Kub, Mas2]
≤ 1235 Fm3m
BiF3 a = 565 [V-C2]

16 20 Fe–O–Si
Pearson
α2, Fe-S cP2 ordered B2 modification of Fe with 10

to 22 at.% Si [1982Kub, Mas2]
≤ 1280 Pm3m
CsCl a = 281 [V-C2]
Fe2Si hP6 33.0 to 34.5 at.% Si [Mas2]
1212 - 1040 P
3m1 a = 405.2 ± 0.2 [V-C2]
Fe2Si c = 508.55 ± 0.3
Fe5Si3 hP16 37.5 at.% Si [1982Kub]
1060 - 825 P63/mmc a = 675.9 ± 0.5 [V-C2]
Mn5Si3 c = 472.0 ± 0.5
≤ 1410 P213 a = 451.7 ± 0.5 [V-C2]
FeSi
FeSi2(h) tP3 69.5 to 73.0 at.% Si [Mas2]
1220 - 937 P4/mmm a = 269.01 [V-C2]
βFeSi2 c = 513.4
FeSi2(r) oC48 66.7 at.% Si [1982Kub]
≤ 982 Cmca a = 986.3 ± 0.7 [V-C2]
αFeSi2 b = 779.1 ± 0.6
c = 783.3 ± 0.6
Fe2O3 hR30 ~60 at.% O
< 1457 R
3c a = 503.42 ± 0.03 [V-C2]
Al2O3 c = 1374.83 ± 0.04
FexO cF8 wustite, 0.845 ≤ x ≤ 0.961
1424 - 570 Fm3m a = 435.35 at 1000˚C [V-C2]
NaCl
Fe3O4+y Fe3O4 cF56
< 1596
Fd
3m a = 841.1 magnetite, 57.1 to 58.0 at.% O
MgAl2O4 at 200˚C [V-C2]
αQ, SiO2 hP9 α-Quartz
< 573 P3221 a = 491.38 ± 2 at 25˚C [V-C2]
SiO2 (low c = 540.52 ± 2 [L-B]
quartz)
βQ, SiO2 hP9 β-Quartz
867-573 P6222 a = 502.0 at 600˚C [V-C2]
SiO2 (high c = 552.3
quartz)
a = 503.8 [L-B]
c = 546

Fe–O–Si 20 17
Pearson
SiO2 Low-Tridymite mC144 a = 1854 at 25˚C [L-B]

(monoclinic) Cc b = 501 metastable
< 60 SiO2 c = 2579
(monoclinic
tridymite)
β = 117˚40´
SiO2 Low-Tridymite oC24 a = 874 at 220˚C [L-B]
(orthorhombic) C2221 b = 505 metastable
350 - 160 SiO2 c = 824
(orthorhomb.
tridymite)
Tr, SiO2 hP12 High-Tridymite
1470 - 350 P63/mmc a = 505.2 ± 0.9 at 550˚C [V-C2]
SiO2 (high b = 827 ± 2
tridymite)
a = 503
b = 822 [L-B]
SiO2 tP12 Low-Cristobalite
< 250 P41212 a = 497.8 25˚C [V-C2]
SiO2 (low c = 694.8
cristobalite)
a = 497 ± 3 [L-B]
c = 691 ± 3
Cr, SiO2 cF104 High-Cristobalite
1723 - 250 Fd3m a = 716.6 220˚C [V-C2]
SiO2 (high a = 712.97 ± 0.08 300˚C [L-B]
cristobalite)
Coes, SiO2 mC48 Coesite, stable between 3-9.5 GPa
C2/c a = 709.8 ± 0.2 [V-C2]
SiO2 (coesite) b = 1233.4 ± 0.3
c = 714.8 ± 0.2
γ = 120.10˚
St, SiO2 tP6 Stishovite, stable above 9.5GPa
P42/mnm a = 417.97 ± 0.02 at 25˚C [V-C2]
TiO2 c = 266.69 ± 0.01
αFe2SiO4 oP28 a = 1045.97 Mineral fayalite, end-member of olivine
solid solution [2002Lot]
Pnma b = 608.18
Mg2SiO4 c = 481.50

18 20 Fe–O–Si
Pearson
γFe2SiO4 cF56 at p > 9 GPa γ-spinel forms continuous

solid solution Fe3–xSixO4 with 0 < x < 1
[2000Woo].
Fd
3m
MgAl2O4
a = 824.13 γ spinel at 9-18 GPa [1990Din]
a = 822.89(1 + 8-396˚C [1985Tay]
23.6·10–6T(˚C))
FeSiO3, oP80 a = 1839.2 20˚C [1997Hug]
orthoferrosilite
Pbca b = 907.8
Orthopyroxene c = 523.6
FeSiO3, highP-clino mC40 a = 954.0 1.87 GPa, 20˚C [1994Hug]
C2/c b = 899.6
Clinopyroxene c = 500.8
β = 103.01
a = 992.8 1050˚C [1984Sue]
b = 917.9
c = 533.8
β = 110.2
FeSiO3, lowP-clino mC40 a = 972.1 20˚C [1997Hug]
P21/c b = 907.6
Clinopyroxene c = 522.7
β = 108.53
FeSiO3, highT (III) - a = 662.8 triclinic (pyroxenoid)
P1 b = 746.7 synthesised at 2 GPa, 1250˚C
[1983Web]
c = 2260.7
α = 115.32
β = 80.56
γ = 95.49

Fe–O–Si 20 19
Pearson
Fe3–xSixO4 oI56 structure wadsleite, β-spinel [2000Woo]

Imma a = 586.64 Spd V, x = 0.45
Mn2GeO4 b = 891.32
c = 836.4
a = 585.7 Spd V, x = 0.54 [1997Oht]
b = 889.1
c = 835.4
a = 585.61 Spd III, x = 0.548 [2000Woo]
b = 1189.29
c = 836.83
a = 584.9 Spd III, x = 0.67 [2000Haz]
b = 1185.57
c = 837.72
a = 585.93 Spd II, x = 0.43 [1998Ang], x = 0.4346
[2000Woo]
b = 1798.0
c = 838.4
Fe7SiO10 mP36 a = 2133.6 stable at 5-6 GPa [2000Woo], mineral
iscorite [1985Mod]
P21/m or P2/m b = 306.79
β = 98.06
or [2005Ake]
I12/m1
. Table 3
Composition (at.%)
Reaction T [˚C] Type Phase Fe Si O
L1 + LFe Ð L + SiO2(Cr) 1664 U1 L 17.19 21.85 60.96

L1 1.00 32.67 66.34
L Ð Fe2O3+Fe3O4+SiO2(Tr) 1443 E1 L 31.02 8.53 60.45
L + (γFe) Ð FexO + αFe2SiO4 1180 U5 L 33.00 11.10 55.90
L + (γFe) Ð αFe2SiO4 + SiO2 1178 U6 L 23.93 17.34 58.73
L + FexO Ð Fe3O4 + αFe2SiO4 1160 U9 L 30.78 12.10 57.12
L Ð Fe3O4+ αFe2SiO4 + (γFe) 1137 E5 L 25.96 15.46 58.58
FexO Ð Fe3O4+(αFe)+αFe2SiO4 559 E6 - - - -

20 20 Fe–O–Si
. Table 4
Quantity, per mol of atoms

Reaction or Transformation T [˚C] [kJ, mol, K] Comments
1/7 {Fe(α) + Si+2O2=αFe2SiO4} 25 H = –211.05 [2004Fab]

1/7 {2Fe(α) + Si+2O2=γFe2SiO4} 25 H = –209.296 [2004Fab]
1/5{Fe(α) + Si+1.5O2=αFeSiO3} 25 H = –238.529 [2004Fab]
. Table 5
Thermodynamic Properties of Single Phases
Temperature
Phase Range [˚C] Property, per mole of atoms [J, mol, K] Comments
αFe2SiO4 2525 - 1177 S = 21.57·Cp = 25.146 – 0.001258·T + 3.53·10–6·T 2 – [2004Fab]

555571·T –2
γFe2SiO4 2525 - 1527 S = 20.975·Cp= 23.9371 + 0.004018·T – [2004Fab]
8.07814·105·T –2 + 1.11769·108·T –3 – 509.2·T –1
FeSiO3(ortho) 2525 - 1527 S = 19.32·Cp = 22.0296 + 0.003044·T – 1.66832·106·T–2 [2004Fab]
+ 1.83445·108·T –3 + 1878·T –1
. Table 6
Investigations of the Fe-O-Si Materials Properties
[1985Mod] Magnetic susceptibility Magnetic properties of Fe7SiO10 (iscorite)

[1986Reg] Susceptibility and magnetization, Magnetic properties of ortho FeSiO3
[1987Yag] In-situ XRD 25-1000˚C, 5.3 GPa Thermal expansion of αFe2SiO4 and γFe2SiO4
[2000Haz] Single crystal X-ray in diamond Isothermal bulk modulus and it’s pressure
anvil cell derivative for modified spinel in the Fe3O4-
Fe2SiO4 join
[2001Yam1] Magnetization Curie and Neel temperature, magnetic
properties for spinel structures in the Fe3O4-
Fe2SiO4 join
[2001Yam2] Resistivity at –265-27˚C Electric conductivity
[2002Lot] Mössbauer spectroscopy Electric field gradient in fayalite Fe2SiO4
[2003Kap] X-ray sessile method at Contact angle between liquid Fe and SiO2
1550-1560˚C substrate

Fe–O–Si 20 21
[2004Kon] Susceptibility at –192-700˚C Curie temperature, magnetic properties for

spinel and spinelloid structures in the Fe3O4-
Fe2SiO4 join
[2006Ama] Vickers mictro-hardness Hardness of oxide scales Fe (0-3)Si after
measurement at room oxidation at 800 and 1000˚C
temperature and 1000˚C
[2006Bas] Impedance measurements over Electric conductivity 55Fe2O3-45SiO2 glass after
100 Hz - 6 MHz at –153-167˚C reduction and heat treatment
[2006Kim] Vibration sample magnetometer at Magnetization of Fe/SiO2 nanocomposite
25˚C and 20 kOe

22 20 Fe–O–Si
. Fig. 1
Fe-O-Si. p-T phase diagram of FeSiO3

Fe–O–Si 20 23
. Fig. 2
Fe-O-Si. p-T phase diagram for the SiO2 system at high pressures

24 20 Fe–O–Si
. Fig. 3
Fe-O-Si. p-T phase diagram for the FeO-SiO2 system at high pressures up to 20 GPa from
[2004Fab]. The melting curve from the experimental study of [1979Oht] is shown by a dashed
line

Fe–O–Si 20 25
. Fig. 4
Fe-O-Si. p-x phase diagram of the Fe3O4-Fe2SiO4 system at 1100˚C

26 20 Fe–O–Si
. Fig. 5
Fe-O-Si. Phase diagram of the FeO-Fe2O3-SiO2 at O2 partial pressure of air

Fe–O–Si 20 27
. Fig. 6
Fe-O-Si. Phase diagram of the Fe2O3-SiO2 quasibinary system (pO2 = 1 bar)

28 20 Fe–O–Si
. Fig. 7a
Fe-O-Si. Phase diagram of the FeO-SiO2 system in presence of metallic Fe

Fe–O–Si 20 29
. Fig. 7b
Fe-O-Si. Content of Fe2O3 in liquid vs SiO2 content

30 20 Fe–O–Si
. Fig. 8a
Fe-O-Si. Phase diagram of the Fe2SiO4-FeSiO3 system at high pressure, p = 6 GPa

Fe–O–Si 20 31
. Fig. 8b
Fe-O-Si. Phase diagram of the Fe2SiO4-FeSiO3 system at high pressure, p = 9 GPa

32 20
Fe-O-Si. Reaction scheme, part 1
. Fig. 9a
Fe–O–Si

. Fig. 9b
Fe–O–Si 20 33

34 20
. Fig. 9c
Fe–O–Si

Fe–O–Si 20 35
. Fig. 10
Fe-O-Si. Calculated liquidus surface projection of the FeO-Fe2O3-SiO2 system

36 20 Fe–O–Si
. Fig. 11
Fe-O-Si. Schematic liquidus surface projection

Fe–O–Si 20 37
. Fig. 12
Fe-O-Si. Schematic liquidus relations of the FeO-SiO2 system at high pressures

38 20 Fe–O–Si
. Fig. 13
Fe-O-Si. p-T phase diagram of the composition Fe2SiO4

Fe–O–Si 20 39
. Fig. 14a
Fe-O-Si. Isothermal sections of the FeO-Fe2O3-SiO2 system calculated at 1300˚C

40 20 Fe–O–Si
. Fig. 14b
Fe-O-Si. Isothermal section of the FeO-Fe2O3-SiO2 system calculated at 1450˚C

Fe–O–Si 20 41
. Fig. 15
Fe-O-Si. Partial isothermal section at 1600˚C

42 20 Fe–O–Si
. Fig. 16
Fe-O-Si. Potential diagram log10 (pCO/pCO2) vs temperature. The relation between CO2/CO ratio
and oxygen partial pressure is based on the SGTE thermodynamic database: log10 (pCO2/pCO) =
(7312/T–2.215)log10 (pO2)

Fe–O–Si 20 43
. Fig. 17
Fe-O-Si. Liquid in equilibrium with solid SiO2 at 1250-1350˚C vs oxygen partial pressure. The lines
go from iron to magnetite saturation

44 20 Fe–O–Si
. Fig. 18
Fe-O-Si. Calculated solubility of silica in liquid iron at 1545, 1600 and 1650˚C

Fe–O–Si 20 45
. Fig. 19a
Fe-O-Si. Calculated activity of FeO in liquid FeO-SiO2 in equilibrium with metallic Fe at 1263,
1315, 1364 and 1407˚C

46 20 Fe–O–Si
. Fig. 19b
Fe-O-Si. Calculated activity of FeO in liquid FeO-SiO2 in equilibrium with metallic Fe at 1785,
1880 and 1960˚C

Fe–O–Si 20 47
. Fig. 20
Fe-O-Si. Enthalpy of mixing of the FeO-SiO2 liquid in equilibrium with metallic Fe

48 20 Fe–O–Si
References
[1927Gre1] Greig, J.W., “Immiscibility in Silicate Melts”, Amer. J. Sci., 13(15), 133–154 (1927) (Experimental, Phase
[1927Gre2] Greig, J.W., “On Liquid Immiscibility in the System FeO-Fe2O3-Al2O3-SiO2”, Amer. J. Sci., 14(5Ser.),
473–484 (1927) (Experimental, Phase Diagram, Phase Relations, Thermodyn., 5)
[1932Bow] Bowen, N.L., Schairer, J.F., “The FeO-SiO2 System”, Amer. J. Sci., 24, 177–213 (1932) (Experimental,
[1932Sch] Schenck, R., Franz, H., Laymann, A., “Investigation of Equilibria of Reduction and Oxidation of Iron”,
Z. Anorg. Allg. Chem. 206, 129–151 (1932) (Experimental, Phase Relations, 3)
[1937Wen] Wentrup, H., “The Phase Diagram of Sulphide Inclusions in Steel” (in German), Techn. Mitt. Krupp, 5,
131–152 (1937) (Morphology, Phase Diagram, Phase Relations, Review, 27)
[1939Cro] Crook, W.J., “The Series Iron Oxides-Silica”, J. Am. Ceram. Soc., 22, 322–334 (1939) (Experimental,
Morphology, Phase Diagram, Phase Relations, 15)
[1943Whi] White, J., “The Physical Chemistry of Open-Hearth Slags”, J. Iron Steel Inst., London, 148, 579–694
(1943) (Phase Diagram, Phase Relations, Review, 195)
[1946Cir] Cirilli, V., “Study of Balance Reduction with Carbon Oxide of the Iron Oxides in Presence of Silica”,
Gazz. Chim. Ital., 76, 331–338 (1946) as quoted in [1997Fab]
[1948Dar] Darken, L.S., “Melting Points of Iron Oxides on Silica; Phase Equilibria in the System Fe-O-Si as a
Function of Gas Composition and Temperature”, J. Am. Chem. Soc., 70, 2046–2053 (1948) (Experi-
mental, Phase Diagram, Phase Relations, Theory, 12)
[1950Hil] Hilty, D.C., Crafts, W., “Solubility of Oxygen in Liquid Iron Containing Silicon and Manganese”,
Trans. Am. Inst. Min. Metall. Eng., 188, 425–436 (1950) (Experimental, Phase Relations, 18)
[1951Sch] Schumann, Jr.R., Ensio, P.J., “Thermodynamics of Iron Silicate Slag: Slag Saturated with γ Iron”, Trans.
AIME, 191, 401–411 (1951) (Experimental, Phase Relations, Thermodyn., Phase Diagram, 15)
[1952Gok] Gokcen, N.A., Chipman, J.C., “Silicon-Oxygen Equilibrium in Liquid Iron”, Trans. Amer. Inst. Min.
Met Eng., 194, 171–181 (1952) (Calculation, Experimental, Phase Diagram, Phase Relations, Thermo-
dyn., 21)
[1952Kin] King, E.F., “Heat of Formation of Manganous Metasilicate (Rhodonite) and Ferrous Orthosilicate
(Fayalite)”, J. Am. Chem. Soc., 74, 4446–4448 (1952) (Experimental, Thermodyn., 3)
[1952Mic] Michal, E.J., Schuhmann, Jr.R., “Thermodynamics of Iron-Silicate Slags: Slags Saturated with Solid
Silica”, Trans. AIME, 194, 723–728 (1952) (Calculation, Experimental, Thermodyn., 6)
[1953Chi] Chipman, J., Gokcen, A., “Silicon-Oxygen Equilibrium in Liquid Iron - A Revision”, Trans. Am. Inst.
Min. Metall. Eng., 197(8), 1017–1018 (1953) (Calculation, Phase Relations, Thermodyn., 10)
[1953Sch] Schumann, R.Jr., Powell, R.G., Michal, E.J., “Constitution of the FeO-Fe2O3-SiO2 System at Slagmak-
ing Temperatures”, Trans. Amer. Inst. Min. Met. Eng.,, 197, 1097–1104 (1953) (Experimental, Morphol-
ogy, Phase Diagram, Phase Relations, 7)
[1953Orr] Orr, R.I., “High Temperature Heat Contents of Magnesium Orthosilicate and Ferrous Orthosilicate”, J.
Am. Chem. Soc., 75, 528–529 (1953) (Experimental, Thermodyn., 9)
[1955All] Allen, W.C., Snow, R.B., “The Orthosilicate-Iron Oxide Portion of the System CaO-FeO-SiO2”, J. Am.
Ceram. Soc., 38(8), 264–280 (1955) (Experimental, Phase Diagram, Phase Relations, 12)
[1955Mua] Muan, A., “Phase Equilibria in the System FeO-Fe2O3-SiO2”, Trans. Amer. Inst. Min. Met. Eng., 203,
965–976 (1955) (Experimental, Phase Diagram, Phase Relations, 16)
[1955Sch] Schuhmann, R., “Application of Gibbs-Duhem Equations to Ternary Systems”, Acta Metall., 3, 219–226
(1955) (Phase Diagram, Phase Relations, Theory, Thermodyn., Calculation, 15)
[1957Fit] Fitterer, G.R., “The Physical Chemistry of Steelmaking - A Tribute to Dr. C. H. Herty, Jr.”, Proc. 40th
Nat. Open Hearth Steel Comm. Iron Steel Division, AIME, Pittsburgh, Pennsylvania, 8-10 April
(1957), Mathews, D.R., Kennedy, E.J., Shearman, R.W., Lovell, K.S., (Eds.), Metall. Soc. Amer. Inst. Min.
Metall. Petrol. Eng., 40, 281–303 (1957) (Assessment, Morphology, Phase Diagram, Phase Relations,
Phys. Prop., 40)
[1957Tur] Turkdogan, E.T., Bills, P.M., “A Thermodynamic Study of FeO-Fe2O3-SiO2, FeO-Fe2O3-P2O5 and FeO-
Fe2O3-SiO2-P2O5 Molten Systems”, J. Iron Steel Inst., London, 186, 329–339 (1957) (Experimental,
Thermodyn., 22)
[1959Bod] Bodsworth, C., “The Activity of Ferrous Oxide in Silicate Melts”, J. Iron Steel Inst., London, 193, 13–24
(1959) (Experimental, Kinetics, Phase Diagram, Phase Relations, Thermodyn., 25)

Fe–O–Si 20 49
[1959Phi] Phillips, B., Muan, A., “Phase Equilibria in the System CaO-Iron Oxide-SiO2 in Air”, J. Am. Ceram.
Soc., 42, 413–423 (1959) (Experimental, Phase Diagram, Phase Relations, 18)
[1960Sch] Schenck, H., Schmidtmann, E., Mueller, H., “Influence of the Thermal Treatment and Alloy
Composition on the Internal Oxidation of Iron Alloys” (in German), Arch. Eisenhuettenwes., 31, 121
(1960) (Experimental, Morphology, Thermodyn., 43)
[1961Hsi] Hsi, C.-C., Polyakov, A.Ya., Samarin, A.M., “Oxygen Solubility in Liquid Fe-Si Alloys at Atmospheric
Pressure and under Vacuum” (in Russian), Izv. Akad. Nauk SSSR, (Tekhn.), (2), 115–118 (1961)
[1962Tur] Turkdogan, E.T., “Activities of Oxides in SiO2-FeO-Fe2O3 Melts”, Trans. Metall. Soc. AIME, 224,
294–299 (1962) (Assessment, Calculation, Phase Relations, Thermodyn., 17)
[1964Lin] Lindsley, D.H., MacGregor, I.D., Davis, B.T.C., “Ferrosilite (FeSiO3) Synthesis at High Pressures and
Temperatures”, Science, 144, 73–74 (1964) (Experimental, Phase Relations, 6)
[1964Tay] Taylor, R.W., Schmalzried, H., “The Free Energy of Formation of Some Titanates, Silicates, and
Magnesium Aluminate from Measurements Made With Galvanic Cells”, J. Phys. Chem., 68(9),
2444–2449 (1964) (Experimental, Phase Relations, Thermodyn., 24)
[1965Aki] Akimoto, S., Fujisawa, I., Katsura, T., “The Olivine-Spinel Transition in Fe2SiO4 and Ni2SiO4”,
J. Geophys. Res., 70(8), 1969–1977 (1965) (Experimental, Phase Relations, 23)
[1965Mua] Muan, A., Osborn, E.F., “Fe-Si-O” in “Phase Equilibria Among Oxides in Steelmaking”, Addison-Wesley
Publ. Comp., 53–69 (1965) (Experimental, Phase Diagram, Phase Relations, Review, 6)
[1965Val] Vallet, P., Raccah, P, “Thermodynamic Properties of Solid Iron (II) Oxide”, Mem. Sci. Rev. Met., 62,
1–29 (1965) as quoted in [1997Fab]
[1966Sch1] Schenck, H., Steinmetz, E., “Activity, Standard Condition and Coefficient of Activity” (in German),
Stahleisen-Sonderberichte, Düsseldorf: Verlag Stahleisen, (7), 1–36 (1966) (Review, 161)
[1966Sch2] Schwerdtfeger, K., Muan, A., Darken, L.S., “Activities in Olivine and Pyroxenoid Solid Solutions of the
System Fe-Mn-Si-O at 1150˚C”, Trans. Metall. Soc. AIME, 236, 201–211 (1966) (Experimental, Phase
Diagram, Phase Relations, Thermodyn., 27)
[1967Aki] Akimoto, S.-I., Komada, E., Kushiro, I., “Effect of Pressure on the Melting of Olivine and Spinel
Polymorph of Fe2SiO4”, J. Geophys. Res., 72(2), 679–686 (1967) (Experimental, Phase Relations,
Thermodyn., 8)
[1967Buz] Buzek, Z., Schindlerova, V., Macoszek, M., “The Influence of Cr, Mn, V, Si, Ti, Al, Zr, Ce and Ca on the
Activity and Solubility of Oxygen in Liquid Iron”, Sb. Ved. Pr. Vys. Sk. Banske Ostrave, Rada Hutn.,
13(2-3), 175–193 (1967) (Experimental, Phase Relations, Thermodyn., 26)
[1967Eib] Eibschuetz, M., Ganiel, U., “Mössbauer Studies of Fe3+ in Paramagnetic Fayalite (Fe2SiO4)”, Sol. State
Comm., 5(4), 267–270 (1967) (Experimental, Crys. Structure, 12)
[1967Lin] Lindsley, D.H., “Pressure-Temperature Relations in the System FeO-SiO2”, Year Book-Carnegie Inst.
(Washington), 65, 226–230 (1967) (Experimental, Kinetics, Phase Relations, Thermodyn., 11)
[1967Sch] Schwerdtfeger, K., “Measurement of Oxygen Activity in Iron, Iron-Silicon, Manganese, and Iron-
Manganese Melts Using Solid Electrolyte Galvanic Cells”, Trans. Nat. Res. Inst. Met. (Jpn.), 239,
1267–1281 (1967) (Electrochemistry, Experimental, Thermodyn., 30)
[1969Kul] Kulikov, I.S., “Thermal Dissociation of Compounds” (in Russian), Metallurgia, Moscow, 533–562 (1969)
(Calculation, Phys. Prop., Thermodyn., 136)
[1969Nov] Novokhatsky, I.A., Belov, B.F., “Concentration Dependence of the Solubility of Oxygen in Alloys” (in
Russian), Izv. Akad. Nauk SSSR, Met., (3), 15–26 (1969) (Experimental, Phase Relations, 29)
[1970For] Forward, G., Elliott, J.F., Kuwabara, T., “Formation of Silica and Silicates During the Solidilication of
Fe-O-Si Alloys”, Metall. Trans., 1, 2889–2898 (1970) (Experimental, Phase Relations, 18)
[1970Nis] Nishikawa, K., Kusano, A., Ito, K., Sano, K., “The Effect of Alloying Elements on the Solubility of
Oxygen in Delta-Iron”, Trans. Iron Steel Inst. Jpn., 10, 83–88 (1970) (Experimental, Kinetics, Phase
[1971Dis] Distin, P.A., Whiteway, S.G., Masson, C.R., “Solubility of Oxygen in Liquid Iron from 1785 to 1960˚C.
A New Technique for Study of Slag-Metal Equilibria”, Can. Metall. Quat., 10, 73–78 (1971) (Experi-
[1971Log] Logani, R.C., Smeltzer, W.W., “Development of the Wustite-Fayalite Scale on an Iron-1.5 wt.% Silicon
Alloy at 1000˚C”, Oxidation of Metals, 3(1), 15–32 (1971) (Experimental, Phase Relations, 28)
[1972Sig] Sigworth, G.K., Elliott, J.F., “Conditions for Nucleation of Oxides in Fe-O-Si Alloys”, Can. Metall.
Quart., 11(2), 337–346 (1972) (Review, Thermodyn., 36)

50 20 Fe–O–Si
[1973Vla] Vladimirov, L.P., Kopitsa, N.M., Sumenkova, V.V., “Activity of Oxygen and Silicon in Fe-O-Si Alloys”,
Russ. Metall., 5, 61–65 (1973) (Experimental, Thermodyn., 13)
[1973Iye] Iyengar, R.K., Philbrook, W.O., “Application of Thermodynamics of Heterogeneous Phase Equilibria
to the Construction of the Fe-O-Si Ternary Phase Diagram”, Metall. Trans., 4, 2181–2188 (1973)
(Theory, Phase Relations, 13)
[1974Ark] Arkahrov, V.I., Belov, B.F., Novokhatskii, I.A., “The Solubility of Oxygen in Metallic Melts” (in
Russian), Ukr. Khim. Zh. (Russ. Ed.), 40(2), 129–134 (1974) (Experimental, Phase Relations, Thermo-
dyn., 15)
[1974Sig] Sigworth, G.K., Elliott, J.F., “The Thermodynamics of Liquid Dilute Iron Alloys”, Met. Sci., 8, 298–310
[1976Mor] Morito, N., Ichida, T., “Transaction from External to Internal Oxidation in Fe-Si Alloy as a Function of
Oxygen Potential of the Ambient Atmosphere”, Scr. Metall., 10, 619–622 (1976) (Experimental, Phase
Relations, 10)
[1977Aki] Akimoto, S., Yagi, T., Inoue, K., “High Temperature-Pressure Phase Boundaries in Silicate Systems
Using in Situ X-Ray Diffraction”, High-Pressure Research (Applicat. Geophys.), 15, 585–602 (1977)
[1977She] Shevtsov, V.E., Brovkov, V.A., Lekhtmets, V.L., “Thermodynamics of Oxygen Solutions in Fe-Si Melts”
(in Russian), Izv. VUZ Chern. Metall, (11), 42–45 (1977) (Experimental, Kinetics, 13)
[1978Hew] Hewitt, D.A., “A Redetermination of the Fayalite-Magnetite-Quartz Equilibrium Between 650˚C and
850˚C”, Amer. J. Sci., 278, 715–724 (1978) (Experimental, Thermodyn., 20)
[1979Kau] Kaufman, L., “Calculation of Quasibinary and Quasiternary Oxide Systems II”, Calphad, 3(1), 27–44
(1979) (Phase Relations, Phase Diagram, Thermodyn., Calculation, 5)
[1979Nav] Navrotsky, A., Pintchovski, F.S., Akimoto, S., “Calorimetric Study of the Stability of High Pressure
Phases in the Systems CoO-SiO2 and "FeO"-SiO2, and Calculation of Phase Diagrams in MO-SiO2
Systems”, Phys. Earth Planet. Interiors, 19, 275–292 (1979) (Calculation, Experimental, Phase Relations,
Thermodyn., 71)
[1979Oht] Ohtani, E., “Melting Relation of Fe2SiO4 up to about 200 kbar”, J. Phys. Earth, 27, 189–208 (1979)
(Experimental, Morphology, Phase Diagram, Phase Relations, 34)
[1980Ban] Ban-Ya, S., Chiba, A., Hikosaka, A., “Thermodynamics of Fe(t)O-M(x)O(y) (M(x)O(y) = CaO, SiO2,
TiO2 and Al2O3) Binary Melts Saturated with Solid Iron” “Austral.-Jap. Extractive Metall. Symp.”,
Sydney, Australia 16-18 July 1980, Australian Inst. Min. Metall., 23, 457–467 (1980) (Experimental,
Thermodyn., 22)
[1980Boh] Bohlen, S.R., Essene, E.J., Boettcher, A.L., “Reinvestigation and Application of Olivine-
Quartz-Orthopyroxene Barometry”, Earth Planet. Sci. Letters, 47, 1–10 (1980) (Experimental, Phase
Relations, 51)
[1980Goe] Goel, R.P., Kellogg, H.H., Larrain, J., “Mathematical Description of the Thermodynamic Properties of
the System Fe-O and Fe-O-SiO2”, Metall. Mater. Trans. B, 11B, 107–117 (1980) (Phase Diagram,
Theory, 30)
[1981Ave] Averbukh, S.M., Smirnov, L.A., Popel, S.I., “Equilibrium of Silicon with Oxygen in Molten Iron” (in
Russian), Izv. VUZ Chern. Metall, (11), 5–11 (1981) (Experimental, Kinetics, Thermodyn., 14)
[1981Fuj] Fujisawa, T., Nomura, M., Sakao, H., “Silicon-Oxygen Equilibrium in Delta Iron at the Solid-Liquid
Equilibrium Temperature”, Trans. Iron Steel Inst. Jpn., 21(9), 624–631 (1981) (Experimental, Thermo-
dyn., 29)
[1981Jac] Jacobson, E., Rosen, E., “Thermodynamic Study of High Temperature Equilibria. 25. Solid State
emf Studies of the Systems Fe-FeO, Ni-NiO and Co-CoO in the Temperature Range 1000-1600˚C”,
Scand. J. Metall., 10, 39–43 (1981) (Electrochemistry, Experimental, Thermodyn., Phase Relations, 9)
[1981Lev] Levitskii, V.A., Popov, S.G., Gerasimov, Y.I., “Studies on the Thermodynamics of Complex Oxides of
Iron Subgroup Metals” (in Russian), in “Fiz. Khim. Okislov Met.”, Balakirev (Ed.), Nauka, Moscow,
[1981Sch] Schwab, R.G., Küstner, D., “ The Equilibrium Fugacities of Important Oxygen Buffers in Technology
and Petrology”, Neues Jb. Mineral. Abhandlungen, 140, 111–141 (1981) as quoted in [1987One]
[1982Ban] Ban-Ya, S., Iguchi, Y., Honda H., “Heat of Mixing of Liquid FetO-SiO2 Slag” in “Proc. International
Symposium on the Physical Chemistry of Iron and Steelmaking”, Toronto, III/39-III-44 (1982) (Experi-

Fe–O–Si 20 51
[1982Ois] Oishi, T., Goto, T., Kahayara, Y., Ono, K., Moriyama, J., “Oxygen Pressure Measurements of Silica
Saturated Iron-Oxygen-Silicon Dioxide Melts by the EMF Method Using Zirconia Solid Electrolyte”,
Metall. Mater. Trans. B, 13B, 423–427 (1982) (Experimental, Thermodyn., Phase Relations, 11)
[1982Rob] Robie, R.A., Finch, C.B., Hemingway, B.S., “Heat Capacity and Entropy of Fayalite (Fe2SiO4) between
5.1 and 383 K: Comparison of Calorimetric and Equilibrium Values for the QFM Buffer Reaction”, Am.
Mineral., 67, 463–469 (1982) (Experimental, Thermodyn., 34)
[1982Rol] Rolls, R., Shahhosseini, M.H., “Effect of Creep on the Oxidation Characteristics of Fe-Si Alloys at
973-1073 K”, Oxidation of Metals, 18(3/4), 115–126 (1982) (Experimental, Mechan. Prop., 24)
[1982Wat] Watanabe, H., “Thermochemical Properties of Synthetic High-Pressure Compounds Relevant to the
Earths Mantle”, High-Press. Research in Geophys., 441–464 (1982) (Experimental, Thermodyn., 78)
[1983Kuh] Kuhn, A.T., Wakeman, D., El Roubi, E.Y., Collins, G.C.S., “Anodic Dissolution and Oxygen Evolution
on Binary and Ternary Iron-Silicon Alloys”, Electr. Acta, 28(4), 515–527 (1983) (Experimental, Phase
Relations, 25)
[1983Mye] Myers, J., Eugster, H.P., “The System Fe-O-Si - Oxygen Buffer Calibrations to 1500 K”, Contribution to
Mineralogy and Petrology, 82(1), 75–90 (1983) (Experimental, Thermodyn., 53)
[1983Web] Weber, H.P., “Ferrosilite, the High Temperature Polymorph of FeSiO3”, Acta Crystallogr., 39C(1), 1–3
[1984Kat] Kato, T., Ohtani, E., Kumazawa, M., “Effect of High Pressure on the Melting Relation of the Fe2SiO4-
FeSiO3 System”, J. Phys. Earth, 32, 97–111 (1984) (Experimental, Phase Relations, Thermodyn., 23)
[1984Ste] Stebbins, J.F., Carmichael, I.S.E., “The Heat of Fusion of Fayalite”, Am. Mineral., 69, 292–297 (1984)
[1984Sue] Sueno, S., Kimata, M., Prewitt, C.T., “The Crystal Structure of High Clinoferrosilite”, Am. Mineral.,
69(3-4), 264–269 (1984) (Experimental, Crys. Structure, 14)
[1984Tak] Takada, J., Kashiwagi, K., Adachi, M., “Internal Oxidation of Fe-Si Alloys in γ-Phase Region”, J. Mater.
Sci., 19(10), 3451–3458 (1984) (Experimental, Phase Relations, 19)
[1985Bjo] Bjoerkman, B., “An Assessment of the System Fe-O-Si Using a Structure Based Model for the Liquid
Silicate”, Calphad, 9(3), 271–282 (1985) (Thermodyn., Phase Relations, Assessment, 37)
[1985Jac] Jacobson, E., “Solid State EMF Studies of the Systems FeO-Fe2O3 and Fe3O4-Fe2O3 in the Temperature
Range 1000-1600 K”, Scand. J. Metall., 14, 252–256 (Experimental, Thermodyn., 21)
[1985Mod] Modaressi, A., Malaman, B., Gleitzer, C., Tilley, R.J.D., “Preparation and Study of the Oxysilicate of the
Mixed Valency Fe7(SiO4)O6 (Iscorite)” (in French), J. Solid State Chem., 60, 107–114 (1985) (Crys.
[1985Sas] Sastri, P., Lahiri, A.K., “Applicability of Central Atoms Models to Binary Silicate and Aluminate Melts”,
Metall. Trans. B, 16, 325–331 (1985) (Calculation, Experimental, Theory, Thermodyn., 35)
[1985Tay] Taylor, D., “Thermal Expansion Data. VI. Complex Oxides, AB2O4, the Spinels”, Br. Ceram. Trans. J.,
84(4), 121–127 (1985) (Calculation, Crys. Structure, Review, 99)
[1986Reg] Regnard, J.R., Guillen, R., Wiedenmann, A., Fillion, G., Hafner, S., Langer, K., “Mössbauer and
Magnetic Studies of Orthorhombic FeSiO3”, Hyperfine Interact., 28, 589–592 (1986) (Crys. Structure,
Mag. Prop., Experimental, 8)
[1986Tak] Takada, J., Adachi, M., “Determination of Diffusion Coefficient of Oxygen in α-Iron from Internal
Oxidation Measurements in Fe-Si Alloys”, J. Mater. Sci., 21(6), 2133–2137 (1986) (Experimental, Phase
Relations, Kinetics, 12)
[1986Wie1] Wiesner, U., “On the Internal and External Oxidation in Fe-Si- Alloys” (in German), Neue Huette,
31(9), 330–3331 (1986) (Experimental, Phase Relations, 12)
[1986Wie2] Wiesner, U., Kunze, J., “On the Oxidation and Decarbonizing Behavior of Fe-Si Alloys” (in German),
Neue Huette, 31(7), 250–253 (1986) (Experimental, Phase Relations, 16)
[1986Zin] Zinevich, T.N., Batalin, G.I., “Mutual Effect of Silicon and Oxygen on their Thermodynamic
Activity in the Fe-O-Si Melts” (in Russian), Ukr. Khim. Zh., 52(3), 242–247 (1986) (Experimental,
Thermodyn., 16)
[1987Lee] Lee, Y.P., Bevolo, A. J., Lynch, D.W., “Studies of the Initial Oxidation of Fe-Si Alloys by AES, XPS and
EELS”, Surface Sci., 188(1/2), 267–286 (1987) (Experimental, Phase Relations, 35)
[1987One] OŃeill, H.St.C., “Quartz-Fayalite-Iron and Quartz-Fayalite-Magnetite Equilibria and the Free Energy
of Formation of Fayalite (Fe2SiO4) and Magnetite (Fe3O4)”, Am. Mineral., 72, 67–75 (1987) (Experi-
mental, Thermodyn., 34

52 20 Fe–O–Si
[1987Yag] Yagi, T., Akaogi, M., Shimomura, O., Suzuki, T., Akimoto, S.-i., “In Situ Observation of Olivine-Spinel
Phase Transformation in Fe2SiO4 Using Synchrotron Radiation”, J. Geophys. Res., 92(B7), 6207–6213
(1987) (Calculation, Experimental, Phase Relations, Thermodyn., 29)
[1988One] OŃeill, H.St.C., “Systems Fe-O and Cu-O: Thermodynamic data for the Equilibria Fe-“FeO”,
Fe-Fe3O4, “FeO”-Fe3O4, Fe3O4-Fe2O3, Cu-Cu2O and Cu2O-CuO from emf Measurements”, Am. Min-
eral., 73, 470–486 (1988) (Experimental, Thermodyn., 46)
[1989Aka] Akaogi, M., Ito, E., Navrotsky, A., “Olivine-Modified Spinel-Spinel Transitions in the System
Mg2SiO4-Fe2SiO4: Calorimetric Measurements, Thermochemical Calculation, and Geophysical Appli-
cation”, J. Geophys. Res., 94(B11), 15671–15685 (1989) (Experimental, Phase Diagram, Phase Relations,
Thermodyn., 60)
[1989And] Anderson, W.W., Svendsen, B., Ahrens, T.J., “Phase Relations in Iron rich System and Implications for
the Earth’s Core”, Phys. Earth Inter., 55, 208–220 (1989) (Review, Phase Relations, 48)
[1989Jac] Jacob, K.T., Kale, G.M., Iyengar, G.N.K., “Chemical Potentials of Oxygen for Fayalite-Quartz-Iron and
Fayalite-Quartz-Magnetite Equilibria”, Metall. Trans. B, 20, 679–685 (1989) (Experimental, Thermo-
dyn., 37)
[1989Rag] Raghavan, V., “The Fe-O-Si System” in “Phase Diagrams of Ternary Iron Alloys”, Indian Inst. Met.,
Calcutta, 5, 260–277 (1989) (Review, Phase Relations, Phase Diagram, 36)
[1989Sve] Svendsen, B., Anderson, W.W., Ahrens, T.J., Bass, J.D., “Ideal Fe-FeS, Fe-FeO Phase Relations and
Earth’s Core”, Phys. Earth Inter., 55, 154–186 (1989) (Review, Phase Relations, 68)
[1990Din] Ding, J., Li, D.-Y., “X-Ray Powder Structural Analysis of the Spinel Polymorph of Fe2SiO4”, Powder
Diffr., 5(4), 221–222 (1990) (Crys. Structure, Experimental, 16)
[1990Wri] Wriedt, H.A., “The O-Si (Oxygen-Silicon) System”, Bull. Alloy Phase Diagrams, 11(1), 43–61 (1990)
[1991Ito] Ito, E., Katsura, T., “Dissolution of Silicon and Oxygen in Molten Iron at High Pressure and
Temperature”, Proc. Japan Acad., Ser. B, 67(9), 153–158 (1991) (Phase Relations, Experimental, 14)
[1991Sun] Sundman, B., “An Assessment of the Fe-O System”, J. Phase Equilib., 12(1), 127–140 (1991) (Phase
Relations, Phase Diagram, Assessment, 53)
[1992Bec] Becker, K.D., Dreher, S., Wissmann, S., “A High-Temperature Mössbauer Study of Fayalite, Fe2SiO4:
Cation Diffusion and Reactivity”, Ber. Bunsen-Ges. Phys. Chem., 96(11), 1778–1783 (1992) (Experi-
mental, Crys. Structure, 21)
[1992Hal] Hallstedt, B., “Thermodynamic Assessment of the Silicon-Oxygen System”, Calphad, 16(1), 53–61
(1992) (Calculation, Phase Diagram, Phase Relations, Thermodyn., 22)
[1992Ros] Ross, C.R., Armbruster, T., Canil, D., “Crystal-structure Refinement of a Spinelloid in the System
Fe3O4-Fe2SiO4”, Am. Mineral., 77, 507–511 (1992) (Experimental, Crys. Structure, 17)
[1993Tyu] Tyurin, A.G., “Thermodynamics of Molecular and Ionic Solutions”, Russ. Metall. (Engl. Transl.), (2),
39–47 (1993), translated from Izv. RAN, Met., (2), 48–56 (1993) (Theory, Thermodyn., 35)
[1993Wu] Wu, P., Eriksson, G., Pelton, A.D., Blander, M., “Prediction of the Thermodynamic Properties and
Phase Diagrams of Silicate Systems – Evaluation of the FeO-MgO-SiO2 System”, ISIJ Int., 33(1) 26–35
(1993) (Assessment, Phase Diagram, Phase Relations, Thermodyn., Calculation, 55)
[1994Hug] HughJones, D.A., Woodland, A.B., Angel, R.J., “The Structure of High-Pressure C2/c Ferrosilite and
Crystal-Chemistry of High-Pressure C2/c Pyroxenes”, Am. Mineral., 79, 1032–1041 (1994) (Experimen-
tal, Crys. Structure, 34)
[1994Mat] Matousek, J.W., “Equilibrium Oxygen Pressures of Iron Silicate Slags”, Metall. Mat. Trans. B, 25(3),
463–465 (1994) (Thermodyn., Calculation, 12)
[1996Boe] Boeher, R., “Experimental Constraints on Melting Conditions Relevant to Core Formation”, Geochim.
Cosmochim. Acta, 60(7), 1109–1112 (Review, Phase Relations, 30)
[1996Hug] HughJones, D., Sharp, T., Angel, R., Woodland, A., “The Transition of Orthoferrosilite to High-
Pressure C2/c Clinoferrosilite at Ambient Temperature”, Eur. J. Mineral., 8, 1337–1345 (1996) (Experi-
mental, Crys. Structure, 36)
[1996Sax] Saxena, S.K., “Earth Mineralogical Model: Gibbs Free Energy Minimization in the System MgO-FeO-
SiO2”, Geochim. Cosmochim. Acta, 60, 2379–2395 (1996) (Assessment, Thermodyn., Phase Rela-
tions, 125)
[1997Fab] Fabrichnaya, O.B., Sundman, B., “The Assessment of Thermodynamic Parameters in the Fe-O and
Fe-O-Si Systems”, Geochim. Cosmochim. Acta, 61(21), 4539–4555 (1997) (Assessment, Thermodyn.,

Fe–O–Si 20 53
[1997Hug] HughJones D., “Thermal Expansion of MgSiO3 and FeSiO3 Ortho- and Cinopyroxenes”, Am. Mineral.
82, 689–696 (1997) (Experimental, Crys. Structure, 31)
[1997Li] Li, G.Q., Suito, H., “Electrochemical Measurement of Critical Supersaturation in Fe-O-M (M = Al, Si,
and Zr) and Fe-O-Al-M (M = C, Mn, Cr, Si, and Ti) Melts by Solid Electrolyte Galvanic Cell”, ISIJ Int.,
[1997Oht] Ohtaka, O., Tobe, H., Yamanaka, T., “Phase Equilibria for the Fe2SiO4-Fe3O4 System Under High
Pressure”, Phys. Chem. Miner., 24(8), 555–560 (1997) (Experimental, Morphology, Phase Relations, 25)
[1997Sel] Selleby, M., “An Assessment of the Fe-O-Si System”, Metall. Mater. Trans. B, 28, 563–576 (1997)
(Assessment, Experimental, Kinetics, Phase Diagram, Phase Relations, Phys. Prop., 45)
[1997Woo] Woodland, A.B., Angel, R.J., “Reversal of the Orthoferrosilite- High-P Clinoferrosilite Transition, a
Phase Diagram for FeSiO3 and Implications for the Mineralogy of the Earth‘s Upper Mantle”, Eur.
J. Mineral, 9, 245–254 (1997) (Experimental, Phase Diagram, Phase Relations, Thermodyn., 33)
[1998Ang] Angel, R.J., Woodland, A.B., “Crystal Structure of Spinelloid II in the System Fe3O4-Fe2SiO4”, Eur.
J. Mineral, 10, 607–611 (1998) (Crys. Structure, Experimental, 23)
[1998Lee] Lee, B.-J., “Thermodynamic Calculation for Stability of Oxides in Steel Systems” (in Japanese),
J. Korean Inst. Met., 36(2), 217–224 (1998) (Calculation, Thermodyn., 57)
[1998Won] Wong-Leung, J., Eagelsham, D.J., Sapjeta, J., Jacobson, D.C., Poate, J.M., “The Precipitation of the
Si-SiO2 Interface”, J. Appl. Phys., 83(1), 580–584 (1998) (Experimental, Phase Relations, 19)
[1998Woo] Woodland, A.B., Angel, R.J., “Crystal Structure of a New Spinelloid with the Wadsleyite Structure in
the System Fe2SiO4 -Fe3O4 and Implications for the Earth‘s Mantle”, Am. Mineral., 83, 404–408 (1998)
[1999Ma] Ma, Z., Janke, D., “Oxygen and Nitrogen Reactions in Fe-X and Fe-Cr-Ni-X Melts”, Steel Research,
70(10), 395–402 (1999) (Calculation, Thermodyn., 69)
[1999Rom] Romero-Serrano, A., Pelton, A.D., “Thermodynamic Analysis of Binary and Ternary Silicate Systems
by a Structural Model”, ISIJ Int., 39(5), 399–408 (1999) (Assessment, Phase Relations, Thermodyn., 23)
[1999Ros1] Ross, N.L., Reynard, B.R., “The Effect of Iron on the P21/c to C2/c Transition in (Mg,Fe)SiO3
Clinopyroxenes”, Eur. J. Mineral, 11(3), 585–589 (1999) (Experimental, Optical Prop., Phase Rela-
tions, 18)
[1999Ros2] Ross, N.L., Sowerby, J.R., “High-Pressure Crystal-Field Spectra of Single-Crystal Clinoferrosilite”, Eur.
J. Mineral, 11, 791–801 (1999) (Experimental, Phase Relations, Thermodyn., 29)
[2000Haz] Hazen, R.M., Yang, H.X., Prewitt, C.T., “High-pressure Crystal Chemistry of Fe+3-wadsleite,
β-Fe2.33Si0.67O4”, Am. Mineral., 85, 778–783 (2000) (Experimental, Crys. Structure, 37)
[2000Woo] Woodland, A.B., Angel, R.J., “Phase Relations in the System Fayalite-Magnetite at High Pressures and
Temperatures”, Contrib. Mineral. Petrol., 139, 734–747 (2000) (Experimental, Phase Relations, 44)
[2001Bel] Belashchenko, D.K., Ostrovski, O.I., Skvortsov, L.V., “Molecular Dynamic Simulation of Binary CaO-
FeO, MgO-SiO2, FeO-SiO2 and Ternary CaO-FeO-SiO2 Systems”, Thermochim. Acta, 372, 153–163
(2001) (Calculation, Thermodyn., 20)
[2001Fri] Frisk, K., Selleby, M., “The Compound Energy Formalism: Applications”, J. Alloys Compd., 320(2),
177–188 (2001) (Assessment, Phase Relations, Review, 41)
[2001Zha] Zhang, J., Wang, P., “The Widespread Applicability of the Mass Action Law to Metallurgical Melts and
Organic Solutions”, Calphad, 25(2), 343–354 (2001) (Calculation, Thermodyn., 19)
[2001Ott] Ottonello, G., “Thermodynamic Constraints Arising from the Polymeric Approach to Silicate Slags:
the System CaO-FeO-SiO2 as an Example”, J. Non-Cryst. Solids, 282, 72–85 (2001) (Assessment, Phase
[2001Yam1] Yamanaka, T., Shimazu, H., Ota, K., “Magnetic Properties of Fe2SiO4-Fe3O4 Spinel Solid Solutions”,
Phys. Chem. Miner., 28, 102–109 (2001) (Crys. Structure, Magn. Properties, Experimental, 28)
[2001Yam2] Yamanaka, T., Shimazu, H., Ota, K., “Electric Conductivity of Fe2SiO4-Fe3O4 Spinel Solid Solutions”,
Phys. Chem. Miner., 28, 110–118 (2001) (Crys. Structure, Electr. Prop., Experimental, 35)
[2002Che] Chen, G.Q., Ahrens, T.J., Stolper, E.M., “Schock-Wave Equations of State of Molten and Solid
Fayalite”, Phys. Earth Planet. Inter., 134, 35–52 (2002) (Experimental, Mechan. Prop., 54)
[2002Dav] Davies, R.H., Dinsdale, A.T., Gisby, J.A., Robinson, J.A.J., Martin, S.M., “MTDATA - Thermodynamic
and Phase Equilibrium Software from the National Physical Laboratory”, Calphad, 26(2), 229–271
(2002) (Calculation, Phase Relations, Thermodyn., 29)

54 20 Fe–O–Si
[2002Lot] Lottermoser, W., Steiner, K., Grodzicki, M., Jiang, K., Scharfetter, G., Bats, J. W., Redhammer, G.,
Treutmann, W., Hosoya, S., Amthauer, G., “The Electric Field Gradient in Synthetic Fayalite α-Fe2SiO4
at Moderate Temperatures”, Phys. Chem. Miner., 29, 112–121 (2002) (Crys. Structure, Electr. Prop.,
Experimental, Optical Prop., 26)
[2003Kap] Kapilashrami, E., Lahiri, A.K., Cramb, A.W., Seetharaman, S., “Investigation of the Reaction between
Oxygen-Containing Iron and SiO2 Substrate by X-Ray Sessile-Drop Technique”, Metall. Mater. Trans. B,
34b(5), 647–652 (2003) (Interface Phenomena, Experimental, 11)
[2004Fab] Fabrichnaya, O., Saxena, S.K., Richet, P., Westrum, E.F., “Thermodynamic Data, Model and Phase
Diagrams in Multicomponent Oxide Systems”, Springer Verlag, Berlin Heidelberg, (2004) (Review, Phase
Diagram, Thermodyn., Phys. Prop., 479)
[2004Fre] Fredriksson, P., Seetharaman, S., “Thermodynamics Activities of FeO in some Binary FeO-Containing
Slags”, Steel Res., 75, 240–246 (2004) (Calculation, Experimental, Thermodyn., 23)
[2004Jun1] Jung, I.-H., Decterov, S.A., Pelton, A.D., “Critical Evaluation and Optimization in the FeO-
Fe2O3-MgO-SiO2 System”, Metall. Mater. Trans. B, 35b(5), 877–889 (2004) (Calculation, Theory,
Thermodyn., 59)
[2004Jun2] Jung, I.-H., Decterov, S.A., Pelton, A.D., “A Thermodynamic Model for Deoxidation Equilibria in
Steel”, Metall. Mater. Trans. B, 35b(3), 493–507 (2004) (Calculation, Theory, Thermodyn., 100)
[2004Kon] Kontny, A., Woodland, A.B., Koch, M., “Temperature-Dependent Magnetic Susceptibility Behaviour of
Spinelloid and Spinel Solid Solutions in the Systems Fe2SiO4-Fe3O4 and (Fe,Mg)2SiO4-Fe3O4”, Phys.
Chem. Miner., 31, 28–40 (2004) (Experimental, Magn. Prop., Phase Relations, 36)
[2004Tyu] Tyurin, A.G., “Thermodynamic Analysis of the Silicon Effect on Chemical and Electrochemical
Stability of Iron-Chromium Alloys”, Prot. Met., 40(1), 14–22 (2004) (Calculation, Phase Diagram,
Phase Relations, Thermodyn., 17)
[2005Ake] van Aken, P.A., Miehe, G., Woodland, A.B., Angel, R.J., “Crystal Structure and Cation Distribution in
Fe7SiO10 (Iscorite)”, Eur. J. Mineral, 17, 723–731 (2005) (Crys. Structure, Experimental, Phys. Prop., 13)
[2005Mik] Miki, T., Hino, M., “Numerical Analysis on Si Deoxidation of Molten Fe, Ni, Fe-Ni, Fe-Cr, Fe-Cr-Ni,
Ni-Cu and Ni-Co Alloys by Quadratic Formalism”, ISIJ Int., 45(12), 1848–1855 (2005) (Calculation,
Phase Diagram, Thermodyn., Phase Relations, 27)
[2005Shi] Shibaev, S.S., Krasovskii, P.V., Grigorovitch, K.V., “Solubility of Oxygen in Iron-Silicon Melts in
Equilibrium with Silica at 1873 K”, ISIJ Int., 45(9), 1243–1247 (2005) (Experimental, Phase Diagram,
Thermodyn., 16)
[2006Ama] Amano, T., Okazaki, M., Takezawa, Y., Shiino, A., Takeda, M., Onishi, T., Seto, K., Ohkubo, A.,
Shishido, T., “Hardness of Oxide Scales on Fe-Si Alloys at Room- and High-Temperatures”, Mat. Sci.
Forum, 522–523, 469–476 (2006) (Experimental, Kinetics, Mechan. Prop., Morphology, Phase Rela-
tions, 15)
[2006Bas] Basu, S., Macdonald, J.R., Chakravorty, D., “Conductivity Relaxation in the Interfacial Phase of Iron
Core-Iron Oxide Shell Nanocomposites”, J. Mater. Res., 21(7), 1704–1711 (2006) (Crys. Structure,
Experimental, Morphology, Nano, 24)
[2006Kim] Kim, J.C., Lee, J.W., Park, B.Y., Choi, C.J., “Synthesis and Magnetic Properties of Fe/SiO2 Nanocom-
posite Powders by the Chemical Vapor Condensation Process”, Mat. Sci. Forum, 510–511, 762–765
(2006) (Crys. Structure, Experimental, Morphology, Nano, 7)
[2006Tak] Takeda, M., Onishi, T., “Oxidation Behavior and Scale Properties on the Si Containing Steels”, Mater.
Sci. Forum, 522–523, 477–488 (2006) (Crys. Structure, Experimental, Kinetics, Morphology, Phase
Relations, 10)
[2007Jak] Jak, E., Hayes, P., Pelton, A., Decterov, S., “Thermodynamic optimization of the FeO-Fe2O3-SiO2 (Fe-
O-Si) system by FactSage”, Int. J. Mater. Res., 98(9), 847–854 (Assessment, Phase Diagram, Thermodyn.,
Phase Relations, Calculation, 55)
[2007Yon] Yong, W., Dachs, E., Withers, A.C., Essene, E.J., “Heat Capacity of γ-Fe2SiO4 Between 5 and 303 K and
Derived Thermodynamic Properties”, Phys. Chem. Min., 34, 121–127, (2007) (Experimental, Thermo-
dyn., 30)

Fe–O–Si 20 55
[L-B] Landolt-Boernstein, Numerical Data and Functional Relationships in Science and Technology (New
Series). Group 3 (Crystal and Solid State Physics), Vol. 6, Eckerlin, P., Kandler, H. and Stegherr, A.,
Structure Data of Elements and Intermetallic Phases (1971); Vol. 7, Pies, W. and Weiss, A., Crystal
Structure of Inorganic Compounds, Part c, Key Elements: N, P, As, Sb, Bi, C (1979); Group 4: Macroscopic
and Technical Properties of Matter, Vol. 5, Predel, B., Phase Equilibria, Crystallographic and Thermody-
namic Data of Binary Alloys, Subvol. a: Ac-Au … Au-Zr (1991); Springer-Verlag, Berlin.
(1990)

Fe–O–U 21 1
Iron – Oxygen – Uranium

Pankaj Nerikar, Hans Jürgen Seifert, Pierre Perrot
Introduction
The Fe-O-U system is a key system in the disposal of nuclear waste where iron oxide is used
with uranium waste and finds relevance in the prediction of high temperature phase behavior
of corium. Two ternary compounds have been reported for the Fe-O-U system: UFeO4 and
UFe2O6 which seems to be stable only under high pressures [1978Col]. The experimental work
is summarized in Table 1. The Fe-O-U ternary system was reviewed by [1989Rag]. [1964Eva]
and [1983Smi] have constructed isothermal sections at different temperatures and partial
pressures. [1973Buz] has reported the solubility of oxygen in (Fe,U) liquid alloys at 1600˚C.
Binary Systems
The Fe-U and O-U binary systems are accepted from the critical assessments of [2003Cha] and
[2004Che], respectively. A precise model of the solid and liquid oxide solutions taking into
account the oxygen vacancies in the O-U system may be found in [2002Gue]. The O-U binary
phase diagram from [2004Che] is presented in Fig. 1. The Fe-O phase diagram is accepted
from the assessment by [1991Sun].
Solid Phases
The crystallographic data for the phases present in the Fe-O-U system and their ranges of
stability are summarized in Table 2.
Table 3 lists the invariant reactions of the Fe-O-U ternary system from investigation of
[1964Eva]. They have identified two ternary eutectic points which occur at oxygen partial
pressures of 0.028 and 0.011 bar, respectively.
Isothermal Sections
[1989Rag] gave the Fe-O-U isothermal section at 400˚C from the experimental investigations
of [1983Smi]. This diagram, shown in Fig. 2, is compatible with the well known fact that Fe3O4
oxidizes into Fe2O3 at lower oxygen pressures than UO2 oxidizes into U4O9. Unfortunately,

2 21 Fe–O–U
neither [1964Eva] nor [1983Smi] took into account the ternary compound UFeO4 obtained
from the reaction:
2U3O8+3Fe2O Ð UFeO4+0.5O2.

[1964Eva] have carefully investigated the equilibrium relationships between uranium and iron
oxides as a function of oxygen pressure (586-21300 Pa) and temperature (1200-1460˚C).
Figures 3 to 8 show the projected isobaric sections under oxygen pressures of 21300 (air
atmosphere), 7093, 3456, 1773, 892 and 586 Pa, respectively. It must be pointed out that the
diagrams presented are not vertical sections because the phases in equilibrium are strongly
dependent of the oxygen pressure. For instance, under air atmosphere Fe2O3, stable under
1415˚C loses its oxygen to give Fe3O4 above that temperature as shown in Fig. 3. The transition
Fe2O3 Ð Fe3O4 occurs at 1359, 1328, 1306, 1289 and 1273˚C under 7093, 3456, 1773, 892 and
586 Pa of oxygen pressure, respectively. In the same way, the transition U3O8 Ð UO2 occurs at
1448, 1385, 1358, 1316 and 1296˚C under 7093, 3456, 1773, 892 and 586 Pa of oxygen pressure,
respectively. The three phases UO2-Fe2O3-Fe3O4 coexist in the solid state at 1248˚C under 200
Pa of oxygen pressure.

The ferric-ferrous buffer (mixture Fe3O4-Fe2O3) found naturally may be used to stabilize the
state of oxidation IV of uranium [1983Smi].
Fe-U oxides can be used in an energetically efficient way as catalysts for the partial
oxidation of propane and propene into formaldehyde which is an industrially important
intermediate [2003Tay] in addition to the applications mentioned in the Introduction.
. Table 1
Investigations of the Fe-O-U Phase Relations, Structures and Thermodynamics
[1964Eva] Thermogravimetric analysis under UO2-U3O8-Fe2O3-Fe3O4, 1260-1460˚C, 586 to

controlled oxygen pressures 21300 Pa of oxygen pressure
[1973Buz] Interaction parameters measurements Liquid Fe-O-U alloy (< 10 mass% U,
<2 mass% O), 1600˚C
[1978Col] High pressure synthesis, X-ray UFe2O6, 600˚C, 3 GPa
diffraction
[1983Smi] X-ray diffraction UO2-U3O8-Fe2O3-Fe3O4, 400˚C

Fe–O–U 21 3
. Table 2
Pearson
Temperature Range Space Group/ Parameters
(αU) oC4 a = 285.37 at 25˚C [Mas2]

< 668 Cmcm b = 586.95
αU c = 495.48
(βU) tP30 a = 1075.9 at 25˚C [Mas2]
776 - 668 P42/mnm c = 565.6
βU
(γU) cI2 a = 352.4 [Mas2]
1135 - 776 Im3m
W
(Fe) cI2 a = 286.65 at 25˚C [Mas2]
1538 - 1394 Im3m a = 293.15 at > 1394˚C [Mas2]
< 912 W
(γFe) cF4 a = 364.67 at 25˚C [Mas2]
1394 - 912 Fm3m
Cu
Fe2U cF24 a = 705.5 [2003Cha]
< 1235 Fd
3m
Cu2Mg
FeU6 tI28 a = 1024.99 [2003Cha]
< 829 I4/mcm c = 525.00
MnU6
Fe1–xO (wüstite) cF8 0.05 < x < 0.12 [1991Sun]
1422 - 569 Fm3m a = 431.0 x = 0.05
NaCl a = 429.3 x = 0.12
Fe3O4 (r) oP56 a = 1186.8 [V-C2]
< 580 Pbcm b = 1185.1
Fe3O4 (r) c = 1675.2
Fe3O4 (h) (magnetite) cF56 a = 839.6 at 25˚C
1597 - 580 Fd
3m a = 854.5 at 1000˚C [V-C2]
MgAl204
αFe2O3 (hematite) hR30 a = 503.42 at 600˚C [Mas2, V-C2]
< 1451 R
3c c = 1374.83
Al2O3
βFe2O3 cI80 a = 939.3 metastable phase [V-C2]
Ia
3
Mn2O3

4 21 Fe–O–U
Pearson
Temperature Range Space Group/ Parameters
γFe2O3 (maghemite) tP60 a = 833.96 metatable phase [V-C2]

P41212 c = 832.21
Mn5Si2 (?)
UO2 cF12 a = 547.0 from 62.7 to 66.7 at.% O [2004Che]
< 2852 Fm3m
CaF2
U4O9 cI832 a = 2176 [2004Che]
< 1123 or
I432
I4132
U3O8 oC44 a = 706.9 [2004Che]
< 1870 Cmcm b = 1144.5
c = 830.3
UO3 cP4 a = 414.6 [2004Che]
< 669 Pm3m
ReO3
* UFeO4 oP* a = 488.80 [1989Rag]
Pbcn b = 1193.7
c = 511.0
* UFe2O6 hP* a = 504.0 ± 0.1 [1978Col] High pressure phase (600˚C,
P
31m c = 469.2 ± 0.1 3 GPa)
PbSb2O6
. Table 3
Composition (at.%)
Reaction T [˚C] Type Phase U Fe O
L Ð U3O8 + Fe2O3 + Fe3O4 1318 E1 L 13.50 21.76 64.74

L Ð U3O8 + UO2 + Fe3O4 1326 E2 L 14.65 20.75 64.60

Fe–O–U 21 5
. Fig. 1
Fe-O-U. The calculated O-U equilibrium phase diagram

6 21 Fe–O–U
. Fig. 2
Fe-O-U. Isothermal section at 400˚C

Fe–O–U 21 7
. Fig. 3
Fe-O-U. Isobaric section under 21300 Pa of oxygen (1355 and 1415˚C)

8 21 Fe–O–U
. Fig. 4
Fe-O-U. Isobaric section under 7093 Pa of oxygen (1328, 1359 and 1448˚C)

Fe–O–U 21 9
. Fig. 5

10 21 Fe–O–U
. Fig. 6

Fe–O–U 21 11
. Fig. 7

12 21 Fe–O–U
. Fig. 8

Fe–O–U 21 13
References
[1964Eva] Evans, W.D.J., White, J., “Equilibrium Relationships in the System UO2-Fe3O4-O”, Trans. Brit. Ceram.
Soc., 63(12), 705–724 (1964) (Phase Diagram, Thermodyn., Experimental, *, #, 10)
Iron at 1600˚C”, Int. Symp. Metallurgical Chemistry - Applications in Ferrous Metallurgy, Iron and Steel
Inst, London, 173–177 (1973) (Crys. Structure, Experimental, Review, 8)
[1978Col] Collomb, A., Capponi, J.J., Gondrand, M., Joubert, J.C., “Hydrothermal Synthesis of Some Mixed
Oxides A6+B3+O6 under High Pressures” (in French), J. Solid State Chem., 23, 315–319 (1978) (Crys.
[1983Smi] Smith, D.K., Freeborn, W.P., Scheetz, B.E., “Compatibility Relationships in the U-Fe-O (-H) at 400˚C:
The Implications of the Ferric-Ferrous Buffer for the Immobilization of Uranium and Transuranic
Elements”, Mater. Res. Soc.: Symp. Proc., Sci. Basis Nucl. Waste Managt., 15(6), 91–95 (1983) (Experi-
mental, *, 6)
[1989Rag] Raghavan, V., “The Fe-O-U (Iron-Oxygen-Uranium) System”, Phase Diagrams of Ternary Iron Alloys
(Indian Inst. Metals, Ed.) 5, 332–335 (1989) (Phase Diagram, Review, 6)
Diagram, Thermodyn., Assessment, #, 53)
[2002Gue] Gueneau, C., Baichi, M., Labroche, D., Chatillon, C., Sundman, B., “Thermodynamic Assessment of the
Uranium-Oxygen System”, J. Nucl. Mater., 304, 161–175 (2002) (Assessment, Phase Diagram, Phase
Relations, Thermodyn., #, 88)
[2003Cha] Chatain, S., Gueneau, C., Labroche D., Rogez, J., Dugne, O., “Thermodynamic Assessment of the Fe-U
Binary System”, J. Phase Equilib., 24(2), 122–131 (2003) (Thermodyn., Assessment, Review, #, 34)
[2003Tay] Taylor, S.H., Hutchings, G.J., Palacios, M.-L., Lee, D.F., “The Partial Oxidation of Propane to
Formaldehyde Using Uranium Mixed Oxide Catalysts”, Catal. Today, 81, 171–178 (2003) (Catalysis,
Experimental, Interface Phenomena, 9)
[2004Che] Chevalier, P.-Y., Fischer, E., Cheynet, B., “Progress in the Thermodynamic Modelling of the O-U-Zr
Ternary System”, Calphad, 28, 15–40 (2004) (Assessment, Calculation, Phase Diagram, Thermodyn., 92)
(1990)

Fe–O–W 22 1
Iron – Oxygen – Tungsten

Introduction
The phase relationships in the Fe-O-W system are of great interest from a number of different
aspects. In particular, ternary phases of this system have been the subject of many experimental
studies aimed to establish the correlation among their structural, magnetic and conducting
properties because these phases have found application in the direct conversion of solar to
electrical energy [1999Gus]. Moreover, the WO3/Fe2O3 composite is the best material for the
manufacture of nanostructured photo-electrodes owing to its enhanced photocurrent-voltage
characteristics [2007Luo]. Multi-component systems of transition metal oxides (in particular,
of tungsten and iron) are of interest because of the catalytic properties of their components,
which can be used to oxidize organic substances.
However, information about the constitution of the Fe-O-W system is incomplete.
Experimental studies of phase equilibria have dealt with the WO3-Fe2O3 temperature-compo-
sition section [1978Gar, 1978Tru, 1993Wal] along with partial sections of the Fe-O-W system
at 1100˚C [1977Eks], 1000˚C [1969Sch, 1970Kot, 1977Gel] and 900˚C [1972Sch]. Further
determinations of the phase relations are needed, especially for the liquid-solid equilibria.
Publications devoted to the experimental study of the phase relations, crystal structures
and thermodynamics are listed in Table 1. Reviews of the literature relating to phase equilibria
and crystal structures of the Fe-O-W phases have been presented in [1976Jeh, 1989Rag].
Binary Systems
The Fe-O boundary binary system is accepted as compiled in [Mas2]. The O-W boundary
system is taken from the important review of [1989Wri], which has been reproduced in
[Mas2]. The Fe-W boundary binary system is accepted according to the thermodynamic
assessment of [1987Gus] as accepted by [1988Fer]. This diagram differs from that given by
[Mas2] in relation to the μ (W6Fe7) phase field. The δ (WFe) phase is considered as
metastable.
Solid Phases
Crystallographic data for the known unary, binary and ternary Fe-O-W phases are given in
Table 2. No solubility of the third element in the binary phases has been reported.
The crystal structure of the τ1, WFeO4, phase has been widely reported in the literature
[1930Bro, 1957Koz, 1967Uel, 1968Cid, 1970Kle, 1972Sle, 1974Lyo, 1982Sie, 1991Sch, 1993Yu,
2003Yu, 2006McK]. The phase possesses a monoclinic symmetry with a value of the β angle of
about 90˚, according to practically unanimous agreement of the different investigators. The
hydrothermal synthesis of WFeO4 crystals has been studied by [1970Kle].
2 22 Fe–O–W
For quite a long period of time, the τ2, WFe2O6, ternary phase was considered as occurring
in two polymorphic varieties. The low-temperature form possessing a columbite type
structure, forming at 800˚C, undergoes a monotropic transformation at 950˚C to a high-
temperature modification with a αPbO2 structure. But [1993Wal] established that the
low-temperature modification, designated as τ2ȳ, WFe2O6 (r) in Table 2, being formed at
650-800˚C, transforms monotropically into a monoclinic modification (τ2´, WFe2O6 (h1))
during heating up to 750-900˚C. At 950˚C, the latter undergoes an enantiotropic polymorphic
transformation to the τ2, WFe2O6 (h2) phase with a αPbO2 structure, that was earlier described
in the literature as the high-temperature form of the compound. The crystal structure of the
τ2 phase has been reported in [1957Koz, 1966Tru, 1973Par, 1974Sen, 1976Wei, 1977Pin,
1982Lei1, 1982Lei2, 1988Bir]. The τ3, WFe0.1O3 and τ4, W0.99Fe0.01O2.80, phases were observed
by [1977Eks, 1978McC].
Other reported ternary phases are not stable. The WFeOx (0.4 ≤ x ≤ 1.0) and W3Fe3O
phases were reported by [1954Sch1] and [1954Sch2], respectively, but subsequently, their
existence in the equilibrium state has not been confirmed. Consequently, the W3Fe3O
phase was not seen by [1970Kot] in their investigations at 1000˚C, and it was concluded
that this phase had been stabilized by the presence of nitrogen in samples used the studies
undertaken by [1954Sch2]. Neither phase was found in studies at 1000˚C undertaken by
[1977Gel]. The tungstate Fe2(WO4)3 (or W3Fe2O12) was reported by [1985Har, 1987Mai,
2003Sri]. It was found to decompose at temperatures above 450˚C to give Fe2WO6 which, at
750˚C, loses oxygen to give 2FeWO4 + WO3. [2003Sri] found it very difficult to prepare
this phase by solid state synthesis starting from the component oxides, but proposed that
aqueous solutions of ferrous ammonium sulfate and sodium tungstate be used as precursor
materials.
Isothermal Sections
Phase relationships in the WO2-WO3-WFe2O6 partial system at 1100˚C were studied by

[1977Eks]. The samples used in the investigations were obtained from WO4H2 and Fe2O3
starting materials. Firstly, WO3 oxide was prepared by heating WO4H2 in air at about 827˚C
for several days, and WO2 was prepared from the trioxide by reduction in a stream of a H2/
H2O gas mixture at 750˚C. In order to obtain a suitable partial pressure of water, the hydrogen
gas was allowed to bubble through water held at a temperature of 85˚C. Appropriate amounts
of the oxides were thoroughly mixed and sealed in evacuated silica tubes or in Pt ampoules and
heated at a temperature of 1100˚C for periods ranging from 3 days up to 3 months. On the
basis of X-ray diffraction, and optical and electron microscopy studies, a partial isothermal
section for 1100˚C was constructed; it is shown in Fig. 1 with amendments to ensure
compatibility with the phase boundaries in the accepted O-W phase diagram. The W24O68
phase that was observed by [1989Wri] in mixtures of WO3 and W that had been annealed at
1100˚C is added, and equilibria involving this phase are given with dashed lines. The W20O58
phase that was reported by [1977Eks] as being stable at this temperature, is shown as it is a
member of the WnO3n–2 series of compositions. No evidence for Fe substituting in any
significant amount for W in the binary tungsten oxides was found by [1977Eks]. The “iron-
tungsten bronze” WFexO3 phases in this region were found to be metastable.
Phase equilibria at 1000˚C were investigated by [1969Sch, 1970Kot, 1977Gel]. [1969Sch]
prepared samples of Fe3O4, FeO, WFeO3, WFeO4 and WO2 by annealing in evacuated quartz
Fe–O–W 22 3
ampoules, followed by further heating of to enable the reactions between them to progress.
It was reported that at 1000˚C, the τ1 phase possesses a wide homogeneity range enclosed by
the WO2-FeO and WO3-FeO lines. [1970Kot] prepared samples at 20 compositions around
W3Fe3O in a two stage process. Firstly, mixtures of Fe, W and Fe2O3 were sintered for 100 h at
1000˚C in evacuated Vycor capsules. This was followed by crushing, pressing and sintering
again for 100 h at 1000˚C. The so-called W3Fe3O phase with a Ti2Ni-type structure reported by
[1954Sch2], was not observed. Instead, the Fe2O3 oxide was found to react with the metals to
produce binary metallic phases. [1977Gel] annealed samples in evacuated quartz tubes at a
temperature of 1000˚C for between 2 and 10 days followed by cooling in air. An isothermal
section for the W-WO2-τ1-τ2-Fe2O3-Fe region was proposed. It is presented in Fig. 2 with
small corrections introduced to take into account the phase boundaries of the accepted binary
systems. In particular, (δαFe) and (γFe) were introduced instead of (Fe) as presented by
[1977Gel]; the three-phase region τ1 + δα + (γFe) was added (marked by dashed lines). The
boundary tie line (W)-τ1 of the (W) + μ + τ1 three-phase region is plotted, also by dashed
lines. As noted in the review of [1989Rag], the phase boundaries of the τ1 phase field could not
be determined accurately owing to experimental difficulties and therefore this boundary is
drawn with dashed lines.
Phase relationships in the W-WO3-Fe2O3-Fe partial system were studied by [1972Sch] at
900˚C by determining chemical equilibria under CO/CO2 atmospheres. It was reported
that at 900˚C, the τ1 phase dissolves 32 mol% Fe3O4. Generally, the characteristics of
phase relations proposed by [1972Sch] are similar to those reported by [1969Sch, 1970Kot,
1977Gel] at 1000˚C but the participation of the λ phase was ignored.
The WO3-Fe2O3 temperature-composition section was presented in [1978Gar, 1978Tru,

1993Wal] as well as in the review of [1989Rag] as quasibinary but actually, the solid liquid
equilibria as well as the oxidation state of the phases depend strongly on the imposed oxygen
pressure. The heat treatment of WO3 and Fe2O3 pelletized mixtures was carried out in the
temperature range 1150-1000˚C [1978Gar]. The temperature-composition section was con-
structed from X-ray diffraction and optical microscopy studies. The congruent melting of the
τ2 phase at 1142 ± 5˚C, together with two eutectic equilibria between this phase and WO3 and
Fe2O3 at the temperatures of 1050˚C and 1120 ± 5˚C, respectively, were proposed. At the same
time, both [1974Sen] and [1978Tru] reported the incongruent melting of τ2; at 1130 and
1156 ± 4˚C, respectively. According to the data of [1978Tru], eutectic solidification takes place
only in the WO3-τ2 part of the system (the eutectic point is placed at 1051˚C and 26 mol. %
Fe2O3). Both [1978Gar] and [1978Tru] concluded that no visible solubility or homogeneity
range exists for the compounds of this section. Later, the section was studied by [1993Wal]
using both X-ray diffraction and differential thermal analysis techniques. Samples were
prepared from mixtures of WO3 and Fe2O3 oxides in appropriate ratios. These mixtures
were homogenized by powdering, pressing and heating at 900˚C for 24 h and at 950˚C for
24 h. DTA measurements were performed at temperatures between 20 and 1200˚C. On the
basis of the experimental results obtained, a temperature-composition section for WO3-Fe2O3
was constructed. It is presented in Fig. 3 with corrections relating to the locations of the phase
boundaries in the accepted O-Fe and O-W systems. With a view to eliminating ambiguity in
the designations of the phase fields containing the different modifications of the τ2 and WO3
4 22 Fe–O–W
phases, the lower temperature limit of the section was increased to slightly higher than 950˚C
(contrary to about 900˚C in [1993Wal]). The incongruent melting temperature of τ2, (WFe2O6
(h2)) was accepted as 1100 ± 10˚C.
Thermodynamics
The thermodynamic properties of dilute solutions of oxygen in Fe-W alloys were studied by
[1965Tan] by means of hydrogen-water vapor equilibria measurements. The reaction studied
was H2 (gas) + O (solution) Ð H2O (gas). The equilibrium constant for this reaction is: K =
pH2O/(pH2 {% O}), where pH2O and pH2 are the partial pressures of water vapor and hydrogen
and {%O} is the amount of dissolved oxygen in mass%. It was shown for the W20Fe80 (mass%;
W7.06Fe92.94 in at.%) alloy that at 1550˚C, the equilibrium constant is relatively independent of
the oxygen content in the range up to 0.1 mass% O. For this alloy, the relationship between the
equilibrium constant and temperature in the temperature range 1550-1700˚C is: log10 K =
{(6917 ± 20)/T)} – (3.05 ± 0.01). The interaction parameter for tungsten contents up to 20
mass% is εOW = 0.008. Later, the oxygen activity in an iron melt containing up to 32 mass% W
was determined by [1971Fis] using solid electrolyte cells. The value of interaction parameter in
the range of compositions 3.86 to 31.5 mass% W at 1600˚C was obtained as εOW = 0.011.
Using equilibria under CO/CO2 gas mixtures, [1972Sch] established that at 900˚C,
the values of ΔrG for the reactions “FeO” + WO3 Ð WFeO4 and Fe2O3 + WO3 Ð WFe2O6
are –43.1 ± 5.0 and –95.3 ± 23.4 kJ·mol–1, respectively.
The heat capacity of WFeO4 was measured by [1974Lyo] in the temperature range 5-550 K
by adiabatic calorimetry. The temperature of the maximum heat capacity of the antiferro-
magnetic anomaly was found to be (75.25 ± 0.1) K. [1980Amo] used high temperature
solution calorimetry to determine the enthalpy of reaction for WO3 (solid, 298.15 K) + FeO
(solid, 298.15 K) Ð WFeO4 (solid, 298.15 K) giving ΔrH0 (WFeO4, solid, 298.15 K) =
– (77.1 ± 6.0) kJ·mol–1. The Gibbs energy of formation of the τ1, WFeO4 phase was deter-
mined by [1980Kle, 1983Kle] by emf measurements using solid galvanic cells using a ThO2
electrolyte. The following equation was obtained for the temperature range 1180-1330 K
(907 to 1057˚C): – 1138200 + 299.2 T ± 2200 J·mol–1. Standard entropy values for the
WFeO4 compound were used by [1988Bag] to calculate (H0298 - H00). Good agreement was
observed between calculated and experimental data.
Fe-O-W alloys are of great interest for a number of practical applications in modern technol-
ogy, in particular in relation to energetics, as catalysts in the chemical industry (W3Fe2O12), as
nanostructured photoelectrodes (WO3/Fe2O3 composite) etc. The experimental techniques
used in the investigation of physical properties of Fe-O-W alloys are listed in Table 3.
P-type conduction has been reported from thermopower investigations of WFeO4
[1991Sch]. The non-stoichiometric samples were produced under slightly oxidizing condi-
tions and exhibited a reduced electrical resistivity which appears to be related to the pre-
sence of an enhanced Fe3+ content in addition to Fe2+. This compound was reported by
[2001Kaw] as possessing antiferromagnetic properties with a Néel temperature of 70 K.
Magnetic susceptibility and EPR measurements using modifications of the τ2, WFe2O6,
Fe–O–W 22 5
phase at low temperatures [1995Gus] revealed a significant paramagnetic contribution,

probably resulting from local distortions of the antiferromagnetic bulk structure induced by
a disturbed cation ordering or the presence of Fe2+ ions. The high-electrical resistivity found
for the modifications of the τ2 phase as observed by [1999Gus] are consistent with the presence
of the dominant antiferromagnetic component of the compounds.
Electrodes of WO3/Fe2O3 were prepared on a FTO substrate by [2007Luo] using a sol-gel
method, and subsequently, their photoelectrochemical properties were studied in a three-
electrode cell. The semiconductor electrodes generated an anode photocurrent, which sug-
gested they were n-type semiconductors.
Miscellaneous
The kinetics of the reactions between iron oxides and WO3 were studied by [1957Koz]. The
kinetics of oxidation in air of the alloy Fe90.23W9.77 (mass%; in at.% - Fe96.82W3.18) at the
temperatures of 740, 830, 900 and 960˚C were investigated by [1962Yat]. An ‘induction period’
of the oxidation lasting from 5 to 20 h at temperatures from 740 to 900˚C was noted. It was
established that the resultant oxide film consisted of three layers. The kinetics of crystallization
of WFeO4 was studied by [1984Buh] using hydrothermally reacting the metal (II)-chlorides
and sodium tungstate in a special autoclave, at 300 and 400˚C and a pressure of 1 kbar. The
rates of crystallization were determined by continual removal of the reactants from the
autoclave. At both temperatures, a decrease in the tungstate concentration in the solution
followed first order reaction kinetics. The rate constants of the reactions were calculated and
the Jerofejev equation was used to describe the kinetics. In order to explain the experimentally
observed influence of the gases on the synthesis of iron tungstate (Fe2O3 + WO3 + WFe2O6),
different solid-solid mechanisms [1984Tho2] and gas-solid mechanisms [1984Tho3] have
been considered. Comparisons between the theoretical and experimental kinetics curves show
that diffusion in the solid state is not the only limiting step in the synthesis, and the strong
influence of gases on the reaction kinetics confirms this conclusion [1984Tho2]. In
[1984Tho3], a gas-solid mechanism for the synthesis of iron tungstate and a description of
its elementary steps (tungsten oxide volatilization, gaseous diffusion and condensation) have
been developed, and new kinetics laws for pure volatilization or condensation have been given.
It was noted that some experimental results agreed with models of sublimation or condensa-
tion, but the comparison between experimental and theoretical kinetics curves indicated that
the iron tungstate synthesis is governed at 800 or 760˚C by a mixed regime of volatilization and
diffusion in the solid phase. Ferric tungstate W3Fe2O12 was investigated by [1985Har] as a
catalyst for the selective oxidation of methanol and was shown to have very different proper-
ties from ferric molybdate for this application. Over the molybdate, the predominant reaction
is the oxidation of methanol to formaldehyde, whereas over the tungstate it is dehydration to
dimethyl ether. Structural changes of coprecipitated and mechanically mixed iron/tungsten
oxides occurring during calcination and reduction were studied by [1987Mai]. The tempera-
ture dependence of the EPR spectrum for the τ2, (WFe2O6 (r)) phase has been investigated by
[1998Gus] over the temperature range 40-260 K.

6 22 Fe–O–W
. Table 1
Investigations of the Fe-O-W Phase Relations, Structures and Thermodynamics
Temperature / Composition
Reference Method / Experimental Technique / Phase Range Studied
[1930Bro] X-ray powder diffraction (XRD) WFeO4

[1954Sch1] XRD (Guinier technique) WFeOx (x = 0.4 to 1.0)
[1954Sch2] XRD (Guinier technique) W3Fe3O, WO2
[1957Koz] Diffusion annealing, XRD, chemical analysis WFeO4, WFe2O6
[1965Tan] Hydrogen-water vapor equilibrium 1550-1700˚C, 70-100 mass%
Fe, ≤ 0.12 mass% O
[1966Tru] XRD 1200˚C, 1000˚C, the WO3-
Fe2O3 section
[1967Uel] XRD WFeO4
[1968Cid] XRD on single crystal, chemical analysis WFeO4
[1969Sch] Solid state reactions in evacuated quartz ampoules, X- 1000˚C, 50 to 75 at.% O
ray diffraction
[1970Kle] Hydrothermal synthesis, XRD, thermal analysis 600-375˚C,
p = 400-1700 atm, WFeO4
[1970Kot] Sintering, XRD, optical microscopy 1000˚C, composition range
around W3Fe3O
[1971Fis] Solid electrolyte cells 1600˚C
[1972Sch] Equilibria measurements under CO/CO2 gas mixture 900˚C, the W-WO3-Fe2O3-Fe
partial system
[1972Sle] XRD (Haegg-Guinier camera) WFeO4
[1973Par] Annealing, XRD WFe2O6
[1974Lyo] Adiabatic calorimetry (Mark II adiabatic cryostat, Mark 5-550 K, WFeO4
IV adiabatic thermostat)
[1974Sen] Annealing, XRD WFe2O6
[1976Wei] Neutron diffraction WFe2O6
[1977Eks] Heating of WO4H2 in air, reduction of WO3, X-ray 1100˚C, the WO2-WO3-
powder diffraction, optical microscopy, electron Fe2WO6 partial system
microscopy
[1977Gel] Annealing, XRD (Guinier camera) 1000˚C, the W-WO2-τ1-τ2-
Fe2O3-Fe region
[1977Pin] XRD, neutron diffraction WFe2O6
[1978Gar] Annealing, quenching, XRD, reflected light microscopy 1150-1000˚C, the WO3-Fe2O3
section
[1978McC] Heating, pressurizing; optical microscopy XRD, ≤ 1100˚C, the WO3-Fe section
Weissenberg X-ray technique

Fe–O–W 22 7
Temperature / Composition
Reference Method / Experimental Technique / Phase Range Studied
[1980Amo] High-temperature solution calorimetry 667˚C, 25˚C, WFeO4, FeO +

WO3
[1980Kle] Emf measurements 907-1057˚C, WFeO4
[1982Lei1] Solid state reactions, XRD, (Debye- Scherrer technique) WFe2O6
[1982Sie] Solid state reactions, single crystals synthesis, XRD WFeO4
[1985Har] XRD Fe2(WO4)3, preparation,
catalytic properties
[1987Mai] XRD, DTA Fe2(WO4)3, preparation,
decomposition
[1988Bir] Calcination in air, Mössbauer, XRD WFe2O6
[1991Sch] Single crystals and polycrystalline samples WFeO4
preparations, XRD (Laue technique)
[1993Wal] Annealing, DTA, XRD 950˚C, 900˚C, the WO3-Fe2O3
section
[1993Yu] Single crystals preparation, XRD, electron microprobe WFeO4
analysis
[2003Sri] XRD, XRD Preparation of Fe2(WO4)3 and
calcination in air
[2003Yu] Hydrothermal treating, XRD WFeO4
[2006McK] XRD, Mössbauer WFeO4; WFeO4 + C
[2007Luo] Sol-gel method; XRD, UV-visible transmission WO3, Fe2O3, the WO3/Fe2O3
spectroscopy, SEM, EDS composites

8 22 Fe–O–W
. Table 2
Pearson
Symbol/
(W) cI2 a =316.52 at 25˚C [Mas2]

< 3422 Im3m Dissolves 2.6 at.% Fe at 1637˚C
W
δα, (δFe,αFe) cI2
Im3m
(δFe) W a = 293.15 at 1394˚C [Mas2]
1538 - 1394 Dissolves 14.3 at.% W at 1548˚C
(αFe) (Ferrite) a = 286.65 pure Fe at 25˚C [Mas2]
< 912
(γFe) (Austenite) cF4 a = 364.67 at 915˚C [Mas2]
1394 - 912 Fm3m Dissolves 1.2 at.% W at 1100˚C [Mas2]
Cu
(εFe) hP2 a = 246.8 at 25˚C, > 13 GPa [Mas2]
P63/mmc c = 396.0
Mg
λ,WFe2 hP12 a = 473.7 [1986Nag, 1987Gus]
< 1062 P63/mmc c = 770.0 C14 structure
MgZn2
μ, W6Fe7 hR39 ~56 to 59.5 at.% Fe
< 1641 R
3m D85 structure [1989Rag]
W6Fe7 a = 476.4 ±⊊0.3 [V-C2]
c = 2585 ±⊊2
δ, WFe oP* - metastable [1988Fer]
P212121
MoNi
FeO (Wüstite) cF8 actually (Fe1–xO with 0.05 < x < 0.12)
1422 - 569
Fm3m a = 431.2 x = 0.05 [V-C2]
NaCl a = 429.3 x = 0.12 [V-C2]
αFe3O4 (r) oP56 a = 1186.8 [V-C2]
< 580 Pbcm b = 1185.1
Fe3O4 I c = 1675.2
βFe3O4 (h) cF56 inverse Spinel
(Magnetite)
1597 - 580 Fd
3m a = 854.5 at 1000˚C [V-C2]
MgAl2O4 a = 839.6 at 25˚C [V-C2]
(Spinel)

Fe–O–W 22 9
Pearson
Symbol/
αFe2O3 (Hematite) hR30 a = 503.42 [1989Rag]

< 1457 R3c αAl2O3 c = 1374.83
(Corundum)
βFe2O3 cI80 metastable phase
Ia3 a = 939.3 [V-C2]
βMn2O3
(Bixbyite)
γFe2O3 cF56 metastable phase
(Maghemite) Fd3m a = 834
MgAl2O4 [1989Rag]
εFe2O3 m*100 metastable
a = 1299 [V-C2]
b = 1021
c = 844
β = 95.33
WO2 mP12 a = 555.6 ~ 66.7 at.% O [1989Wri]
< 1530 P21/c b = 489.31
VO2 c = 565.77
β = 120.42˚
W18O49 mP67 a = 1832.4 ~73.1 at.% O [1989Wri]
> 1700 - 585 P2/m b = 378.4
W18O49 c = 1403.5
β = 115.20˚
W24O68 m*92 a = 1931 ~ 73.9 at.% O [1989Wri]
W24O68 b = 378.1
c = 1707
β= 104.4˚
W20O58 mP78 a = 1205 74.4 at.% O; member of the WnO3n–2 series
P2/m b = 376.7 [1989Wri]
W20O58 c = 2359
β = 85.47˚
W24O70 mP94 a = 1207 74.5 at.% O; member of the WnO3n–2 series
W24O70 b = 378 [1989Wri]
c = 2890
β = 98.6˚
W25O73 mP98 a = 1193 74.5 at.% O; member of the WnO3n-2 series
P2/c b = 382 [1989Wri]
W25O73 c = 5972
β = 98.3˚

10 22 Fe–O–W
Pearson
Symbol/
W25O74 mP99 a = 1190 74.7 at.% O; probable member of the WnO3n–1

P2/m b = 382.6 series [1989Wri] labelled as WO2.96
W25O73 c = 2982
β = 98.4˚
WO3 (h4) tP8 (?) 75.0 at.% O [1989Wri] labelled as WO3-A
1474 - 1230 P4/nmm (?)
WO3 (h4) a = 525.7 T = 1260˚C [1989Wri]
c = 391.2
WO3 (h3) tP8 75.0 at.% O; labelled as WO3-B
1230 - 900 P4/nmm a = 527.2 T = 950˚C [1989Wri]
WO3 (h3) c = 392.0
WO3 (h2) tP8 75.0 at.% O; labelled as WO3-C
900 - 740 P4/nmn a = 525.0 T = 770˚C [1989Wri]
WO3 (h2)a c = 391.5
WO3 (h1) oP32 75.0 at.% O; labelled as WO3-D
740 - 330 Pmnb a = 734.1 T = 480˚C [1989Wri]
WO3 (h1)a b = 757.0
c = 775.4
WO3 (r) mP32 75.0 at.% O; labelled as WO3-E
330 - 17 P21/n a = 730.6 at 25˚C [1989Wri]
WO3 (r)a b = 754.0
c = 769.2
β = 90.881˚
WO3 (l1) aP32 75.0 at.% O; labelled as WO3-F
17 - (–40) P1 a = 730.9 at 25˚C [1989Wri]
WO3 (l1) b = 752.2
c = 767.8
α = 88.81˚
β = 90.92˚
γ = 90.93˚
WO3 (l2) mP16 75.0 at.% O; labelled as WO3-G
(–40) - (–143) Pc a = 527.5 T = –70˚C [1989Wri]
WO3 (l2) b = 515.5
c = 767.2
β = 91.7˚
WO3 (l3) - - 75.0 at.% O; labelled as WO3-H [1989Wri]
(–143) - (–208)
WO3 (l4) - - 75.0 at.% O; labelled as WO3-J [1989Wri]
(–208) - (–233)

Fe–O–W 22 11
Pearson
Symbol/
WO3 (l5) - - 75.0 at.% O; labelled as WO3-K [1989Wri]

(–233) - (–257)
WO3 (l6) - - 75.0 at.% O; labelled as WO3-M [1989Wri]
< –257
τ1, WFeO4 mP12 a = 473.4 [1989Rag, 2003Yu]
(Ferberite) P2/c b = 570.9
WFeO4 c = 496.3
β = 90˚
τ2, WFe2O6 (h2) oP9 a = 457.6 [1982Lei1, 1989Rag] labelled as γWFe2O6
1100 - 900 Pbcn b = 1676.6 [1999Gus]
αPbO2 c = 496.7
τ2´, WFe2O6 (h1) m** - labelled as βWFe2O6
840 - 750 - [1999Gus]
τ2´´, WFe2O6 (r) oP9 a = 1374.9 [1973Par, 1993Wal] labelled as αWFe2O6
< 800 Pbcn b = 1679.3 [1999Gus]
columbite c = 995.8
τ3, WFe0.1O3 h** a = 742.2 iron-tungsten bronze [1978McC]
- c = 376.6
τ4, W0.99Fe0.01O2.80 tP* a = 2329 [1977Eks]
P421m c = 379.4
-
WFeOx hP3 a = 431 x = 0.4 to 1.0 [1954Sch1]
P63/mmc c = 275
Fe2N
W3Fe3O cF96 a = 1096 ± 1 [1954Sch2]
Fd3m
Ti2Ni
W3Fe2O12 - a = 1586 or Fe2(WO4)3
b = 929.5 metastable phase [2003Sri]
c = 1842
β = 125.1˚
a)Often described as a slightly distorted ReO3-type [1989Wri, Mas2]

12 22 Fe–O–W
. Table 3
Investigations of the Fe-O-W Materials Properties
[1967Uel] Neutron diffraction Antiferromagnetic ordering

[1976Wei] Neutron diffraction Magnetic structure of the τ2, WFe2O6 (h2)
phase
[1977Gel] Picnometer method, Mössbauer Density, electronic structure
spectroscopy
[1977Pin] Neutron diffraction Magnetic structure of the τ2, WFe2O6 (h2)
phase
[1981Bha] Electrical conductivity and thermoelectric d.c. and a.c. electrical conductivity,
power measurements thermoelectric power of the τ2, WFe2O6
(h2) phase
[1982Lei1] Faraday balance method van der Pauw The τ2, WFe2O6 (h2) phase: magnetic
technique, photoelectrolytic susceptibility, dependence of
measurements photocurrent on anode potential,
electrical resistivity, quantum efficiency
[1982Sie] Hydrostatic technique, The τ1, WFeO4 phase: density, stability
thermogravimetric analysis (Cahn towards oxidation, electrical resistivity,
electrobalance), Faraday balance method, magnetic susceptibility
van der Pauw technique
[1984Tho1] Thermomagnetic analysis The τ2, WFe2O6 (h2) phase - magnetic
susceptibility
[1988Bir] Mössbauer spectroscopy Mössbauer parameters for the WFe2O6-
phase containing samples
[1991Sch] Electrical resistivity measurements The τ1, WFeO4 phase: d.c. and a.c.
(Wheatstone- and Schering-type bridges), electrical resistivity, thermoelectric power
thermoelectric power measurements
[1995Gus] EPR measurements (a standard X-band The WFe2O6 phases: d.c. magnetic
spectrometer Bruker 200D), d.c. magnetic susceptibility, EPR spectra
measurements (vibrating sample
magnetometer)
[1998Gus] EPR measurements (a standard X-band The τ2, WFe2O6 (r) phase - EPR spectra
spectrometer Radiopan R-10), NMR
technique
[1999Gus] EPR measurements (a standard X-band The WFe2O6 phases: electrical resistivity,
spectrometer Radiopan SEX-104), d.c. EPR spectra
electrical resistivity measurements
(Keithley 181 electrometer)
[2001Kaw] Mössbauer spectroscopy The τ1, WFeO4 phase: electronic structure
[2003Yu] TEM, selected area electron diffraction Morphology of nanorods
(SAED)

Fe–O–W 22 13
[2006Azi] X-ray photoelectron spectroscopy (XPS), The (WO3)1–x-(Fe2O3)x thin films:

atomic force microscopy optical density, electrochromic properties
[2006Eji] Optical (absorption and reflection) Single WFeO4 microcrystals: absorption
spectroscopy, ultraviolet photoelectron coefficient and reflectance spectra,
spectroscopy (UPS) valence band photoelectrons spectra
[2007Luo] CH1600B electrochemical analysis, mono- Photocurrent under different applied
chrome filters, photometry potentials, incident photon conversion
efficiency (IPCE), light intensity

14 22 Fe–O–W
. Fig. 1
Fe-O-W. Partial isothermal section at 1100˚C

Fe–O–W 22 15
. Fig. 2
Fe-O-W. Partial isothermal section at 1000˚C

16 22 Fe–O–W
. Fig. 3
Fe-O-W. Temperature - composition section WO3-Fe2O3

Fe–O–W 22 17
References
[1930Bro] Broch, E.K., “Investigation of Crystal Structures of Wolframit-Type and Sheelit-Type Compounds” (in
German), Mat.-Nat. Klasse, (8), 3–62 (1930) (Crys. Structure, Experimental, Review, 64)
[1954Sch1] Schoenberg, N., “On the Existence of Metallic Ternary Oxides Me’Me’’O with the Metal Atoms in
Hexagonal Close-Packing”, Acta Chem. Scand., 8 (4), 630–632 (1954) (Crys. Structure, Experimental, 5)
[1954Sch2] Schoenberg, N., “On the Existence of Ternary Transition Metal Oxides”, Acta Chem. Scand., 8(6),
[1957Koz] Kozmanov, Yu.D., “An X-Ray Study of the Reaction Between Solid Iron Oxides and the Oxides of
Tungsten and Molybdenum” (in Russian), Zh. Fiz. Khim., 31(8), 1861–1865 (1957) (Crys. Structure,
Experimental, Kinetics, 6)
[1962Yat] Yatsyuk, M.A., Solomko, V.Ya., “Kinetics of Oxidation of the Iron Alloy with 9.77% of Tungsten at
740-960˚C” (in Russian), Zh. Prikl. Khim., 35(10), 2336–2338 (1962) (Morphology, Experimental,
Kinetics, 2)
[1965Tan] Tankins, E.S., Thomas, M.K., Erthal, J.F., Williams, F.S., “The Activity of Oxygen in Liquid Iron-
Molybdenum and Iron-Tungsten Alloys”, Trans. Am. Soc. Met., 58(3), 245–252 (1965) (Phase Relations,
Thermodyn., Experimental, 10)
[1966Tru] Trunov, V.K., Kovba, L.M., “Interaction of Molybdenum and Tungsten Trioxides with Iron (III) and
Chromium (II) Oxides”, Izv. Akad. Nauk SSSR, Neorg. Mater., 2(1), 151–154 (1966) (Crys. Structure,
Experimental) as quoted by [1978Gar]
[1967Uel] Uelkue, D., “Investigations of Crystal Structure and Magnetic Structure of the Ferberits FeWO4” (in
German), Z. Kristallogr., 124(3), 192–219 (1967) (Crys. Structure, Experimental, Magn. Prop., 15)
[1968Cid] Cid-Dresdner, H., Escobar, C., “The Crystal Structure of Ferberite, FeWO4”, Z. Kristallogr., 127, 61–72
[1969Sch] Schroecke, H., “Solid Phase Equilibria in the Fe-Mn-W-O System” (in German), Neues Jahrb. Mineral,
Abhandl., 110(2), 115–127 (1969) (Phase Diagram, Phase Relations, Experimental, *, 24)
[1970Kle] Klevtsov, P.V., Novgorodtseva, N.A., Kharchenko, L.Yu., “Hydrothermal Synthesis of FeWO4 Crystals”
(in Russian), Kristallografiya, 15(3), 609–610 (1970) (Crys. Structure, Experimental, 9)
[1970Kot] Kotyk, M., Stadelmaier, H.H., “Study of Filled Ti2Ni-Type Phases with Hf, Ta, and W”, Metall. Trans., 1,
899–903 (1970) (Crys. Structure, Morphology, Phase Diagram, Phase Relations, Experimental, *, 16)
[1971Fis] Fischer, W.A., Janke, D., “The Activity of Oxygen in Iron Melts Containing Molybdenum, Tungsten,
Niobium or Tantalum” (in German), Arch. Eisenhuettenwes., 42(10), 695–698 (1971) (Thermodyn.,
Experimental, 15)
[1972Sch] Schmahl, N.G., Dillenburg, H., “Phase Equilibria and Thermodynamics of the Ternary Systems
Fe-Mo-O and Fe-W-O” (in German), Z. Physik. Chem. Neue Folge, 77, 113–126 (1972) (Phase Diagram,
Phase Relations, Thermodyn., Experimental, 40)
[1972Sle] Sleight, A.W., “Accurate Cell Dimensions for ABO4 Molybdates and Tungstates”, Acta Crystallogr., B28,
[1973Par] Parant, C., Bernier, J.C., Michel, A., “Two Orthorhombic Forms of Iron Tungstate” (in French), Compt.
Rend., Ser. C, 276C, 495–497 (1973) (Crys. Structure, Experimental, 10)
[1974Lyo] Lyon, W.G., Westrum, E.F., Jr., “Heat Capacities of Zinc Tungstate and Ferrous Tungstate from 5 to
550 K”, J. Chem. Thermodyn., 6, 763–780 (1974) (Crys. Structure, Thermodyn., Calculation, Experi-
mental, 39)
[1974Sen] Senegas, J., Galy, J., “The Double Oxide Fe2WO6. I. Crystal Structure and Filiation Structures” (in
French), J. Solid State Chem., 10, 5–11 (1974) (Crys. Structure, Experimental, 8)
[1976Jeh] Jehn, H., “Wolfram” (in German), in “Gase und Kohlenstoff in Metallen”, Springer-Verlag Berlin
Heidelberg New York, 552–563 (1976) (Phase Diagram, Phase Relations, Thermodyn., Review, Kinetics,
Phys. Prop., 112)
[1976Wei] Weitzel, H., “Magnetic Structures of NiNb2O6 and Fe2WO6” (in German), Acta Crystallogr., Sect. A:
Found. Crystallogr., A32, 592–597 (1976) (Crys. Structure, Experimental, Magn. Prop., 16)
[1977Eks] Ekstroem, T., Tilley, R.J.D., “Phase Relations in the Dioxide-Trioxide Region of Some 3d Transition
Metal-W-O Ternary Systems”, J. Solid State Chem., 22, 331–340 (1977) (Crys. Structure, Phase Relations,
Experimental, #, 30)

18 22 Fe–O–W
[1977Gel] Geller, R., Kostakis, G., Trumm, A., Weitzel, H., Schroecke, H., “Examinations in the System Fe-W-O”
(in German), Neues Jahrb. Mineral. Abh., 129(2), 211–231 (1977) (Phase Diagram, Phase Relations,
Experimental, Phys. Prop., #, 18)
[1977Pin] Pinto, H., Melamud, M., Shaked, H., “Magnetic Structure of Fe2WO6, a Neutron Diffraction Study”,
Acta Crystallogr., Sect. A: Found. Crystallogr., A33, 663–667 (1977) (Crys. Structure, Experimental,
Magn. Prop., 6)
[1978Gar] Gardiner, C.F., Chang, L.L.Y., “Phase Relations in the Systems Cr2O3-WO3 and Fe2O3-WO3”, J. Am.
Ceram. Soc., 61(7), 376 (1978) (Crys. Structure, Phase Diagram, Phase Relations, Experimental, 4)
[1978McC] McColm, I.J., Steadman, R., Wilson, S.J., “Iron-Promoted Phases in the Tungsten-Oxygen System”,
J. Solid State Chem., 23, 33–42 (1978) (Crys. Structure, Morphology, Phase Relations, Experimental, 27)
[1978Tru] Trumm, A., “Phase Diagram of the Fe2O3-WO3 System” (in German), Neues Jahrb. Mineral., Monatsh.,
(11), 481–484 (1978) (Phase Diagram, Phase Relations, Experimental, *) as quoted by [1989Rag] and
[1993Wal]
[1980Amo] Amosse, J., Mathieu, J.C., “The Enthalpies of Formation of FeWO4, MnWO4, and their Solid Solu-
tions”, J. Chem. Thermodyn., 12(7), 683–689 (1980) (Thermodyn., Experimental, 16)
[1980Kle] Kleykamp, H., “Thermodynamics of the Systems Fe-W, Fe-W-O and Fe-W-C” (in German), J. Less-
Common Met., 71(1), 127–134 (1980) (Thermodyn., Experimental, 23)
[1981Bha] Bharati, R., Singh, R.A., “The Electrical Properties of Fe2WO6”, J. Mater. Sci., 16, 511–514 (1981)
(Morphology, Experimental, Electr. Prop., 19)
[1982Lei1] Leiva, H., Dwight, K., Wold, A., “Preparation and Characterization of Conducting Iron Tungstates”,
J. Solid State Chem., 42, 41–46 (1982) (Crys. Structure, Experimental, Electr. Prop., Magn. Prop.,
Optical Prop., 23)
[1982Lei2] Leiva, H., Sieber, K., Khazai, B., Dwight, K., Wold, A., “Structural and Electronic Relationships
between Conducting Iron Niobates and Iron Tungstates”, J. Solid State Chem., 44, 113–118 (1982)
(Crys. Structure, Review, Theory, Electronic Structure, 20)
[1982Sie] Sieber, K., Kourtakis, K., Kershaw, R., Dwight, K., Wold, A., “Preparation and Photoelectronic
Properties of FeWO4”, Mater. Res. Bull., 17 (6), 721–725 (1982) (Crys. Structure, Experimental, Electr.
Prop., Optical Prop., 13)
[1983Kle] Kleykamp, H., “Experimental Aspects of Solid Galvanic Cell Methods for Thermodynamic Studies on
Alloys”, Ber. Bunsen-Ges. Phys. Chem., 87(9), 777–781 (1983) (Phase Diagram, Phase Relations, Ther-
modyn., Review, 32)
[1984Buh] Buhl, J.C., Willgallis, A., “Kinetics and Mechanism of Huebnerite (MnWO4) and Ferberite (FeWO4).
Crystallization under Hydrothermal Conditions”, Z. Naturforsch., Teil A, 39A (10), 963–965 (1984)
(Morphology, Experimental, Kinetics, 18)
[1984Tho1] Thomas, G., Ropital, F., “Influence of Gas on the Summary of Iron Tungstate Fe2WO6 1. Experimental
Study” (in French), Mater. Chem. Phys., 11, 549–562 (1984) (Morphology, Experimental, Magn.
Prop., 16)
[1984Tho2] Thomas, G., Ropital, F., “Influence of Gas on the Summary of Iron Tungstate Fe2WO6 2. Study of
Mechanism Solide-Solide” (in French), Mater. Chem. Phys., 11, 563–575 (1984) (Morphology, Experi-
mental, Kinetics, 9)
[1984Tho3] Thomas, G., Ropital, F., “Influence of Gas on the Summary of Iron Tungstate Fe2WO6 3. Study of
Machinery Gas-Solid” (in French), Mater. Chem. Phys., 11, 577–590 (1984) (Morphology, Calculation,
Experimental, Kinetics, 4)
[1985Har] Harrison, W.T.A., Chowdhry, U., Machiels, C.J., Sleight, A.W., Cheetham, A.K., “Preparation of Ferric
Tungstate and its Catalytic behavior Toward Methanol”, J. Solid State Chem., 60, 101–106 (1985) (Crys.
Structure, Experimental, Kinetics, 23)
[1986Nag] Nagender Naidu, S.V., Sriramamurthy, A.M., Rama Rao, P., “Fe-W (Iron-Tungsten)”, J. Alloy Phase
Diagrams, 2(3), 176–188 (1986) (Crys. Structure, Phase Diagram, Phase Relations, Review, 80)
[1987Gus] Gustafson, P., “A Thermodynamic Evaluation of the C-Fe-W System”, Metall. Trans. A, 18A(2), 175–188
(1987) (Phase Diagram, Phase Relations, Thermodyn., Assessment, 53)
[1987Mai] Maiti, G.C., Loechner, U., Baerns, M., “Studies on the Reduction of Iron/Tungsten Mixed Oxides”,
Thermochim. Acta, 112, 221–229 (1987) (Crys. Structure, Experimental, Kinetics, 61)
[1988Bag] Bagdavadze, D.I., Tsagareishvili, D.Sh., Tskhadaya, R.A., Gvelesiani, G.G., “Method of Computation of
Enthalpy Increment of Crystalline Inorganic Compounds at 0-298.15 K Temperature Range” (in
Russian), Izv. Akad. Nauk Gruz. SSR, Ser. Khim, 14(3), 199–206 (1988) (Thermodyn., Calculation,
Review, 8)

Fe–O–W 22 19
[1988Bir] Birchall, T., Hallett, C., Vaillancourt, A., Ruebenbauer, K., “A Study of Iron-Tungsten Oxides and Iron-
Chromium-Tungsten Oxides”, Can. J. Chem., 66(4), 698–702 (1988) (Crys. Structure, Experimental,
Electronic Structure, 18)
[1988Fer] Fernandez-Guillermet, A., “Thermodynamic Calculation of the Fe-Co-W Phase Diagram”,
Z. Metallkd., 79(10), 633–642 (1988) (Phase Diagram, Phase Relations, Assessment, Thermodyn., 34)
[1989Rag] Raghavan, V., “The Fe-O-W (Iron-Oxygen-Tungsten) System” in “Phase Diagrams of Ternary Iron
Alloys”, Indian Inst. Metal., Calcutta, 5, 349–354 (1989) (Crys. Structure, Phase Diagram, Review, #, 17)
[1989Wri] Wriedt, H.A., “The O-W (Oxygen-Tungsten) System”, Bull. Alloy Phase Diagrams, 10(4), 368–384
(1989) (Crys. Structure, Phase Diagram, Phase Relations, Assessment, Review, 154)
[1991Sch] Schmidbauer, E., Schanz, U., Yu, F.J., “Electrical Transport Properties of Mono- and Polycrystalline
FeWO4”, J. Phys.: Condens. Matter, (3), 5341–5352 (1991) (Crys. Structure, Experimental, Electr.
Prop., 28)
[1993Wal] Walczak, J., Rychlowska-Himmel, I., “Phase Equilibria in the Systems Fe2O3-WO3 and FeVO4-WO3”,
Thermochim. Acta, 221(1), 115–121 (1993) (Phase Diagram, Phase Relations, Experimental, #, 20)
[1993Yu] Yu, F., Schanz, U., Schmidbauer, E., “Single Crystal Growth of FeWO4 and CuWO4”, J. Cryst. Growth,
132, 606–608 (1993) (Crys. Structure, Morphology, Experimental, 13)
[1995Gus] Guskos, N., Sadlowski, L., Typek, J., Likodimos, V., Gamari-Seale, H., Bojanowski, B., Wabia, M.,
Walczak, J., Rychlowska-Himmel, I., “Magnetic and EPR Studies of α-, β- and γ-Fe2WO6 Phases at Low
Temperatures”, J. Solid State Chem., 120, 216–222 (1995) (Morphology, Experimental, Electronic
[1998Gus] Guskos, N., Typek, J., Wabia, M., Likodimos, V., Fuks, H., Rychlowska-Himmel, I., Walczak, J., “Phase
Transition Study in α-Fe2WO6 Compound by EPR”, Appl. Magn. Resonance, 14(2-3), 397–402 (1998)
(Morphology, Experimental, Electronic Structure, Magn. Prop., 13)
[1999Gus] Guskos, N., Likodimos, V., Glenis, S., Patapis, S.K., Palilis, L.C., Typek, J., Wabia, M., Rychlowska-
Himmel, I., “Electrical Transport and EPR Properties of the α, β, and γ Phases of Fe2WO6”, Phys. Rev. B,
60 (11), 7687–7690 (1999) (Morphology, Experimental, Electr. Prop., Magn. Prop., 27)
[2001Kaw] Kawanaka, H., Miyamoto, R., Nishihara, Y., “Electronic State of Iron Oxides FeWO4 (Mössbauer
Study)”, J. Magn. Soc. Jpn., 25(4, part 2), 715–718 (2001) (Morphology, Experimental, Electronic
Structure, Magn. Prop.) cited from abstract
[2003Sri] Sriraman, A.K., Tyagi, A.K., “A New Method of Fe2(WO4)3 Preparation and its Thermal Stability”,
Thermochim. Acta, 406, 29–33 (2003) (Crys. Structure, Experimental, 8)
[2003Yu] Yu, S.-H., Liu, B., Mo, M.-S., Huang, J.-H., Liu, X.-M., Qian, Y.-T., “General Synthesis of Single-Crystal
Tungstate Nanorods/Nanowires: A Facile, Low-Temperature Solution Approach”, Adv. Func. Mater., 13
(8), 639–647 (2003) (Crys. Structure, Morphology, Experimental, 55)
[2006Azi] Azimirad, R., Akhavan, O., Moshfegh, A.Z., “An Investigation on Electrochromic Properties of
(WO3)1–x-(Fe2O3)x Thin Films”, Thin Solid Films, 515, 644–647 (2006) (Morphology, Experimental,
Optical Prop., 16)
[2006Eji] Ejima, T., Banse, T., Takatsuka, H., Kondo, Y., Ishino, M., Kimura, N., Watanabe, M., Matsubara, I.,
“Microscopic Optical and Photoelectron Measurements of MWO4 (M = Mn, Fe, and Ni)”, J. Lumin.,
119–120, 59–63 (2006) (Morphology, Experimental, Optical Prop., 20)
[2006McK] McKenzie, K.J.D., Temuujin, J., McCammon, C., Senna, M., “Mechanochemical Activation of Mixtures
of Wolframite (FeWO4) with Carbon, Studied by 57Fe Mössbauer Spectroscopy”, J. Eur. Ceram. Soc., 26,
[2007Luo] Luo, W., Yu, T., Wang, Y., Li, Z., Ye, J., Zou, Z., “Enhanced Photocurrent-Voltage Characteristics of
WO3/Fe2O3 Nano-Electrodes”, J. Phys. D: Appl. Phys., 40, 1091–1096 (2007) (Crys. Structure, Morphol-
ogy, Experimental, Optical Prop., 33)
(1990)

Fe–O–Y 23 1
Iron – Oxygen – Yttrium

Pierre Perrot
Introduction
The Fe-O-Y system has provided much interest because of the ferrimagnetic garnet Y3Fe5O12,
known as YIG (Yttrium Iron Garnet) interesting for its applications in microwave devices.
This garnet has an incongruent melting and the knowledge of its crystallization field is of
interest for the single crystals growth. The main experimental results about the Fe-O-Y
diagram are presented in Table 1. A review was presented by [1989Rag]. No Calphad
assessment has been carried out.
Binary Systems
The Fe-Y system is accepted from the assessment of [1992Zha]. The Fe-O system is accepted
from [Mas2], where it is mainly based on the fundamental work of [1945Dar, 1946Dar]. Later
it has been carefully assessed by [1991Sun, 1995Kow]. The O-Y binary system is accepted from
[1990Car].
Solid Phases
Solid phases are presented in Table 2.

τ1,YFeO3 presents a congruent melting at 1720˚C and has a perowskite like structure,
explained by the small size of the Fe3+ ion which has the minimum radius (55 pm) to occupy
the octahedra sites of the oxygen lattice [2004Li] so that a stable perowskite structure cannot
be expected.
τ2,YFe2O4, was observed by [1975Kim] and its stability above 1010˚C was confirmed by
[1979Pie, 1980Mat]. However, [2004Kit] considers τ2 as metastable at 1100˚C.
τ3,Y3Fe5O12 presents an incongruent melting at 1555˚C under air and at 1582˚C under
pure O2 [1962Hoo]. Its non stoichiometry has been clearly put into evidence by [1961Hoo] on
samples water quenched from 1400˚C to 1540˚C and confirmed by [1980Vor]. Its composition
range varies from 37 to 37.5 mol% Y2O3, which means that Fe may substitute Y to a small
extent in the Y sublattice. Under low oxygen potentials, τ3 may loose oxygen leading to
Y3Fe5O12–δ (δ < 0.9). A DTA analysis of τ3 was carried out by [1963Ber], but it is probable
that the sample hold unreacted Fe2O3 because the observed peaks correspond to the oxygen
loss by Fe2O3 under air (1380˚C) and to the eutectic Fe3O4-τ3 (1469˚C).
τ5,YFe3+xO1.5(4+x) was synthesized by [2004Sug1] under radiofrequency Ar-O2 thermal
plasma and was shown to be paramagnetic [2004Sug2]. The values of x are not well deter-
mined because τ5 was contaminated with by-products such as γFe2O3 and τ1,YFeO3.

2 23 Fe–O–Y
The crystal parameter constant for 0.1 < x < 1 is an indication that τ5 may be a stoichiometric
compound whose exact composition has to be defined.
Quasibinary Systems
The αY2O3-αFe2O3 quasibinary system under air atmosphere is presented in Fig. 1 according
to the measurements of [1958Nie, 1962Hoo, 1975Lev]. This system is not truly binary because
Fe2O3 looses its oxygen to form Fe3O4 above a temperature which increases with the imposed
oxygen potential (1380˚C under air, 1460˚C under 0.1 MPa of O2 pressure). The Fe2O3-τ1,
YFeO3 part of the diagram is reproduced from [1975Lev]. The incongruent melting point of
τ3,Y3Fe5O12 depends also on the imposed oxygen potential: 1495˚C under pure CO2, 1555˚C
under air and 1582˚C under 0.1 MPa of O2 pressure [1961Hoo, 1962Hoo].
The liquidus lines in the Y3Fe5O12-Fe2O3-FeO part of the diagram, investigated by [1962Hoo],
are shown in Fig. 2 together with some solidus lines. The primary crystallization field of the
garnet τ3,Y3Fe5O12 is narrow, opposite to thee wide primary crystallization field of τ1,YFeO3.
The ternary eutectic E was measured at 1453˚C under 90 kPa of oxygen pressure. The ternary
transformation point U1 was measured at 1465˚C under an oxygen pressure lower than 10 Pa
which is the oxygen pressure of pure CO2 at the same temperature. The ternary transforma-
tion point U2 is estimated lower than 1420˚C under an oxygen pressure lower than 0.1 Pa
which is the oxygen pressure of the equilibrium FeO-Fe3O4 at 1420˚C. The maximum on the
EU1 line is estimated at a temperature higher than 1469˚C.
Isothermal Sections
The isothermal section at 1200˚C, mainly from [1975Kim], is represented in Fig. 3. The
isothermal section at 1000˚C shown in Fig. 4 is drawn from the thermodynamic measurements
of [1977Tre, 1978Pie, 1983Fet]. The difference between both sections comes from the phases in
equilibrium with τ1,YFeO3. Below 1078˚C, τ1 is in equilibrium with Fe and FeO, whereas above
1080˚C, τ1 is in equilibrium with FeO and Fe3O4. [2004Kit] presents a phase diagram at 1100˚
C which agrees with that presented at 1200˚C by [1975Kim], but considers τ2,YFe2O4 as a
metastable compound. Y is a stronger oxidizer than Fe and, whatever the temperature, pure Fe
and (Fe-Y) intermetallic compounds are in equilibrium with Y2O3. Between 700 and 1200˚C,
under low oxygen pressure (0.04 Pa), pure Fe oxidizes into FeO, Fe3O4 and Fe2O3 whereas
Y-doped Fe oxidizes with formation of τ1,YFeO3 and τ2,YFe2O4 [1999Cau, 2001Cau]. Under
0.1 MPa of O2 pressure, Fe-Y alloys are oxidized at 700-800˚C with formation of τ1,YFeO3 and
τ3,Y3Fe5O12 together with iron oxides [1999Li], so that Y cannot prevent the Fe oxidation. In
low oxygen pressures generated by H2-CO2 mixtures (~10–15 Pa at 700˚C), yttrium-iron oxides
are observed together with pure Y2O3 [1998Niu], which form a non protective layer.

Fe–O–Y 23 3
Thermodynamics
The interaction coefficient between O and Y in liquid iron has been calculated by [1973Buz]
from solubility measurements and found eO(Y) = (∂ log10 fO / ∂ mass% Y) = – 0.46 at 1600˚C
where fO = (mass% O in pure Fe / mass% O in the alloy). Such a value, very negative, means
that Y in liquid iron increases the oxygen solubility. The interaction coefficient, evaluated later
by [1985Tin] and reproduced in [1987Lon], two order of magnitude higher, is not credible. An
evaluation by [1995Ish] gives a result one order of magnitude higher. On the other hand, as Y
presents one of the greatest affinity for oxygen, the increase of the oxygen solubility in liquid
iron is quickly limited by the precipitation of Y2O3, whence a difficulty to evaluate the slope of
the curve fO vs {mass% Y}, which explains the discrepancy observed between the various
experimental results. The solubility product of Y2O3 in liquid Fe is given in Table 3.
The thermodynamic quantities of formation of τ1,YFeO3, τ2,YFe2O3.9 and τ3,Y3Fe5O12
from Fe, Y2O3 and O2 are given at 1200˚C in Table 3. The reactions are expressed for 1 mole
O2, which allows the comparison of the oxygen pressures at equilibria (Fe + Y2O3 + YFeO3),
(Fe + Y2O3 + YFe2O3.9) and (Fe + Y2O3 + Y3Fe5O12). For the sake of comparison, the oxygen
pressures at equilibria (Fe + FeO) and (FeO + Fe3O4) at 1200˚C are 1.20 · 10–7 and 7.20 · 10–5
Pa, respectively. As a consequence, only τ2,YFe2O3.9 may be in equilibrium with Fe and FeO at
1200˚C. τ1,YFeO3 may be in equilibrium with Fe, FeO and Fe3O4 whereas τ3,Y3Fe5O12 may be
in equilibrium with Fe3O4 and Fe2O3. The equilibria (Fe + Y2O3 + YFeO3) and (Fe + Y2O3 +
Y3Fe5O12) are metastable at 1200˚C. An investigation of the (Fe + Y2O3 + YFeO3) equilibrium
by [1977Tre, 1979Pie, 1985Sko] in a wider temperature range (900-1250˚C) shows that this
equilibrium is stable below 1010˚C, temperature of formation of τ2,YFe2O4. An extrapolation
of the oxygen pressure measured towards higher temperature shows that, at 1110˚C, the
oxygen pressure is the same for the equilibria (Fe + Y2O3 + YFeO3) and (Fe + FeO), which
means that, above 1110˚C, YFeO3 cannot be in equilibrium with Fe, in agreement with
the observation of [1975Kim] at 1200˚C. A further extension of the temperature range
(900-1250˚C) investigated by [1978Pie, 1979Pie] shows that the invariant equilibrium is at
1078˚C, temperature accepted in this report. The τ2,YFe2O4 was shown to be stable only
above 1010˚C [1979Pie]. However, [2004Kit] by investigating the Fe-Fe2O3-Y2O3 equilibria at
1100˚C under CO2-H2 atmospheres did not observe the formation of τ2 and concluded to its
instability. It is probable that the narrowness of the stability domain of τ2 at 1100˚C prevents
its observation. The thermodynamic properties of the ferrites τ1, τ2 and τ3, from [1979Pie,
1988Pie] are given in Table 4. A general review of the thermodynamic properties of the rare
earth and iron mixed oxides was presented by [1978Kat]. The stabilities of rare earth and iron
mixed oxides are compared in [1983Kim]. A general trend is the increase of stability with the
size of the rare earth ion, which puts iron and yttrium mixed oxides amongst the less stable of
the iron and rare earth mixed oxides. This trend has been modelled by [1984Pie] which
proposes empirical expressions of the thermodynamic quantities taking into account the ionic
radius of the rare earth ions.
The main experimental works regarding properties are summarized in Table 5. Y may be used
as deoxidizer in steelmaking. Although it is known as one the best deoxidizer, its use is limited
by its price.
4 23 Fe–O–Y
τ1,YFeO3 has been proposed for a number of applications from catalysis, reflective coat-
ings, electrode material to fast ion conductor. It may be synthesized by ceramics methods
(Fe2O3 + Y2O3 annealed several days above 1000˚C) but more efficiently at lower temperature
(2 h at 800˚C) from a fused salts flux YCl3 + FeCl3 + Li2O [1996Par].
τ2,YFe2O4 is a ferrimagnetic compound whose Neel temperature is 205 K. Below the Neel
point, the non stoichiometric ferrite τ2,YFe2O3.9 presents extra reflections in the electron
diffraction pattern [1980Mat] which may possibly be related to the magnetic behavior known
as “parasitic ferrimagnetism”.
τ3,Y3Fe5O12, a ferrimagnetic garnet (YIG) whose Neel temperature is 275˚C, has led to very
intensive studies on the crystallographic, magnetic and electrical properties. It is very effective
as microwave filter, as well as transducer and transmitter of acoustic energy. YIG is also of
interest because its ferrimagnetic properties are tunable by partial substitution of non mag-
netic ions for magnetic ones at different sites. It may be synthesized from homogenized
mixtures of hematite and yttria, but the garnet formation starts above 1000˚C and is complete
at 1400˚C [2000Pet]. It has been prepared by combustion synthesis [2000Kuz] from a mixture
(Y2O3 + Fe2O3 + Fe + NaClO4) followed by an annealing for 4 h at 1450˚C or grown by laser
heating [2003Che]. Nanoparticles have also been obtained by a sol-gel combustion synthesis
(metal nitrates + citric acid) process [2007Hos]. TIG crystals are never grown from the melt,
even when undercooled at temperatures lower than 1582˚C, the peritectic temperature of the
Fe2O3-YIG system [2002Nag]. The first phase to precipitate is always the pseudo-perowskite
YFeO3. The formation of YIG from the melt needs hyperquenching. Single crystals are easily
grown in a PbO flux [1958Nie], the most convenient composition for the bath being 52.5 PbO,
44 Fe2O3, 3.5 Y2O3 (in mol%).
τ4,Y12Fe32O2 is ferromagnetic [1976Dar] with a Curie temperature at 182 K; its saturation
magnetization at 4.2 K is 32.4 B per unit formula. τ4 is sometimes encountered as a by product
in the preparation of τ3,Y3Fe5O12 [2000Tak].
τ5,YFe3+xO1.5(4+x) is a paramagnetic compound [2004Sug2].
Miscellaneous
The formation mechanism of YIG from its oxides has been investigated by [2000Pet]. It may
be described by a two-step process:
3 Y2O3 + 5 Fe2O3 Ð 6 YFeO3 + 2 Fe2O3 Ð 2 Y3Fe5O12
The orthoferrite formation starts at 816 ± 25˚C whereas the garnet formation started at
1011 ± 25˚C.
The YIG has also been prepared in 10 min by microwave heating (2.45 GHz) of a mixture
Y2O3 + Fe3O4 in the ratio Y/Fe = 3/5 under air atmosphere [1997Ost, 2001Pee]. Fe3O4 is used
instead of Fe2O3 because hematite is a poor microwave absorber. During the synthesis,
orthoferrite YFeO3 appears always as an intermediate compound and even YFe2O4 may be
observed.
The temperature dependence of electrical conductivity and Seebeck coefficient was
measured on YIG single crystals for various orientations and different degrees of perfection
[2003Lom]. The electrical properties of YIG are completely determined by the mechanism of

Fe–O–Y 23 5
scattering of charge carriers and by their energy spectrum. The intensity ratio of coherent and
incoherent X-ray scattering characterizes the fraction of conduction electrons in a given
sample.
. Table 1
Investigations of the Fe-O-Y Phase Relations, Structures and Thermodynamics
[1958Nie] Thermal analysis, crystal growth of 1400-1750˚C, the Fe2O3-YFeO3 phase

Y3Fe5O12 in a PbO flux diagram
[1961Hoo] XRD, thermogravimetry, thermal analysis 1150-1550˚C, Fe2O3-YFeO3-Fe3O4 under
(water quenching) air
[1962Hoo] Thermal analysis, liquidus determination 1400-1600˚C, Fe2O3-YFeO3-FeO under
O2, air and CO2 atmospheres
[1963Ber] Differential thermal analysis < 1500˚C, Y3Fe5O12, under air
[1975Kim] XRD, chemical analysis, emf 1200˚C, Fe-Fe2O3-Y2O3 diagram, ΔfG˚
measurements (YFe2O3.9, YFeO3, Y3Fe5O12)
[1977Tre] emf measurements (Y2O3 stabilized ZrO2 900-1100˚C, pO2 at equilibrium (Fe +
as solid electrolyte) Y2O3 + YFeO3)
[1978Pie] emf measurements (CaO stabilized ZrO2 900-1250˚C, ΔfG˚(YFeO3 and Y3Fe5O12)
as solid electrolyte)
[1979Pie] emf measurements (CaO stabilized ZrO2 900-1250˚C, ΔfG˚(YFeO3, Y3Fe5O12 and
as solid electrolyte) YFe2O4)
[1980Vor] XRD, microscopy, Seebeck coefficient 800-1400˚C, Y3Fe5O12, departure to
measurements stoichiometry
[1983Fet] XRD, thermogravimetry 1000˚C, Y3Fe5O12, reduction under
H2-H2O atmospheres
[1985Sko] EMF measurements (CaF2+YF3 or 900-1150˚C, ΔfG˚(YFeO3 and Y3Fe5O12)
CaF2+YOF as solid electrolyte)
[1985Tin, XRD, solubility measurements in (Fe,Y) 1575-1625˚C, < 0.2 mass% Y,
1987Lon] liquid alloys < 0.2 mass% O
[1995Ish] XRD, solubility measurements in (Fe,Y) 1600-1700˚C, < 0.11 mass% Y,
liquid alloys < 0.2 mass% O
[2004Kit] XRD, thermogravimetry 1100˚C, Fe-Fe2O3-Y2O3 diagram, CO2-H2
and CO2-O2 atmospheres

6 23 Fe–O–Y
. Table 2
Pearson
Symbol/
(αδFe) cI2
(δFe) Im3m a = 293.15 pure Fe at 1394˚C
1538 - 1394 W
a = 286.65
(αFe) (Ferrite) pure Fe at 25˚C [Mas2, V-C2]
< 912
(εFe) hP2 a = 246.8 at 25˚C, > 13 GPa
P63/mmc c = 396.0 [Mas2]
Mg
(γFe) (Austenite) cF4 a = 364.67 at 915˚C [V-C2, Mas2]
1394 - 912 Fm3m
Cu
(βY) cI2 a = 407 dissolves up to 30.4 at.% O at 1560˚C
1522 - 1478 Im3m [1990Car, 1992Zha]
W
(αY) hP2 a = 364.82 Dissolves up to 14.3 at.% O at 1180˚C
< 1478 P63/mmc c = 573.18 [1990Car, 1992Zha]
Mg
YFe2 cF24 a = 735.6 [Mas2] cubic Laves phase
≲ 1125 Fd
3m
MgCu2
YFe3 hR36 a = 513.3 [1989Rag]
≲ 1330 R
3m c = 2460.0
PuNi3
Y6Fe23 cF116 a = 1212.0 [1989Rag]
≲ 1300 Fm3m
Th6Mn23
βY2Fe17 hP38 a = 846.3 [1989Rag, 1992Zha]
≲ 1400 P63/mmc c = 828.2
Th2Ni17
αY2Fe17 hR57 a = 846.0 [1989Rag, 1992Zha]
R
3m c = 1241.0
Th2Zn17
Fe1–xO (Wüstite) cF8 a = 431.0 x = 0.05
1422 - 569 Fm3m a = 429.3 x = 0.12 [1989Rag]
NaCl

Fe–O–Y 23 7
Pearson
Symbol/
Fe3O4 oP56 a = 1186.8 [V-C2, 1989Rag]

< 580 Pbcm b = 1185.1
Fe3O4 c = 1675.2
βFe3O4 (Magnetite) cF56 inverse spinel
1597 - 580 Fd
3m a = 854.5 at 1000˚C
MgAl2O4 a = 839.6 at 25˚C
αFe2O3 (Hematite) hR30 a = 503.42 [1989Rag]
< 1457 R
3c c = 1374.83
αAl2O3
(Corundum)
βFe2O3 cI80 a = 939.3 metastable phase
Ia
3 [V-C2, 1989Rag]
βMn2O3
(Bixbyite)
γFe2O3 (Maghemite) cF56 a = 834 metastable phase [1989Rag]
Fd
3m
MgAl2O4
βY2O3 hP* a = 381.3 at 2380˚C [1990Car]
2430 - 2325 P
3m1 c = 609
γY2O3 mC* a = 1391 high pressure phase
C2/m b = 348.3 (> 250 MPa at 1000˚C) [1990Car]
c = 859.3
αY2O3 (Yttria) cI80 a = 1060.73 59.3 to 60 at.% O [1990Car]
< 2325 Ia
3
βMn2O3
* τ1, YFeO3 oP20 a = 528.19 ± 0.02 [1965Cop] Distorted perowskite
< 1720 Pbmn b = 559.57 ± 0.05 structure
c = 760.46 ± 0.04
cI* a = 1059.6 [1957Cur] (Metastable?)
* τ2, YFe2O4 hR* a = 609.0 ± 0.4 [1975Kim]. Probably YFe2O4–x
R
3m c = 2478.8 ± 0.4 (x < 0.1)
* τ3, Y3Fe5O12 (Yttrium cI160 quenched from 1400˚C
Iron Garnet) Ia
3d
< 1555 (under air) a = 1237.4 37 mol% Y2O3
a = 1237.8 37.5 mol% Y2O3 [1961Hoo]

8 23 Fe–O–Y
Pearson
Symbol/
* τ4, Y12Fe32Ox cI46 x<2

Im3m a = 888.32 ± 0.05 x = 2 [1976Dar]
* τ5, YFe3+xO1.5(4+x) cF* a = 486.7 x = – 0.6
a = 485.5 0.1 < x < 1 [2004Sug1]
. Table 3
Temperature Quantity, per mol of O2

Reaction or Transformation [˚C] [J, mol, K] Comments
(5/3) Fe + (5/12) Y2O3 + O2 Ð (5/6) 1200 ΔfG˚ = – 337500 ± 800 [1975Kim]

YFe2O3.9
pO2 = 1.08 · 10–7 Pa
1010 - 1250 ΔfG˚ = – 549150 + 144.2 T [1979Pie]
pO2 = 1.15 · 10 –7
Pa at
1200˚C
(4/3) Fe + (2/3) Y2O3 + O2 Ð (4/3)YFeO3 1100 ΔfG˚ = – 350100 [2004Kit]
pO2 = 4.79 · 10–9 Pa
ΔfG˚ = – 333600 ± 1000 [1975Kim]
1200 pO2 = 1.48 · 10 –7
Pa
ΔfG˚ = – 561700 + 153.1 T [1978Pie]
1078 - 1250 pO2 = 4.24 · 10 –9
Pa at
1100˚C
pO2 = 1.19 · 10–7 Pa at
1200˚C
18 YFeO3 + 4 Fe3O4 + O2 Ð 6Y3Fe5O12 1100 ΔfG˚ = –180850 [2004Kit]
pO2 = 1.32 · 10 –2
Pa
900 - 1250 ΔfG˚ = – 504750 + 232.2 T [1979Pie]
pO2 = 8.47 · 10 –3
Pa at
1100˚C

Fe–O–Y 23 9
Temperature Quantity, per mol of O2

Reaction or Transformation [˚C] [J, mol, K] Comments
(4/3) Fe + (2/5) Y2O3 + O2 Ð (4/15) 1200 ΔfG˚ = – 322400 ± 600 [1975Kim]

Y3Fe5O12
pO2 = 3.69 · 10–7 Pa
900 - 1250 ΔfG˚ = – 554200 + 156.0 T [1979Pie]
pO2 = 3.13 · 10 –7
Pa at
1200˚C
Y2O3 Ð 2 {Y} + 3 {O} (in liquid Fe) 1575 - 1625 ΔrG˚ = 1793000 – 658.0 T [1985Tin]
(Standard state: 1 mass% in
Fe)
{mass% Y}2 {mass% O}3 1600 - 1700 4.19 – (18810 / T) [1995Ish]
. Table 4
Thermodynamic Properties of Single Phases
Temperature Range Property, per mole of atoms

Phase [˚C] [J, mol, K] Comments
(1/5)YFeO3 25 ΔfH ˚ = – 273200 ± 200 [1979Pie]

ΔfS ˚ = – 50.5 ± 1.0
S˚ = 24.902 [1988Pie]
900-1250 Cp = 21.072 + 3.764 · 10 T – 1.996 · 10 T
–3 5 –2
(1/7) YFe2O4 1010-1250 ΔfH ˚ = – 230800 ± 800 [1979Pie]

ΔfS ˚ = – 43.8 ± 2.0
(1/20) Y3Fe5O12 25 ΔfH ˚ = – 245600 ± 150 [1979Pie]
ΔfS ˚ = – 49.9 ± 0.60
S˚ = 23.214 [1988Pie]
900-1250 Cp = 22.749 + 2.858 · 10 T – 1.511 · 10 T
–3 5 –2

10 23 Fe–O–Y
. Table 5
Investigations of the Fe-O-Y Materials Properties
[1957Cur] XRD, powder diffraction τ1,YFeO3, crystal structure

[1957Gel] XRD, single crystal τ3,Y3Fe5O12, crystal structure
[1965Cop] XRD, powder diffraction τ1,YFeO3, crystal structure
[1976Dar] XRD, powder diffraction τ4,Y12Fe32O2, crystal structure
[1980Mat] Electron diffraction τ2,YFe2O4, parasitic ferrimagnetism
[1988Pie] CVD, transport by Cl or CCl4 at 800- τ1,YFeO3 and τ3,Y3Fe5O12, single crystal
1000˚C growth
[1992Boc] XRD, XPS τ1,YFeO3, electronic structure
[1996Par] XRD, SEM, energy dispersive analysis τ1,YFeO3 synthesis by mixture YCl3 + FeCl3 +
by X-Rays (EDAX), Fourier transform IR Li2O (2 h at 800˚C)
(FT-IR)
[1997Ost] XRD, magnetism, monomodal < 500˚C, synthesis of Y3Fe5O12, YFeO3 and
microwave oven at 2.45 GHz YFe2O4 from oxides
[1998Niu] High temperature XRD, 600-700˚C, 15 and 30 mass% Y in Fe under
thermogravimetry H2-CO2 atmospheres
[1999Cau, High temperature XRD, 700˚C, Y-doped and undoped Fe under
2001Cau] thermogravimetry 0.04 Pa of O2 pressure
[1999Li] High temperature XRD, 700-800˚C, 15 and 30 mass% Y in Fe under
thermogravimetry 0.1 MPa of O2 pressure
[2000Kuz] XRD, SEM, EDAX, IR and Mössbauer τ3,Y3Fe5O12, combustion synthesis from Y2O3
spectrometry + Fe2O3 + Fe + NaClO4 then annealing 4 h at
1450˚C
[2000Pet] High temperature XRD, Rietveld < 1400˚C, formation mechanism of Y3Fe5O12
analysis in situ from 3 Y2O3 + 5 Fe2O3
[2000Tak] XRD, TEM, SAES (Selected Area Nanocrystalline Y3Fe5O12 prepared by the
Electron Diffraction) alkoxide method
[2001Pee] Multimodal microwave oven at 900-1300˚C, synthesis of Y3Fe5O12 from Y2O3
2.45 GHz + Fe3O4 under air
[2002Nag] XRD, SEM, micrography Crystallization from undercooled Y3Fe5O12
melts below 1582˚C
[2003Che] XRD, SQUID (Superconducting Composition of Y3Fe5O12 obtained by Laser
Quantum Interference Device) Heated Pedestal Growth
[2003Lom] Resistivity, thermoelectric power, 200-410˚C, Y3Fe5O12 single crystal
X-ray scattering

Fe–O–Y 23 11
[2004Sug1, XRD, TEM, Mössbauer, saturation τ5,YFe3+xO1.5(4+x), prepared by rf Ar-O2

2004Sug2] magnetization thermal plasma
[2004Wu] XRD, SEM, TEM, FT-IR, Raman YFeO3 nano prepared by self-propagating
spectroscopy, DSC, TGA combustion synthesis
[2007Hos] XRD, SEM, DTA/TGA Y3Fe5O12, nanoparticles prepared by a sol-gel
autocombustion process

12 23 Fe–O–Y
. Fig. 1
Fe-O-Y. The Y2O3-Fe2O3 quasibinary system under air atmosphere

Fe–O–Y 23 13
. Fig. 2
Fe-O-Y. Liquidus surface projection

14 23 Fe–O–Y
. Fig. 3
Fe-O-Y. Phase equilibria at 1200˚C

Fe–O–Y 23 15
. Fig. 4
Fe-O-Y. Phase equilibria at 1000˚C

16 23 Fe–O–Y
References
[1945Dar] Darken, L.S., Gurry, G.W., “The System Iron-Oxygen. I- The Wuestite Field and Related Equilibria”,
J. Am. Chem. Soc., 67, 1398–1412 (1945) (Experimental, Phase Diagram, Thermodyn., *, 26)
[1946Dar] Darken, L.S., Gurry, G.W., “The System Iron-Oxygen. II- Equilibria and Thermodynamics of Liquid
Oxides and Other Phases”, J. Am. Chem. Soc., 68, 798–816 (1946) (Experimental, Phase Diagram,
Thermodyn., *, 24)
[1957Cur] Curtis, C.E., “Properties of Yttrium Oxide Ceramics”, J. Am. Ceram. Soc., 40(8), 274–278 (1957) (Crys.
[1957Gel] Geller, S., Gilleo, M.A., “The Crystal Structure and Ferrimagnetism of Yttrium-Iron Garnet,
Y3Fe2(FeO4)3”, J. Phys. Chem. Solids, 3, 30–36 (1957) (Crys. Structure, Experimental, 28)
[1958Nie] Nielsen, J.W., Dearborn, E.F., “The Growth of Single Crystals of Magnetic Garnets”, J. Phys. Chem.
Solids, 5, 202–207 (1958) (Phase Diagram, Phase Relations, Experimental, 8)
[1961Hoo] Van Hook, H.J., “Phase Relations in the System Fe2O3-Fe3O4-YFeO3 in Air”, J. Am. Ceram. Soc., 44(5),
208–214 (1961) (Experimental, Phase Diagram, 6)
[1962Hoo] Van Hook, H.J., “Phase Relations in the Ternary Systems Fe2O3-FeO-YFeO3”, J. Am. Ceram. Soc., 45(4),
162–165 (1962) (Experimental, Phase Diagram, 9)
[1963Ber] Beretka, J., “Differential Thermal Analysis of Yttrium Iron Garnet”, J. Phys. Chem. Solids, 24(1), 169–171
[1965Cop] Coppens, P., Eibschutz, M., “Determination of the Crystal Structure of Yttrium Orthoferrite and
Refinement of Gadolinium Orthoferrite”, Acta Crystallogr., 19, 524–531 (1965) (Crys. Structure,
Experimental, 13)
Iron at 1600˚C”, Int. Symp. Metall. Chem. - Appl. Ferrous Metall., Sheffield, July 1971, Iron and Steel Inst,
London, 173–177 (1973) (Phase Relations, Thermodyn., Review, 8)
[1975Lev] Levin, E.M., McMurdie, H.F., Phase Diagrams for Ceramists, Am. Ceram. Soc. Vol. 3, p. 44, Fig. 4212
(1975), as quoted in Cassedanne, J., Compt. Rend. Acad. Sci., Paris, 252, 3262 (1961)
[1975Kim] Kimizuka, N., Katsura, T., “Standard Free Energy of Formation of YFeO3, Y3Fe5O12, and a New
Compound YFe2O4 in the Fe-Fe2O3-Y2O3 System at 1200˚C”, J. Solid State Chem., 13, 176–181 (1975)
(Experimental, Thermodyn., Phase Diagram, 8)
[1976Dar] Dariel, M.P., Pickus, M.R., “Structural and Magnetic Study of Some Oxygen Stabilised Rare-Earth-Iron
Intermetallic Compounds”, J. Less-Common Met., 50, 125–137 (1976) (Crys. Structure, Experimental,
18)
[1977Tre] Tretyakov, Yu.D., Kaul, A.R., Portnoy, V.K., “Formation of Rare Earth and Yttrium Orthoferrites:
A Thermodynamic Study”, High Temp. Sci., 9, 61–70 (1977) (Experimental, Phase Relations, Thermo-
dyn., 19)
[1978Kat] Katsura, T., Sekine, K., Kitayama, K., Sugihara, T., Kimizuka, N., “Thermodynamic Properties of
Fe-Lanthanoid-O Compounds at High Temperatures”, J. Solid State Chem., 23, 43–57 (1978) (Phase
Diagrams, Thermodyn., Review, 24)
[1978Pie] Piekarczyk, W., Weppner, W., Rabenau, A., “Dissociation Pressure and Gibbs Energy of Formation of
Y2Fe5O12 and YFeO3”, Mater. Res. Bull., 13, 1077–1083 (1978) (Experimental, Thermodyn., 11)
[1979Pie] Piekarczyk, W., Weppner, W., Rabenau, A., “Solid State Electrochemical Study of Phase Equilibria and
Thermodynamics of the Ternary System Y-Fe-O at Elevated Temperatures”, Z. Naturforsch. A, 34(4),
430–436 (1979) (Experimental, Phase Diagram, Thermodyn., 23)
[1980Mat] Matsui, Y., “Extra Electron Reflections Observed in YFe2O4, YbFe2O4, Yb2Fe3O7 and Yb3Fe4O10”,
J. Appl. Crystallogr., 13, 395–397 (1980) (Crys. Structure, Experimental, 8)
[1980Vor] Vorobev, Yu.P., Dragoshanskaya, T.I., Matskevich, S.L., Men, A.N., “Determination of Departure of
Y3Fe5O12, Gd3Fe5O12 and Y1.5Gd1.5Fe5O12 from Stoichiometry at 800-1400˚C”, Inorg. Mater., 16(6),
754–758 (1980), translated from Izv. Akad.. Nauk SSSR, Neorgan. Mater., 16(6), 1083–1087 (1980) (Crys.
[1983Fet] Fetisov, V.B., Dvinina, M.A., Vorobev, Yu.P., Sapozhnikova, T.V., Shapovalov, A.G., Pankov, Yu.V.,
Sovkov, V.E., Men, A.N., “Phase Equilibria in the Y-Fe-O System at 1270K”, Inorg. Mater., 19(11),
1650–1652 (1983), translated from Izv. Akad. Nauk SSSR, Neorgan. Mater., 19(11), 1871–1874 (1983)
(Phase Relations, Experimental, 12)

Fe–O–Y 23 17
[1983Kim] Kimizuka, N., Yamamoto, A., Ohashi, H., Sugihara, T., Sekine, T., “The Stability of the Phases in the
Ln2O3-FeO-Fe2O3 Systems which are Stable at Elevated Temperatures (Ln: Lanthanide Elements and
Y)”, J. Solid State Chem., 49, 65–76 (1983) (Review, Thermodyn., 30)
[1984Pie] Piekarczyk, W., Rabenau, A., Weppner, W., “Relations between the Thermodynamic Potentials for the
Formation of Yttrium and Rare Earth Iron Perovskites and Garnets and the Ionic Radii of Yttrium and
the Rare Earth Elements”, (in German), Z. Anorg. Allg. Chem., 516, 153–158 (1984) (Review, Calcula-
tion, Thermodyn., 22)
[1985Sko] Skolis, Yu.Ya., Kitsenko, S.V., Levitskii, V.A., “Measurement of the Thermodynamic Properties of
Yttrium Ferrites by the E.m.f. Method with a Solid Fluoride-ion Electrolyte”, Russ. J. Phys. Chem., 59(9),
1403–1404 (1985), translated from Zh. Fiz. Khim., 59(9), 2356–2358 (1985) (Experimental, Thermo-
dyn., 9)
[1985Tin] Ting, D., Longmei, W., “Thermodynamics of Fe-Y-S, Fe-Y-O and Fe-Y-S-O Metallic Solutions”, J. Less-
Common Met., 110, 179–185 (1985) (Experimental, Phase Relations, Thermodyn., 10)
[1987Lon] Longmei, W., Ting, D., Kexiang, Y., “A Study of Thermodynamics and Phase Equilibria in Order to
Predict the Behavior of Yttrium in Iron and Steel”, Inorg. Chim. Acta, 140(1-2), 189–191 (1987)
(Experimental, Phase Relations, Thermodyn., 8)
[1988Pie] Piekarczyk, W., “Thermodynamic Model of Chemical Vapour Transport and its Application to some
Ternary Compounds”, J. Cryst. Growth, 89, 267–286 (1988) (Experimental, Review, Calculation, Ther-
modyn., 27)
[1989Rag] Raghavan, V., “The Fe-O-Y (Iron-Oxygen-Yttrium) System”, Phase Diagrams of Ternary Iron Alloys, Ind.
Inst. Metals, Calcutta, 5, 355–365 (1989) (Phase Diagram, Crys. Structure, Review, 22)
[1990Car] Carlson, O.N., “The O-Y (Oxygen-Yttrium) System”, Bull. Alloy Phase Diagrams, 11(1), 61–66, (1990)
(Phase Diagram, Crys. Structure, Thermodyn., Calculation, 28)
Diagram, Thermodyn., Assessment, Calculation, 53)
[1992Boc] Bocquet, A.E., Fujimori, A., Mizokawa, T., Saitoh, T., Namatame, H., Suga, S., Kimizuka, N., Takeda, Y.,
Takano, M., “Electronic Structure of SrFe4+O3 and Related Fe Perovskite Oxides”, Phys. Rev. B, 45(4),
1561–1570 (1992) (Experimental, Electronic Structure, 35)
[1992Zha] Zhang, W., Liu, G., Han, K., “The Fe-Y (Iron-Yttrium) System”, J. Phase Equilib., 13(3), 304–308 (1992)
(Phase Diagram, Crys. Structure, Review, 29)
[1995Ish] Ishii, F., Ban-ya, S., “Equilibrium between Yttrium and Oxygen in Liquid Iron and Nickel”, ISIJ Int.,
35(3), 280–285 (1995), translated from Tetsu to Hagane, 80(5), 359–364 (1994) (Phase Relations,
Thermodyn., Experimental, 29)
[1995Kow] Kowalski, M., Spencer, P.J., “Thermodynamic Revaluation of the Cr-O, Fe-O and Ni-O Systems:
Remodelling the Liquid, BCC and FCC Phases”, Calphad, 19(3), 229–243 (1995) (Assessment, Phase
Diagram, Thermodyn., Review, 47)
[1996Par] Parkin, I.P., Komarov, A.V., Fang, Q., “Alternative Solid State Routes to Mixed Metal Oxides (LnCrO3,
LnFeO3)”, Polyhedron, 15(18), 3117–3121 (1996) (Crys. Structure, Phase Relations, Experimental, 10)
[1997Ost] Ostorero, J., Gasgnier, M., Petit, A., “Yttrium Iron Garnet and Y, Fe Oxides Synthesized by Microwave
Monomode Energy Transfert”, J. Alloys Compd., 262/263, 275–280 (1997) (Crys. Structure, Phase
[1998Niu] Niu, Y., Yan, R.Y., Fu, G.Y., Wu, W.T., Gesmundo, F., “The Oxidation of two Fe-Y Alloys under Low
Oxygen Pressures at 600-800˚C”, Oxid. Met., 49, 91–114 (1999) (Experimental, Phase Relations,
Kinetics, 26)
[1999Cau] Caudron, E., Buscail, H., Riffard, F., “Initial Oxidation Stages of Yttrium-Implanted Pure Iron at 700˚C
by In-situ High Temperature X-Ray Diffraction”, Eur. Phys. J. - Applied Phys., 8(3), 233–240 (1999)
(Experimental, Phase Relations, Kinetics, 38)
[1999Li] Li, Y.S., Niu, Y., Gesmundo, F., “High Temperature Scaling of Binary Fe-Y Alloys in Pure Oxygen”, High
Temp. Mater. Proc., 18(3), 185–195 (1999) (Experimental, Phase Relations, Kinetics, 29)
[2000Kuz] Kuznetsov, M.V., Pankhurst, Q.A., Parkin, I.P., Affleck, L., Morozov, Y.G., “Self-Propagating High
Temperature Synthesis of Yttrium Iron Chromium Garnets Y3Fe5–xCrxO12 (x < 0 < 0.6)”, J. Mater.
Chem., 10, 755–760 (2000) (Crys. Structure, Phase Relations, Experimental, 30)
[2000Pet] Petras, L., Preisinger, A., “Reaction Kinetics of Yttrium Iron Garnet Formation in Air up to 1400˚C”,
Mater. Sci. Forum, 321–324, 368–373 (2000) (Experimental, Phase Relations, Kinetics, 4)

18 23 Fe–O–Y
[2000Tak] Taketomi, S., Sai, Z.R., Ohuchi, F.S., “Electron Diffraction of Yttrium Iron Oxides Nanocrystals
Prepared by the Alkoxide Method”, J. Magn. Magn. Mater., 217, 5–13 (2000) (Experimental, Phase
Relations, Morphology, Nano, 22)
[2001Cau] Caudron, E., Buscail, H., “Initial Stages of Oxidation of Yttrium-Implanted Pure Iron and Various
Steels at 700˚C under Low Oxygen Partial Pressure”, Corros. Sci., 43(8), 1477–1495 (2001) (Experimen-
tal, Phase Relations, Kinetics, 39)
[2001Pee] Peelamedu, R.D., Roy, R., Agrawal, D.K., “Reaction Kinetics and Anisothermal Effects in Microwave
Fields: System Y2O3-Fe3O4”, J. Mater. Res., 16(10), 2770–2772 (2001) (Experimental, Phase Relations,
Kinetics, 13)
[2002Nag] Nagashio, K., Kuribayashi, K., “Phase Selection in the Undercooled Peritectic Y3Fe5O12 Melt”, Acta
Mater., 50, 1973–1981 (2002) (Experimental, Phase Relations, Transport Phenomena, 27)
[2003Che] Chen, C., Hu, C.C., “Quantitative Analysis of YIG, YFeO3 and Fe3O4 in LHPG-Grown YIG Rods”,
J. Cryst. Growth, 249, 245–250 (2003) (Crys. Structure, Phase Relations, Magn. Prop., 12)
[2003Lom] Lomako, I.D., Pavlov, V.I., Shishkin, N.Ya., “Transport Properties of Y3Fe5O12 Garnet Crystals”,
Crystallography Reports, 48(1), 116–123 (2003), translated from Kristallografiya, 48(1), 121–129
(2003), (Experimental, Electric Prop., Transport Phenomena, 22)
[2004Kit] Kitayama, K., Sakaguchi, M., Takahara, Y., Endo, H., Ueki, H., “Phase Equilibrium in the System
Y-Fe-O at 1100˚C”, J. Solid State Chem., 177(6), 1933–1938 (2004) (Experimental, Phase Diagram,
Thermodyn., 17)
[2004Li] Li, C., Soh, K.C.K., Wu, P., “Formability of ABO3 Perovskites”, J. Alloys Compd., 372, 40–48 (2004)
(Crys. Structure, Theory, 28)
[2004Sug1] Sugasava, M., Kikukawa, N., Nagano, Y., Kayano, N., Kimura, T., “Characterisation of the Y-Fe-O
Ultrafine Particles Containing a New Compound YFe3+xO1.5(4+x) Sythesized by rf Thermal Plasmas”,
Ceramic Intl., 30(4), 515–523 (2004) (Crys. Structure, Magn. Prop., Experimental, 13)
[2004Sug2] Sugasava, M., Kikukawa, N., Nagano, Y., Kayano, N., Kimura, T., “Magneic Properties of Y-Fe-O
Ultrafine Particles YFe3+xO1.5(4+x) Sythesized by rf Thermal Plasma”, Ceramic Intl., 30(8), 2191–2201
(2004) (Crys. Structure, Magn. Prop., M‘ssbauer, Experimental, 16)
[2004Wu] Wu, L., Yu, J.C., Zhang, L., Wang, X., Li, S., “Selective Self-propagating Combustion Synthesis of
Hexagonal and Orthorhombic Nanocrystalline Yttrium Iron Oxide”, J. Solid State Chem., 177(10),
3666–3674 (2004) (Crys. Structure, Experimental, Magn. Prop., Morphology, Nano, Phase Relations,
43)
[2007Hos] Hosseini Vajargah, S., Madaah Hosseini, H.R., Nemati, Z.A., “Preparation and Characterization of
Yttrium Iron Garnet (YIG) Nanocrystalline Powders by Auto-Combustion of Nitrate-Citrate Gel”,
J. Alloys Compd., 430(1-2), 339–343 (2007) (Crys. Structure, Experimental, Nano, 18)
(1990)

Fe–O–Zr 24 1
Iron – Oxygen – Zirconium

Olga Fabrichnaya
Introduction
The ZrO2 and FeO are the major components in systems significant for understanding
whether refractories would react with metallurgical slag and whether the melt in the active
zone of a nuclear reactor would react with its housing material and with a device designed to
keep the melt in active zone of a reactor in case of severe nuclear accident. The phase relations
in the Zr-Fe-O system are also of interest because of deoxidation and inclusion shape control
in steels. Stabilized ZrO2 are widely used as oxygen sensors [2001Cao]. Fe2O3 stabilization of
ZrO2 decreases operating temperature down to 320˚C. The ZrO2-Fe2O3 samples prepared by
co-precipitation followed by calcination revealed catalytic activity for different organic chem-
istry reactions [1981Jin, 1993Wu].
The phase relations in the FeO-ZrO2 system were experimentally studied in an inert
atmosphere by [1957Fis]. Recently the phase relations in this system were studied by
[2006Bec] and [2006Bes] under an inert atmosphere and the eutectic temperature and
composition were refined. [1967Jon] presented a phase diagram of the ZrO2-Fe3O4 system.
[1975Kat] used thermogravimetric analysis in oxygen controlled atmosphere and presented
the isothermal section of the ZrO2-FeO-Fe2O3 system at 1200˚C. [1987Kim] and [1988Kim]
studied the ZrO2-FeO-Fe2O3 system using thermogravimetry at air condition and partial
oxygen pressure of 2.1·102 Pa.
[2002Pet] studied the ZrO2-FeO-Fe2O3 system at air conditions in the temperature range
of 1870-2230˚C and found liquid immiscibility in the composition range 34-82 mass% ZrO2.
The liquidus surface and phase diagram of the ZrO2-FeO1.357 join were calculated by [2002Pet]
using regular solution model.
The solubility of oxygen in Fe-Zr melts was experimentally studied by equilibration
technique in [1965Buz, 1973Buz, 1974Fru, 1976Jan]. Minimum solubility of oxygen (0.0008
mass% O) was found by [1974Fru] at 0.08 mass% Zr and 1680˚C. Oxygen activity in Fe-Zr
melts was measured by emf method in [1973Tep, 1976Jan].
Investigation of thermal stability and properties of the ZrO2-Fe2O3 solid solutions pro-
duced by high-energy ball milling at room temperature was performed by [1996Ton, 2000Cao,
2001Cao, 2002Cao, 2006Fig].
Co-precipitation method was used in several studies [1977Heu, 1997Nar, 1999Ste,
2000Laj, 2000Ste, 2001Ste] to produce an amorphous phase in the ZrO2-Fe2O3 system. The
microstructures and phase development were observed for different temperatures and times of
heat treatment. It was shown that in this system metastable phases were formed first, which
transform to the stable phases during heat treatment.
An evaluation of the experimental data for the Fe-O-Zr system was performed by
[1989Rag1] and the isothermal section at 1000˚C was constructed as well as the solubility
curves of oxygen at 1680 and 1800˚C based on the available experimental data of [1974Fru,
1967Buz].

2 24 Fe–O–Zr
Wagner’s formalism was used in studies of [1965Buz, 1967Buz, 1973Buz, 1974Fru,

1976Jan, 1986Gho] to calculate interaction parameters and deoxidation constant.
[2004Hua] made a Calphad-type assessment for the Fe-O-Zr system using ionic model for
the liquid description. However experimental data on the Fe solubility in βZrO2 and γZrO2
were not taken into account as well as Zr solubility in hematite and magnetite phases. The
derived database was used to calculate solubility of oxygen in Fe-Zr melt. [2004Jun] used
associate model to calculate solubility curves at 1600 and 1680˚C as well as activity of oxygen
in Fe-Zr melt.
Experimental studies and modelling in the Fe-O-Zr system are summarized in Table 1.
Binary Systems
The Fe-Zr binary system is accepted from the experimental study of [2002Ste]. In this study it
was shown that the Fe23Zr6 phase shown by [Mas2] is oxygen stabilized and is not an
equilibrium phase. According to [2002Ste] the Zr2Fe phase is stable in a quite narrow
temperature range of 780-951˚C, while according to [Mas2] it is stable below 974˚C. The
phase diagram of the Fe-O system is accepted from [1991Sun]. The thermodynamic assess-
ment of [1991Sun] gives results very close to [Mas2]. The phase diagram of the Zr-O system is
accepted from a thermodynamic assessment of Wang et al. [2004Wan, 2006Wan] which is in
good agreement with [Mas2].
Solid Phases
The crystallographic data for solid phases are listed in Table 2. Polymorphic modifications of
ZrO2 dissolve some amount of FeO [2006Bes]. The cubic phase γZrO2 with the fluorite
structure dissolves up to 13 mol% FeO at T~1800˚C and the tetragonal phase βZrO2 up to
2.2 mol% at 1332˚C. According to [1957Fis] the FeO solubility in the tetragonal phase is
higher (6.7 and 5 mol% FeO at 1450 and 1800˚C, respectively). It should be mentioned that a
tetragonal phase t’ obtained by fast quenching from high temperature forms by diffusionless
mechanism and differs in the unit cell parameters from the tetragonal phase obtained by slow
cooling (equilibrium phase). For the t’ phase the c/a ratio is slightly above 1. Probably, in fact,
[2006Bes] obtained the t’ phase, therefore the unit cell parameters were different from βZrO2.
The monoclinic phase αZrO2 does not dissolve any detectable amount of FeO. FexO wüstite
does not dissolve any detectable amount of ZrO2 [1989Rag1]. According to [1975Kat]
magnetite Fe3O4+x dissolves ~2.7 mol% of ZrO2. Kiminami [1987Kim, 1988Kim] reported
data on the reaction of decomposition of magnetite to hematite. The temperature of this
reaction increases from 1300 to 1437˚C with an increase of the partial pressure of oxygen
from 2·102 to 2·104 Pa accompanied by an increase of the solubility of ZrO2 in Fe2O3 from 2 to
6 mol% and decrease of the solubility of Fe2O3 in ZrO2 from 8 to 3 mol% of Fe2O3. The results
of [1967Jon] on the solubility of ZrO2 in hematite and magnetite and solubility of Fe3O4 in
ZrO2 are in reasonable agreement with [1987Kim]. [2002Pet] found the maximal solubility of
FeO1.357 in the monoclinic ZrO2 as high as 6.6 mass% and maximal solubility of ZrO2 in Fe3O4
as high as 2.5 mass%. The iron oxide solubility in monoclinic ZrO2 seems to be too high and
probably refers to another modification of ZrO2.

Fe–O–Zr 24 3
[2002Kov] reported solid solutions Zr3FeOx of the BRe3 type forming at 800˚C in the range
of x = 0-1.
[1960Nev] found a Ti2Ni type cubic ternary compound τ1 with a small homogeneity range
(Zr2Fe)1–xOx stable at 1000˚C. The maximal concentration of oxygen in this compound was
around 10 mol%. The same structure TiNi2 was reported by [1967Hol] and by [1998Zav] after
annealing at 800-1000˚C in the purified Ar. The composition of the τ1 phase determined by
[1998Zav] (Zr4Fe2O0.6) was close to the data of [1967Hol] (Zr6Fe3O) and [1960Nev]. A cubic
ternary compound of ZrFe2.67O0.67 was mentioned by [1989Rag1] by mistake referring
[1984Pap]. The compound studied by [1984Pap] is oxifluoride and it is not relevant to the
Fe-O-Zr system. [2001Wu] reported on the synthesis of iron zirconate by aging at 850˚C of
sintered mixture of ZrO2 and αFe2O3. This phase with the Zr/Fe ratio of approximately 1 has
the monoclinic crystallographic symmetry and it is most probably metastable.
Quasibinary Systems
[1957Fis] experimentally studied the phase relations in the FeO-ZrO2 system. It is a simple
eutectic system with no significant solubility of ZrO2 in FeO and small solubility of iron oxide
in ZrO2. Later this system was studies by [2006Bec, 2006Bes]. The position of the eutectic
point was refined at 1332˚C and 10.3 mol% ZrO2. The maximal solubility of FeO in the
tetragonal ZrO2 (βZrO2) was determined as 2.2 mol% FeO at 1332˚C. The obtained tempera-
ture is in agreement with [1957Fis], while eutectic composition (ZrO2 content) is higher than
one obtained by [1957Fis]. The position of the metatectic reaction γZrO2 Ð βZrO2+L was
approximately determined by [2006Bes] at the temperature of 1800˚C or below with the
maximal solubility of FeO in the cubic ZrO2 (γZrO2) ~13 mol%. The experimental phase
diagram of the ZrO2-FeO system from the work of [2006Bes] is presented in Fig. 1. Strictly
speaking this system is not quasibinary because metallic Fe was in equilibrium with FeO.
The ZrO2-Fe2O3 system was extensively studied in many works [1977Heu, 1996Pop,
1997Nar, 1999Ste, 2000Ste, 2001Ste], but many of them dealt with metastable phase forma-
tions at low temperature (500-900˚C). An equilibrium study was performed at 1100˚C by
[1996Pop] and the maximal mutual solubility of ZrO2 and Fe2O3 was determined by XRD. It
was up to 2 mol% of Fe2O3 in the monoclinic ZrO2 (αZrO2) and 1 mol% of ZrO2 in αFe2O3.
For the composition range between 2 and 99 mol% Fe2O3 two solid solution phases αZrO2
and αFe2O3 were found in equilibrium.
The data on the invariant reactions obtained by [2006Bes] and [1967Jon] are presented
in Table 3. [1991Zhu] studied a eutectoid reaction in the Zr-Fe-O (0.98 mass% Fe,
0.21 mass% O) alloy using DTA, but these data are not accepted in the present evaluation
due to difference in the transformation temperatures in pure Zr and Fe-Zr system.
The liquidus surface in the ZrO2-FeO-Fe2O3 was calculated by [2002Pet]. However, the
thermodynamic data were not presented by [2002Pet] and polymorphic transformations in
4 24 Fe–O–Zr
ZrO2 were not taken into account. The ZrO2 phase with the hexagonal structure found by
[2002Pet] seems to be erroneous. The monovariant line FeO+Fe3O4+L was missing. Therefore
the calculated liquidus surface and invariant reactions from [2002Pet] are not presented in this
evaluation. According to the calculations of [2002Pet] there is a quite large liquid miscibility
gap starting in the ZrO2-Fe2O3 system extending into the ternary system up to 40 mass% of
FeO. The presence of the miscibility gap was also confirmed by the experimental studies
performed in [2002Pet]. However, it should be mentioned that the miscibility gap was not
indicated in other ZrO2 based systems (see [2005ACS]). It is not clear why the miscibility gap
appears only in the ZrO2-Fe2O3 system, but not in the ZrO2-Al2O3. It should be also
mentioned that the samples investigated by [2002Pet] contained a remarkable amount of
impurities.
Isothermal Sections
The isothermal section of the Fe-O-Zr system at 1000˚C presented in Fig. 2 is from the
evaluation of [1989Rag1] who took into account data of [1960Nev] and data of [1975Kat]
obtained at 1200˚C with the corrected solubility of Zr in magnetite ~0.3 at.% at 1000˚C instead
of 0.8 at.% at 1200˚C. Some corrections were made in Fig. 2 according to the accepted binary
Fe-Zr system. The isothermal section in the ZrO2-FeO-Fe2O3 system at 1200˚C from
[1975Kat] is shown in Fig. 3. The solubility of FeO in ZrO2 and ZrO2 in Fe2O3 was not
determined. The isothermal section at 1437˚C at air oxygen partial pressure from [1987Kim]
and at T ≤1380˚C at p(O2) = 2.1·102 Pa from [1988Kim] are presented in Figs. 4a and 4b.
The system Fe3O4-ZrO2 was studied by [1967Jon]. Two invariant reactions an eutectic and a
peritectic were found at 1525 and 1434˚C, respectively. The phase diagram from [1967Jon] is
presented in Fig. 5. At high temperatures the phase diagram is shown tentatively and the
cubic-tetragonal transformation was not presented. As mentioned in the section of Solid
Phases, according to [1967Jon], the ZrO2 phase dissolved ~6 mol% of Fe3O4 and the Fe3O4
and Fe2O3 phases dissolve limited amount of ZrO2. However, it was not indicated which ZrO2
modification participate in the equilibrium. The data of [1987Kim] indicated that the
solubility of ZrO2 in Fe2O3 increases the temperature of decomposition of hematite to
magnetite and oxygen from 1380 to 1437˚C in air condition, that is in agreement with
[1967Jon] within uncertainty limits. [1988Kim] studied a reaction of the hematite decompo-
sition at lower partial pressure of oxygen (p(O2)=2.1·102 Pa) than in [1987Kim] and it was
found that due to the solubility of ZrO2 in hematite the temperature of its decomposition
increased from 1265˚C in pure Fe-O system to 1300˚C in the ZrO2 containing system.
Thermodynamics
The effect of Zr in liquid iron on oxygen activity along liquid/ZrO2 equilibrium was experi-
mentally studied by emf method in [1973Tep] and [1976Jan]. The experimentally determined
oxygen content in the Fe-Zr melts by [1976Jan] was higher than the calculated from the
Fe–O–Zr 24 5
activity data using Wagner’s formalism. The calculation of [2004Jun] based on the associate
model reproduce experimental data on oxygen activity very well. The calculated activities of
oxygen in the Fe-Zr liquid alloys at 1550-1650˚C from [2004Jun] are presented in Fig. 6. The
calculated oxygen solubility at 1600 and 1680˚C in the composition range 0.1-1.5 mass% Zr by
[2004Jun] is in reasonable agreement with the experimental data of [1976Jan] and [1974Fru],
respectively. However, at lower Zr content the calculated solubility is lower than that measured
experimentally. It should be mentioned that there is a large scatter in the experimental data on
the solubility of oxygen in [1965Buz] and [1976Jan].
The calculated activity and solubility of oxygen in molten Fe based on partially ionic
liquid model by [2004Hua] seems to be inconsistent with experimental data. The calculated
O solubility [2004Hua] is one order of magnitude lower than the experimental data and
the calculated minimum of oxygen solubility is at much higher Zr content. This implies
that the measured O-Zr interaction is much stronger that predicted by the modelling of
[2004Hua].
Fruehan [1974Fru] applied Wagner’s formalism for dilute solutions to derive eZrO = –3
and KOZr = 3.5·10–8 using his own experimental data on oxygen solubility in Fe-Zr melt.
[1986Gho] treated experimental data of [1974Fru] using Wagner’s formalism to calculate
first and second order interaction parameters as well as deoxidation constant at 1680˚C.
ZrO2 based oxygen gas sensors have wide applications [2000Tan, 2001Cao, 2002Cao].
[2000Tan] prepared nanostructured non-equilibrium solid solution in the ZrO2-Fe2O3 system
by high-energy ball milling and annealing at 400-650˚C and studied gas sensing properties.
According to [2001Cao] the ZrO2-Fe2O3 oxygen sensors obtained by ball milling, annealed at
400-800˚C have low operating temperature of 350˚C. [2000Cao] studied oxygen sensitivity
and electric conductivity of 0.8ZrO2-0.2Fe2O3 mixtures depending on time of annealing.
[2001Cao] studied oxygen sensitivity for different annealing temperatures depending on
time of annealing. Additionally, the effect of composition, annealing temperature and milling
time on sensitivity were studied. Also the response time for the composition of 0.8ZrO2-
0.2Fe2O3 annealed at 600˚C was quite good for such a low operating temperature as 320˚C.
[2002Cao] used XPS spectra to estimate oxygen vacancy concentration in ZrO2-Fe2O3 solid
solutions obtained by high energy ball milling.
Thin films in the ZrO2-Fe2O3 system were annealed in two stages at 77 and 97-997˚C and
optical properties of these films were studied by [2002Koz]. A decomposition of the solid
solution and the formation of Fe2O3 was observed with increasing of the annealing tempera-
ture from 427-727˚C. This was accompanied by increase of light absorbtion in the visible
region. The thin films are dielectric with high refractive indexes. They absorb radiation in
210-340 nm and 500-800 nm, the latter can be referred to high energy-gap semiconductors.
[1998Zav] studied hydrogenation of Zr4Fe2O0.6 composition and magnetic properties of
this compound and products of hydrogenation.
[1992Lou] performed thermoelectric-power and resistivity measurements to study pre-
cipitation kinetics of the Fe-O-Zr alloys between 450 and 600˚C. The correlation between
these two properties was shown due to the precipitation. The solubility of Fe in Zr alloys
between 450 and 550˚C depended on the presence of oxygen. Experimental studies of material
properties are presented in Table 4.
6 24 Fe–O–Zr
Miscellaneous
There are several papers devoted to microstructure and phase development during heat
treatment of amorphous precursors obtained by co-precipitation method in the ZrO2-Fe2O3
system [1977Heu, 1997Nar, 1999Ste, 2000Ste, 2001Ste]. [1977Heu] indicated that in the
ZrO2-Fe2O3 system a metastable cubic phase crystallized first then transformed to a stable
phase assemblage by heat treatment. Similar observation was made by [1997Nar]. [1997Nar]
also indicated an amorphous phase first crystallized as a single-phase solid solution appeared
as cubic by XRD and tetragonal by electron diffraction. At higher temperatures this phase
transforms to the tetragonal phase and γFe2O3 (observed only by TEM), which transformed to
αFe2O3 at even higher temperatures. Thermal stability of the ZrO2-Fe2O3 amorphous pre-
cursors obtained by co-precipitation from aqueous solutions were studied after calcination at
500-1100˚C by XRD, Raman and Mössbauer spectroscopy by [1999Ste, 2000Ste, 2001Ste].
[2000Ste] additionally studied thermal stability under low pressure (4·10–3 Pa). Amorphous
samples were studied by thermal analysis and gravimetry. It was found that incorporation of
Fe+3 stabilized cubic polymorph of ZrO2 occurring at Fe2O3 content ≥10 mol%. The presence
of Fe2O3 above solubility limit caused transformation to monoclinic ZrO2. Terminal solubility
limit of Fe2O3 in the ZrO2 decreased with temperature increase from 33 mol% at 600˚C to 2%
at 1100˚C. Mössbauer spectroscopy indicated incorporation of Zr+4 into αFe2O3 structure
decreasing with temperature increase. A comparison of the results obtained at atmospheric
pressure and at low pressure showed that Fe+3 destabilized cubic ZrO2 at low pressure
[2001Ste]. Also, it was found by [2001Ste] that the solubility of Fe2O3 in ZrO2 was higher at
low pressure. The effect of pressure was attributed to the influence of oxygen vacancies
introduced during calcination at low pressure. Nanocrystallized cubic Fe-stabilized zirconia
were prepared by co-precipitation method and heat treated at different temperatures between
400 and 900˚C in [2000Laj]. It transformed to the tetragonal phase at the temperatures above
800˚C and then to the monoclinic phase at 900˚C. An addition of 30 mol% of Fe+3 stabilized
cubic phase above 800˚C in Ar. Higher Fe2O3 content resulted in phase separation of hematite.
The greatest thermal stability was found at 20 mol% of Fe+3. Particle size was a primary factor
determining cubic-tetragonal transformation.
The mixtures of ZrO2-Fe2O3 (16.7 mass% Fe2O3) obtained by high energy ball milling at
room temperature were investigated by XRD and TEM in work of [1996Ton]. It was shown
that nanocrystalline structure was forming during milling that enables the formation of the
tetragonal phase. TEM study showed that grains were slading and overlapping each other. The
obtained patterns could be ascribed to tetragonal or cubic phases. Cao et al. [2000Cao,
2001Cao, 2002Cao] studied thermal stability, electric conductivity and gas sensitivity of
powders obtained by ball milling at room temperature. [2000Cao] showed using XRD, DTA
and TEM that after 60 h of milling monoclinic ZrO2 transformed to Fe+3 stabilized cubic
structure which forms to amorphous-like conglomerates at 120 hours of milling. After heat
treatment at 650˚C the Fe+3 expelled from the metastable cubic phase forming αFe2O3
[2000Cao]. [2002Cao] obtained XPS spectra and calculated oxygen vacancy concentration.
Thermal stability of the ZrO2-15 mol% Fe2O3 solid solutions obtained by ball milling at
room temperature was studies by [2006Fig] using Mössbauer spectroscopy, XRD and DTA.
It was shown that all Fe2O3 was incorporated in cubic ZrO2 structure by ball milling,
producing very disrupted solid solution which crystallized in cubic form after annealing at
620˚C. After annealing at 900˚C cubic solid solution decomposed to hematite and tetragonal
solid solution. Annealing at 1100˚C results in the formation of the monoclinic ZrO2 phase.
Fe–O–Zr 24 7
The temperature of 900˚C is indicated as a limit of the stability of the tetragonal metastable
solid solution.
[2005Str] studied interaction of stabilized ZrO2 solutions with Fe2O3 at 1750˚C. It was
found that only MgO stabilized cubic zirconia reacted with Fe2O3 forming MgFe2O4 spinel,
while Ca, Y and Nd stabilized ZrO2 resisted decomposition by Fe2O3 attack. Some dissolution
of Fe2O3 in cubic structure was indicated.
Influence of Fe2O3 on martensitic transformation of tetragonal to monoclinic phase in the
ZrO2 was studied in works of [1990Kim] and [1999Boh].
Supersaturation phenomenon when deoxidation products precipitate from liquid was
studied in Fe-0.04 mass% Zr alloy by [1997Li] by EMF technique in Ar-20 vol% H2 atmo-
sphere. Supersaturation ratio (aZr·a2O)ss/(aZr·a2O)eq was found to be equal to 1.3.
. Table 1
Investigations of the Fe-O-Zr Phase Relations, Structures and Thermodynamics
[1957Fis] Equilibrium study, thermal analysis, XRD, 1300-1800˚C in air, ZrO2-FeO

optical microscopy
[1960Nev] Arc melting, annealing in vacuum, 1000˚C, vacuum 5·10–5 mm Hg, x < 0.1
metallography, XRD
[1965Buz], Equilibrium studies, thermodynamic 1800˚C, Fe-Zr 0.15-1.5 mass% Zr
[1967Buz] calculations
[1967Jon] Vertical tube furnace with quenching, 1250-1600˚C, p(O2) = 2.1·10–2 Pa, ZrO2-
optical microscopy and XRD Fe3O4
[1973Buz] Equilibrium studies, thermodynamic 1600˚C Ar, Fe-Zr 0.01-1.85 mass% Zr
calculations
[1973Tep] EMF, chemical analysis 1550, 1600 and 1650˚C,
0.001-0.3 mass% Zr
[1974Fru] Equilibrium studies in He atmosphere ZrO2 1680˚C, Fe-Zr alloys 0.05-1 mass% Zr
crucibles
[1975Kat] Thermogravimetry (TGA), equilibration 1200˚C, p(O2) = 10–3.76-10–12.82 atm,
with gas mixture CO2/H2, oxygen control ZrO2-FeO-Fe2O3
by gas sensors
[1976Jan] Equilibrium studies, chemical analysis, EMF 1600˚C, Fe-Zr alloys 0.0009-1.7 mass%
Zr
[1977Heu] Co-precipitation, XRD, DTA, dilatometry, IR- 400-1200˚C, ZrO2-Fe2O3 (0-90 mol%
spectrometry Fe2O3)
[1986Gho] Thermodynamic calculations 1680˚C, Fe-Zr (up to 1 mass% Zr)
[1987Kim] TGA p(O2) = 2.1·10–2 Pa, T up to 1500˚C
ZrO2-FeO-Fe2O3
[1988Kim] TGA p(O2) = 2.1·10–4 Pa, T up to 1380˚C
ZrO2-FeO-Fe2O3

8 24 Fe–O–Zr
[1990Kim] HT-XRD, DTA Up to 1400˚C, ZrO2-Fe2O3 (0-98 mol%

Fe2O3)
[1991Zhu] DTA in Ar 792-856˚C, Zr-0.98Fe-0.21O (mass%)
[1996Pop] Co-precipitation, XRD, Mössbauer 1100˚C, ZrO2-Fe2O3
spectroscopy
[1996Ton] High-energy ball milling, XRD, TEM ZrO2-Fe2O3 (16.7 mass% Fe2O3)
[1997Li] EMF in Ar-20 vol% H2 1600˚C, supersaturation during
deoxidation and ZrO2 precipitation of
Fe-0.04 mass% Zr liquid alloy
[1997Nar] Co-precipitation, XRD, TEM/EDX, SEM 500-1300˚C, ZrO2-Fe2O3 (10-40 mol%
Fe2O3)
[1998Zav] Arc-melting in Ar, XRD, Mössbauer 800 and 1000˚C annealing, Zr4Fe2O0.6
spectroscopy
[1998Zio] X-ray radial electronic density distribution Co-precipitation, calcination at 110
spectra and 400˚C, ZrO2-Fe2O3 (Zr:Fe =
0.907:0.093)
[1999Boh] XRD, SEM/EDX 840-950˚C, ZrO2-Fe2O3 (50 mass%)
[2000Laj] XRD, HT-XRD, electron paramagnetic Co-precipitation, 400-900˚C heat
resonance spectra treatment, ZrO2-Fe2O3 (5-40 mol%
FeO1.5)
[2000Cao] High-energy ball milling, XRD, TEM, DTA 200-1000˚C, 0.8ZrO2-0.2αFe2O3
[2000Tan] High-energy ball milling, XRD Annealing 400-650˚C, ZrO2-Fe2O3 with
0-20 mol% ZrO2
[1999Ste], Co-presipitation and calcination of 600-1100˚C calcination, ZrO2-Fe2O3
[2000Ste], amorphos samples, XRD, Raman, DTA, TGA, (0-50 mol% Fe2O3)
[2001Ste] Mössbauer spectroscopy
[2001Cao] High-energy ball milling, XRD, TEM ZrO2-Fe2O3 with 5-25 mol% Fe2O3
[2001Wu] XRD, analytical electron microscopy, EDX Sintering of oxide mixture at 1200˚C
and aging at 850˚C, Fe/Zr ≈ 1
[2002Cao] High-energy ball milling, XPS ZrO2-Fe2O3 with 5-30 mol% Fe2O3
[2002Kov] XRD Annealing at 800˚C, Zr3FeOx (x = 0, 0.2,
0.4, 0.6, 0.8, 1)
[2002Pet] Induction melting, XRD, microprobe Air condition, 1870-2230˚C, ZrO2-FeO-
analysis, SEM, calculation Fe2O3
[2004Hua] CALPHAD, ionic liquid model 1600, 1680˚C, Zr-Fe-O
[2004Jun] CALPHAD, associate model 1600, 1680˚C, Zr-Fe-O

Fe–O–Zr 24 9
[2006Bec] DSC, chemical analysis, visual polythermal 1100-2710˚C, inert atm. Ar/He, ZrO2-
[2006Bes] analysis in induction melting in cold FeO
crucible or Galakhov furnace, XRD, SEM/
EDX
[2006Fig] High energy ball milling, Mössbauer 25˚C, 250-1100˚C (annealing
spectra, Perturbed Angular Correlation temperature), Zr0.7Fe0.3O1.85
spectra, XRD, DTA
. Table 2
Pearson
(δFe) cI2 a = 293.15 pure Fe at 1390˚C [Mas2]

1538 - 1394 Im3m
W
1394 - 912 Fm3m
Cu
< 912 Im3m
W
P63/mmc c = 396.0
Mg
(βZr) cI2 a = 352.4 up to 4 at.% Fe
1855 - 775 Im3m a = 360.9 805˚C 100% Zr [1989She]
W
(αZr) hP2 a = 323.17 at 25˚C 100% Zr [1989She]
< 863 P63/mmc c = 514.7
Mg
αFe2O3 hR30 ~60 at.% O, ~6 mol% ZrO2 at 1437˚C
< 1457 R
3c [1987Kim]
Al2O3 a = 503.42 ± 0.03 [V-C2]
c = 1374.83 ± 0.04
γFe2O3 cF56 a = 834 [1989Rag2]
Fd
3m metastable
MgAl2O4

10 24 Fe–O–Zr
Pearson
FexO cF8 wustite, 0.845 ≤ x ≤ 0.961

1424 - 570 Fm3m a = 435.35 at 1000˚C [V-C2]
NaCl
Fe3O4+y cF56
Fe3O4 Fd
3m magnetite
< 1596 MgAl2O4 57.1 to 58.0 at.% O, ~6 mol% ZrO2
a = 841.1 at 1437˚C [1987Kim]
at 200˚C [V-C2]
ZrFe2 cF24 a = 702 to 709 27.5 to 34.4 at.% Zr [2002Ste]
(h1) Fd
3m C15 structure
< 1673 MgCu2
λZrFe2 hP24 a = 495 26.5 to 27 at.% Zr [2002Ste]
(h2) P63/mmc c = 1614 C36 structure
1345 - 1240 MgNi2
Zr2Fe tI12, 66.7 to 67.2 at.% Zr, C16 structure
951 - 780 I4/mmc a = 638 [2002Ste]
CuAl2 c = 560
Zr3FeOx oC16 solid solution 0 ≤ x ≤ 1 [2002Kov]
Cmcm a = 332.28 x=1
BRe3 b = 1111.37
c = 872.3
Zr3Fe 74.8 to 75.4 at.% Zr [2002Ste]
≤ 851 a = 332 x = 0 [2002Ste]
b = 1100
c = 882
Zr6Fe23 cF116 a = 1172 metastable, stabilized by oxygen
Fm3m [2002Ste]
Th6Mn23
γZrO2 cF12 [1989Rag1], [2006Wan]
2710 - 2311 Fm3m 13 mol% FeO at 1800˚C
CaF2 a = 509 pure ZrO2 [V-C2]
a = 508.5 11.3 mol% FeO [2006Bes]
βZrO2 tP6 up to 2.2 mol% FeO at 1332˚C
2311 - 1094 P42/nmc [2006Bes]
ZrO2 a = 360.55 pure ZrO2 [V-C2]
c = 517.97
t’ (?) a = 507 2.2 mol% FeO [2006Bes]
c = 517

Fe–O–Zr 24 11
Pearson
αZrO2 mP12 a = 514.15 baddeleyite pure ZrO2 [V-C2]

≤1094 P21/c b = 520.56
ZrO2 c = 531.28
β = 99.30
τ1 (Zr2Fe)1–xOx cF96 a = 1218.9 60.2-65.6 at.% Zr, 3.1-8.6 at.% O
Fd
3m [1960Nev]
NiTi2 a = 1221 x = 0 metastable [2002Ste]
. Table 3
Composition (at.%)
Reaction T [˚C] Type Phase Fe O Zr
γZrO2 Ð βZrO2+L ~1800 p γZrO2 4.53 65.16 30.31

βZrO2 0.67 66.44 32.89
L 36.36 54.54 9.09
L Ð βZrO2+FexO 1332 e L 42.65 52.45 4.9
βZrO2 0.74 66.42 32.84
FexO 49.7 51.30 0
L Ð Fe3O4+y+ZrO2 1525 e L 38.71 58.06 3.23
Fe2O3 Ð Fe3O4+y +O2 (ZrO2) 1434 d Fe2O3 38.52 60.25 1.23
Fe3O4+y 42.49 57.22 0.29
βZrO2 5.56 65.43 29.01
. Table 4
Investigations of the Fe-O-Zr Materials Properties
[1992Lou] Voltage between sample and metallic reference Thermal electric power and
blocks at T and T+ΔT temperature, voltage and resistivity of Zr-Fe-O alloys
electric current measurements
[1998Zav] Mössbauer spectroscopy, magnetic susceptibility Magnetic properties
measurements

12 24 Fe–O–Zr
[2000Cao] Gas sensing measurement system Oxygen gas sensitivity, electric

conductivity
[2001Cao] Gas sensing measurement system Oxygen gas sensitivity, response
time
[2002Cao] Gas sensing measurement system, XPS Oxygen gas sensitivity and
concentration of oxygen
vacancies
[2002Koz] Spectrophotometry and elipsometry Optical properties of thin films
[2002Sei] Transmission Mössbauer spectroscopy Magnetic properties

Fe–O–Zr 24 13
. Fig. 1
Fe-O-Zr. Phase diagram of the FeO-ZrO2 system

14 24 Fe–O–Zr
. Fig. 2
Fe-O-Zr. Isothermal section at 1000˚C

Fe–O–Zr 24 15
. Fig. 3
Fe-O-Zr. Isothermal section of the ZrO2-FeO-Fe2O3 system at 1200˚C together with isobars

16 24 Fe–O–Zr
. Fig. 4a
Fe-O-Zr. Isothermal section of the ZrO2-FeO-Fe2O3 system at 1437˚C and p(O2) = 2.1·104 Pa

Fe–O–Zr 24 17
. Fig. 4b
Fe-O-Zr. Isothermal section of the ZrO2-FeO-Fe2O3 system at T ≤ 1380˚C and p(O2) = 2.1·102 Pa

18 24 Fe–O–Zr
. Fig. 5
Fe-O-Zr. Phase diagram for the Fe3O4-ZrO2 system from [1967Jon] in air. The β Ð γ
transformation in ZrO2 is accepted according to [2006Wan], the γ Ð β+L transition is tentatively
shown by a dashed line

Fe–O–Zr 24 19
. Fig. 6
Fe-O-Zr. Calculated oxygen activity in liquid Fe-O-Zr alloys in equilibrium with solid ZrO2 at
1550-1650˚C

20 24 Fe–O–Zr
References
[1957Fis] Fischer, W.A., Hoffmann, A., “Equilibrium Studies in the System FeO-ZrO2” (in German), Arch.
Eisenhuettenwes., 28(11), 739–743 (1957) (Experimental, Phase Relations, #, 23)
[1960Nev] Nevitt, M.V., Downey, J.W., Morris, R.A., “A Further Study of Ti2Ni-Type Phases Containing Titanium,
Zirconium or Hafnium”, Trans. Met. Soc. AIME, 218, 1019–1023 (1960) (Crys. Structure, Experimental,
Phase Diagram, #, 7)
[1965Buz] Buzek, Z., “The Effect of Aluminium, Titanium, Zirconium, and Cerium on the Solubility of Oxygen in
Liquid Iron at 1800˚C”, Sb. Ved. Pr. Vys. Sk. Banske Ostrave, Rada Hutn., 11, 395–400 (1965) (Experi-
[1967Buz] Buzek, Z., Schindlerova, V., Macoszek, M., “The Influence of Cr, Mn, V, Si, Ti, Al, Zr, Ce and Ca on
the Activity and Solubility of Oxygen in Liquid Iron”, Sb. Ved. Pr. Vys. Sk. Banske Ostrave, Rada Hutn.,
13(2-3), 175–193 (1967) (Experimental, Phase Relations, 26)
[1967Hol] Holleck, H., Thuemmler, F., “Investigations on the Formation of Metalloid-Stabilised Zr-Rich
Transition” (in German), J. Nucl. Mater., 23, 88–94 (1967) (Crys. Structure, Experimental, 12)
[1967Jon] Jones, T.S., Kimura, S., Muan, A., “Phase Relations in the System FeO-Fe2O3-ZrO2-SiO2”, J. Amer.
Ceram. Soc., 50(3), 137–142 (1967) (Experimental, Phase Diagram, Phase Relations, #, 16)
[1973Tep] Teplitsky, E.B., Vladimirov, L.P., “Thermodynamics of Steel Killing by Zirconium” (in Russian), Izv.
Vyss. Uchebn. Zaved., Chern. Metall., (3), 5–7 (1973) (Experimental, Thermodyn., 6)
Iron at 1600˚C” in “Metall. Chem. - Appl. Ferrous Metall.”, Int. Symp., Sheffield, July 1971, Iron Steel
Inst., London, 173–177 (1973) (Crys. Structure, Experimental, Review, 8)
[1974Fru] Fruehan, R.J., “The Effect of Zr, Ce, and La on the Solubility of Oxygen in Liquid Fe”, Metall. Trans., 5,
[1975Kat] Katsura, T., Wakihara, M., Hara, S.I., Sugihara, T., “Some Thermodynamic Properties in Spinel Solid
Solutions with the Fe3O4 Component”, J. Solid State Chem., 13(1-2), 107–113 (1975) (Calculation,
Experimental, Phase Diagram, Phase Relations, Thermodyn., #, 11)
[1976Jan] Janke, D., Fischer, W.A., “Deoxidation Equilibria of Ti, Al and Zr in Fe Melts at 1600˚C” (in German),
Arch. Eisenhuettenwes., 47(4), 195–198 (1976) (Experimental, Phase Relations, 30)
[1977Heu] Heughebaert-Therasse, M., “Study Contribution to the Evolution and Sintering of Several Oxides
Stabilized Zirconia, at Temperatures below 1300˚C” (in French), Ann. Chim., 2, 229–243 (1977) (Crys.
Structure, Phase Diagram, Phase Relations, 38)
[1981Jin] Jin, T., Hattori, H., Tanabe, K., “Formation of Butane from Butanol Catalyzed by Fe2O3, Fe2O3-ZrO2,
and Fe2O3-ZnO”, Chem. Lett., 10(11), 1533–1534 (1981) (Experimental, Catalysis, 2)
[1984Pap] Papiernik, R., Frit, B., “Crystal Structure of Cubic Phase Disordered Anion Excess ZrFe2.67 Related to
the ReO3” (in French), Mater. Res. Bull., 19(4), 509–516 (1984) (Crys. Structure, Experimental, 20)
[1986Gho] Ghosh, A., Murthy, G.V.R., “An Assessment of Thermodynamic Parameters for Deoxidation of Molten
Iron by Cr, V, Al, Zr and Ti”, Trans. Iron Steel Inst. Jpn., 26(7), 629–637 (1986) (Assessment, Phase
Diagram, Thermodyn., Phase Relations, 41)
[1987Kim] Kiminami, R.H.G.A., “Study of the ZrO2-FeO-Fe2O3 System by Thermogravimetry at Air-Oxygen
Partial Pressures and Temperatures up to 1500˚C” (in Portuguese), Ceramica (Sao Paulo), 33(213),
207–209 (1987) (Experimental) as quoted in [2005ACS]
[1988Kim] Kiminami, R.H.G.A., “Study of the ZrO2-FeO-Fe2O3 System by Thermogravimetry at Oxygen Partial
Pressures 2.1·102 Pa and Temperatures up to 1380˚C” (in Portuguese), Ceramica (Sao Paulo), 34(223),
121–123 (1988) (Experimental) as quoted in [2005ACS]
[1989Rag1] Raghavan, V., “The Fe-O-Zr System” in “Phase Diagrams of Ternary Iron Alloys”, Indian Inst. Met.,
Calcutta, 5, 374–379 (1989) (Phase Diagram, Phase Relations, Review, 11)
[1989Rag2] Raghavan, V., “The Fe-O System”, Phase Diagrams of Ternary Iron Alloys, Indian Inst. Met., Calcutta, 5,
5–8 (1989) (Phase Diagram, Phase Relations, Crys. Structure, Review, 3)
[1989She] Sheldon, R.I., Peterson D.E., “The U-Zr (Uranium-Zirconium) System”, Bull. Alloy Phase Diagrams, 10
(2), 165–171 (1998) (Review, Crys. Structure, Phase Diagram, Phase Relations, Thermodyn., 33)
[1990Kim] Kiminami, R.H.G., “The Monoclinic-Tetragonal Phase Transformation of Zirconia in the System ZrO2-
Fe2O3”, J. Mater. Sci. Lett., 9(4), 373–374 (1990) (Experimental, Phase Relations, 9)
[1991Sun] Sundman, B., “An assessment of the Fe-O system”, J. Phase Equilib., 12(1), 127–140 (1991) (Phase
Relations, Phase Diagram, Thermodyn., Assessment, 53)

Fe–O–Zr 24 21
[1991Zhu] Zhu, Y.T., Devletian, J.H., “Precise Determination of Isomorphous and Eutectoid Transformation
Temperatures in Binary and Ternary Zr Alloys”, J. Mater. Sci., 26, 6218–6222 (1991) (Experimental,
Thermodyn., 13)
[1992Lou] Loucif, K., Borrelly, R., Merle, P., “Study by Thermoelectric-Power and Resistivity Measurements of the
Precipitation Kinetics in Zirconium Alloys Between 450˚C and 600˚C”, J. Nucl. Mater., 189(1), 34–45
(1992) (Electr. Prop., Experimental, Kinetics, Thermodyn., 24)
[1993Wu] Wu, J.-C., Liu, D.-S., Ko, A.-N., “Dehydrogenation of Ethylbenzene over TiO2-Fe2O3 and ZrO2-Fe2O3
Mixed Oxide Catalysts”, Catal. Lett., 20(3-4), 191–201 (1993) (Experimental, Phase Relations, Phys.
Prop., 28)
[1996Pop] Popovic, S., Grzeta, B., Stefanic, G., Czako-Nagy, I., Music, S., “Structural Properties of the System
m-ZrO2-α-Fe2O3”, J. Alloys Compd., 241(1-2), 10–15 (1996) (Crys. Structure, Experimental, Phase
Relations, 19)
[1996Ton] Tonejc, A.M., Tonejc, A., “Zirconia Solid Solutions ZrO2-Y2O3 (CoO or Fe2O3) Obtained by Mechani-
cal Alloying”, Mater. Sci. Forum, 225–227(pt.1), 497–502 (1996) (Experimental, Morphology, 10)
[1997Li] Li, G.Q., Suito, H., “Electrochemical Measurement of Critical Supersaturation in Fe-O-M (M = Al, Si,
and Zr) and Fe-O-Al-M (M = C, Mn, Cr, Si, and Ti) Melts by Solid Electrolyte Galvanic Cell”, ISIJ Int.,
[1997Nar] Narwankar, P.K., Lange, F.F., Levi, C.G., “Microstructure Evolution of ZrO2-(Fe2O3, Al2O3) Materials
Synthesized with Solution Precursors”, J. Am. Ceram. Soc., 80(7), 1684–1690 (1997) (Experimental,
Morphology, Phase Relations, 8)
[1998Zav] Zavaliy, I.Yu., Riabov, A.B., Yartys, V.A., Wiesinger, G., Michor, H., Hilscher, G., “(Hf,Zr)2Fe
and Zr4Fe2O0.6 Compounds and Their Hydrides: Phase Equilibria, Crystal Structure and Magnetic
Properties”, J. Alloys Compd., 265, 6–14 (1998) (Crys. Structure, Experimental, Magn. Prop., Phase
Relations, 22)
[1998Zio] Ziouzin, D.A., Moroz, E.M., Ivanova, A.S., “X-Ray Diffraction Study of Amorphous Zr-Fe-O System”,
Mater. Sci. Forum, 278–281(2), 826–832 (1998) (Crys. Structure, Experimental, 3)
[1999Boh] Bohe, A.E., Gamboa, J.J.A., Pasquevich, D.M., “Enhancement of the Martensitic Transformation of
Tetragonal Zirconia Powder in the Presence of Iron Oxide”, Mater. Sci. Forum, 273, 218–221 (1999)
(Crys. Structure, Experimental, Morphology, 15)
[1999Ste] Stefanic, G., Music, S., Popovic, S., Nomura, K., “A Study of the ZrO2-Fe2O3 System by XRD, 57Fe
Mössbauer and Vibrational Spectroscopies”, J. Mol. Struct., 480–481, 627–631 (1999) (Electr. Prop.,
Experimental, 11)
[2000Cao] Cao, W., Tan, O.K., Zhu, W., Jiang, B., “Mechanical Alloying and Thermal Decomposition of (ZrO2)0.8-
(α-Fe2O3)0.2 Powder for Gas Sensing Applications”, J. Solid State Chem., 155, 320–325 (2000) (Crys.
Structure, Electrical Properties, Experimental, Phase Relations, 14)
[2000Laj] Lajavardi, M., Kenney, D.J., Lin, Sh.H., “Time-Resolved High and Low Temperature Phase Transitions
of the Nanocrystalline Cubic Phase in the Y2O3-ZrO2 and Fe2O3-ZrO2 System”, J. Chin. Chem. Soc., 47,
[2000Ste] Stefanic, G., Grzeta, B., Music, S., “Influence of Oxygen on the Thermal Behavior of the ZrO2-Fe2O3
System”, Mater. Chem. Phys., 65(2), 216–221 (2000) (Crys. Structure, Experimental, Phase Relations, 14)
[2000Tan] Tan, O.K., Cao, W., Zhu, W., “Alcohol Sensor Based on a Non-Equilibrium Nanostructured xZrO2-
(1–x)α-Fe2O3 Solid Solution System”, Sens. Act. B (Chemical), 63(1-2), 129–134 (2000) (Crys. Structure,
Experimental, Nano, Phase Relations, 15)
[2001Cao] Cao, W., Tan, O.K., Zhu, W., Jiang, B., Gopal Reddy, C.V., “An Amorphous-Like xα-Fe2O3-(1–x)ZrO2
Solid Solution System for Low Temperature Resistive-Type Oxygen Sensing”, Sens. Act. B, 77(1-2),
[2001Ste] Stefanic, G., Grzeta, B., Nomura, K., Trojko, R., Music, S., “The Influence of Thermal Treatment on
Phase Development in ZrO2-Fe2O3 and HfO2-Fe2O3 Systems”, J. Alloys Compd., 327, 151–160 (2001)
[2001Wu] Wu, M.L., Gan, D., Shen, P., “Precipitation of Iron Zirconate from Zr4+ -Oversaturated Fe2O3–x (I)”,
Mater. Sci. Eng. A, 297(1-2), 119–123 (2001) (Crys. Structure, Experimental, Morphology, Phase
Relations, 20)
[2002Cao] Cao, W., Tan, O.K., Pan, J.S. Zhu, W., Gopal Reddy, C.V., “XPS Characterization of xα-Fe2O3-(1–x)
ZrO2 for Oxygen Gas Sensing Application”, Mater. Chem. Phys., 75(1-3), 67–70 (2002) (Experimental,

22 24 Fe–O–Zr
[2002Kov] Kovalchuk, I.V., Zavaliy, I.Y., “Hydrogenation of Oxygen-Stabilized Zr3FeOx Phase with Filled Re3B-
Type of Structure” in “Crys. Chem.”, VII Int. Conf., Lviv., 133 (2002) (Crys. Structure, Experimental, 4)
[2002Koz] Kozik, V.V., Shul‘pekov, A.M., Borilo, L.P., “The Structure and Optical Properties of Thin ZrO2, ZrO2-
Y2O3, and ZrO2-Fe2O3 Films”, Russ. Phys. J., 45(12), 1228–1230 (2002), translated from Izv. Vyss. Ucheb.
Zaved., Fiz., 45(12), 77–78 (2002) (Crys. Structure, Experimental, Optical Prop., 3)
[2002Pet] Petrov, Yu.B., Udalov, Yu.P., Slovak, J., Morozov, Yu.G., “Liquid Immiscibility Phenomena in Melts of
the ZrO2-FeO-Fe2O3 System”, Glass Phys. Chem., 28(3), 139–146 (2002), translated from Fiz. Khim.
Stekla, Russia, 28(3), 139–146 (2002) (Experimental, Morphology, Phase Diagram, Phase Relations, 14)
[2002Sei] Seifu, D., Li, F., “Mössbauer Study of Nano-Crystalline Thin Films of Fe-Zr-O”, Phys. Status Solidi A,
189(3), 731–734 (2002) (Experimental, Crys. Structure, 3)
(2002) (Crys. Structure, Experimental, Phase Relations, Phase Diagram, 88)
[2004Hua] Huang, W., “Oxygen Solubility in Fe-Zr-O Liquid”, Calphad, 28(2), 153–157 (2004) (Calculation, Phase
Diagram, Phase Relations, Thermodyn., 15)
[2004Jun] Jung, I.-H., Decterov, S.A., Pelton, A.D., “A Thermodynamic Model for Deoxidation Equilibria in
Steel”, Metall. Mater. Trans. B, 35b(3), 493–507 (2004) (Calculation, Theory, Thermodyn., 100)
[2004Wan] Wang, C., Zinkevich, M., Aldinger, F., “On the Thermodynamic Modeling of the Zr-O System”,
Calphad, 28(3), 281–292 (2004) (Calculation, Phase Diagram, Phase Relations, Thermodyn., 77)
[2005ACS] American Ceramic Society – NIST “Phase Equilibria Diagrams”, CD-ROM Database, Version 3.1,
ACerS-NIST (2004-2005)
[2005Str] Strakhov, V.I., Ivanova, I.V., Arsirii, A.I., Velkova, K., Migal, V.P., Gershkovich, S.I., “Phase
Transformations in Stabilized ZrO2-Fe2O3 Compositions”, Refract. Indust. Ceram., 46(5), 322–324
[2006Bec] Bechta, S.V., Krushinov, E.V., Almjashev, V.I., Vitol, S.A., Mezentseva, L.P., Petrov, Yu.B., Lopukh, D.B.,
Khabensky, V.B., Barrachin, M., Hellmann, S., et al, “Phase Diagram of the ZrO2-FeO System”, J. Nucl.
Mater., 348(1-2), 114–121 (2006) (Crys. Structure, Experimental, Morphology, Phase Diagram, Phase
Relations, #, 26)
[2006Bes] Beshta, S.V., Krushinov, E.V., Al‘myashev, V.I., Vitol‘, S.A., Mezentseva, L.P., Petrov, Yu.B., Lopukh, D.
B., Khabenskii, V.B., Barrachin, M., Hellmann, S., Gusarov, V.V., “Phase Relations in the ZrO2-FeO
System”, Russ. J. Inorg. Chem. (Engl. Transl.), 51(2), 325–331 (2006), translated from Zh. Neorgan. Khim.,
51(2), 367–374 (2006) (Experimental, Morphology, Phase Diagram, Phase Relations, #, 25)
[2006Fig] Figueroa, S., Desimoni, J., Rivas, P.C., Caracoche, M.C., de Sanctis, O., “Local Structures in the ZrO2-
15 mol% Fe2O3 System Obtained by Ball Milling”, J. Am. Ceram. Soc., 89(12), 3759–3764 (2006) (Crys.
Structure, Electr. Prop., Experimental, #, 16)
[2006Wan] Wang, C., Zinkevich, M., Aldinger, F., “The Zirconia - Hafnia: DTA Measurements and
Thermodynamic Calculations”, J. Am. Ceram. Soc., 89(12) 3751–3758 (2006) (Experimental, Calcula-
tion, Phase Relations, Thermodyn., 78)
(1990)

Fe–P–Si 25 1
Iron – Phosphorus – Silicon

Introduction
Phase relations in the Fe-P-Si system are of great interest mainly in two aspects - application of
phosphorus as dopant in Si-semiconductors containing iron, and development of nanocrys-
talline materials produced by controlled crystallization of amorphous alloys containing phos-
phorus and iron in combination with silicon or with d metals. At the same time, the amount of
information on the constitution of the Fe-P-Si system is still insufficient. Most of the experi-
mental data on phase equilibria were published long ago [1930Hum, 1933Sau, 1959Vog]. The
reaction scheme, liquidus surface projection and isothermal section at room temperature of
the Fe-FeP2-FeSi-Si partial system as well as a series of vertical sections were reported. Later
certain information about the effect of silicon on the solubility of phosphorus in iron at
different temperatures was presented in [1965Kan2]. The phase contents of the Fe-P-Si alloys
annealed at different temperatures were reported in [1997Vav, 1998Vav, 1999Vav]. At the same
time, new data on dissolution of the third component in the binary Fe-P and Fe-Si phases
[1962Run, 1965Sab, 1984Jer] and about new crystal structures identified in the ternary
system contradict the earlier version of the phase relations, and therefore, reinvestigation of
the Fe-P-Si system using modern physico-chemical analysis techniques is required.
The experimental works on the phase relations, crystal structures and thermodynamics
are listed in Table 1. The crystal structure data of the binary and ternary phases existing in the
Fe-P-Si system were published in [1933Sau, 1959Vog, 1962Run, 1965Sab, 1983And, 1984Jer,
1991Men, 1993Bal, 1995Per, 1998Vav, 1999Vav, 2002Ito, 2002Tan, 2003Bal]. Information on
thermodynamic properties, in particular activity of phosphorus in liquid iron with silicon
additions, was experimentally obtained by [1979Yam, 1983Ban, 1983Yam, 1997Ued]. Reviews
of literature data on phase equilibria in the Fe-P-Si system are presented in [1949Jae,
1965Kan1, 1988Rag], crystal structures - in [1988Rag], thermodynamics - in [1979Yam,
1983Ban]. A database of thermochemical parameters for liquid Fe based alloys containing Si
and P was proposed by [1995Bou].
Binary Systems
The Fe-P binary boundary system is accepted from [2002Per]. The Fe-Si and P-Si boundary
systems are accepted from [Mas2].
Solid Phases
Crystallographic data for the known unary, binary and ternary Fe-P-Si phases are listed in
Table 2. The investigations of the crystal structures of the phases deal mainly with the
additions of the third component to the solid solutions based on the binary phases
2 25 Fe–P–Si
[1962Run, 1983And, 1984Jer, 2002Ito, 2002Tan] and with the ternary phases [1959Vog,
1965Sab, 1968Sab, 1984Jer, 1995Per].
[1962Run] experimentally determined that solubility of silicon in δ (FeP) reaches about
25 at.%. X-ray diffraction patterns of the ζ2, FeSi2–xPx phase (x = 0 to 0.10) obtained after hot
pressing at 900˚C for 3.6 ks under the pressure of 25 MPa were published by [2002Ito]. The
geometrical and electronic structures of this phase at x = 0.125 studied using the first
principles pseudopotential calculations based on generalized gradient approximation (GGA)
density function theory are presented in [2002Tan]. It was noted that the calculated structural
parameters depend strongly on the kinds of dopants and sites.
The ternary phase τ1 was identified first by [1959Vog] at an approximate composition of
FeSi4P4, with a negligible range of homogeneity. This phase was reported to melt congruently
at a temperature of about 1210˚C. The existence of the τ1 phase was confirmed by [1965Sab,
1968Sab], but its crystal structure was identified much later by [1995Per] from single crystal
studies. It was noted that this phase, similar to the NiSi3P4 structure type reveals a new family
of ternary phases rich in silicon and phosphorus. The existence of a new ternary phase (τ2) was
established in [1984Jer]. They observed a crystallographic hexagonal/orthorhombic transfor-
mation in the partially Si-substituted γ (Fe2P) solid solution. The transformation temperature
dependence is shown to increase linearly with increasing P/Si substitution. The τ2, Fe2SixP1–x
phase with a body-centered orthorhombic structure was reported to be stable in the range of
0.20 < x < 0.36 at the temperature of 997˚C (Table 2). [1997Vav, 1998Vav, 1999Vav] reported
a new metastable ternary phase of an undetermined composition and type of structure
labeled as FexSizPy. It was found in alloys rapidly quenched and then annealed at 500˚C during
10 minutes. The compositions are Fe82Si2P16 and Fe78Si10P12 (in at.%). The presence of the
same phase was determined also in the alloys Fe80Si6P14, Fe78Si10P12 and Fe78Si2P20 rapidly
quenched and then annealed at 600˚C during 10 minutes. In Table 2 this phase is labeled as
ψ (Fe-P-Si).
Quasibinary Systems
The Fe2P-FeSi quasibinary system was experimentally explored by [1930Hum, 1933Sau]. Its
phase diagram is of the eutectic type, the eutectic temperature was reported to be 1185˚C
(corrected later by [1959Vog] to 1183˚C). The eutectic point e7 is located at the Fe58.6Si24.2P17.2
composition (Table 3). Solubilities of the third component in the γ (Fe2P) and λ (FeSi) phases
were declared by [1930Hum, 1933Sau] as negligible. However this statement contradicts the
later reported data of [1984Jer] and [1965Sab] (Table 2), therefore the Fe2P-FeSi phase
diagram needs a revision. A similar situation turned out with the quasibinary systems FeP-
FeSi, FeSi- FeSi4P4 and ζ1-FeSi4P4, proposed in [1959Vog], because a visible solubility of the
third component was observed in the δ (FeP) [1962Run], λ (FeSi) and ζ1 (FeSi2(h)) phases
[1965Sab]. The reported coordinates of the invariant points obtained in these three systems
are listed in Table 3. The Si-FeSi4P4 system was also declared by [1959Vog] to be quasibinary.
The temperatures, types of reactions and available compositions of the phases taking part
in the invariant equilibria in the partial Fe-FeP2-FeSi-Si system are listed in Table 3.
Fe–P–Si 25 3
The presented coordinates and a partial reaction scheme (Fig. 1) are adopted mainly from the
data of [1959Vog] on the invariant reactions and liquidus surface constitution, with certain
corrections according to the accepted boundary binary systems. In addition, the data of
[1930Hum] about the invariant four-phase equilibria with the participation of liquid at
1110˚C (U2) and 1018˚C (E6) are accepted. Like in the reaction scheme proposed by
[1988Rag], the transition reaction U1 has been introduced to eliminate the κ phase from the
liquid equilibria. Also the invariant reactions at high phosphorous concentrations with
the participation of a vapor phase at ambient pressure reported by [1959Vog] are omitted.
But the solid-state transition reactions proposed by [1988Rag] were also omitted because of
their hypothetical character, insufficiently confirmed by experimental results.
A liquidus surface projection of the partial Fe-FeP2-FeSi-Si system shown in Fig. 2 is based
on [1988Rag]. It is compiled mainly on the basis of the [1959Vog] experimental results
involving data from [1930Hum] on the partial Fe2P-related range. Two quasibinary eutectics
e10 and e13 are inserted on the joins τ1-μ and τ1-δ respectively, although their positions can be
very roughly given on these joins. The dashed monovariant lines indicate their tentative
character.
One can see in Fig. 2 that the constitution of the liquidus surface projection in the
composition ranges rich in Fe and P require further investigations.
Isothermal Sections
The isothermal section of the partial Fe-FeP2-SiP-Si system at room temperature was con-
structed by [1959Vog] from his own experimental results. It was shown that at this tempera-
ture the phases α, β, γ, δ, ε, λ, ζ2, μ, (Si) and τ1 take part in equilibria. No visible solubility of
the third component in the binary phases was detected. Phase relations in the Fe rich corner
(Fe-Fe3P-FeSi partial system) were plotted by dotted lines indicating the tentative character.
Later in his review [1988Rag] attempted to correct this section in accordance with the newer
boundary binary systems and using the data of [1962Run] on the solubility of up to 25 at.% Si
in the δ phase. But this section needs further verification, because an essential solubility of the
third component was determined also in the λ and ζ2 phases.
A schematic isothermal section of the Fe-Fe3P-SiP-Si partial system at 800˚C is shown in
[1965Kan1]. It’s peculiarity consists in the participation of the λ (FeSi) phase in equilibria with
other binary phases (β and μ). According to the data of [1965Kan2], the solubility of
phosphorus in (αFe) at 1000˚C decreases from 4.4 at.% (2.5 mass%) without silicon down
to 2.2 at.% (1.3 mass%) at 7.6 at.% (4.0 mass%) Si. With temperature decreasing from 1000 to
800˚C the solubility of P in (αFe) containing 1 at.% Si decreases from 4.0 to 1.9 at.%.
A series of temperature-composition sections was constructed by [1930Hum, 1959Vog] from

their own experimental data.
4 25 Fe–P–Si
The Fe3P-FeSi and Fe83P17-FeSi sections [1930Hum] need corrections according to the
established visible phosphorus solubility in the λ phase. The position of the liquidus curve of
the joint crystallization of the β and λ phases also needs verification. The section at 5 mass% P
(Fe91.3P8.7-Fe53.4Si39.6P7.0 in at.%), according to [1930Hum] is shown in Fig. 3. The position of
the border of the primary crystallization fields of the α and λ phases needs further amendment.
The section at 8 mass% P (Fe86.4P13.6-Fe55.7Si33.0P11.3 in at.%) which was also presented by
[1930Hum] is omitted here because mutual positions of the α, β, γ and λ liquidus surfaces are
not established reliably. Phase contents of some alloys lying along the sections constructed in
[1930Hum], in the as-cast and annealed states, were later reported by [1933Sau].
Three temperature-composition sections were proposed by [1959Vog]. The Fe63.7P36.3-
Si60.4P39.6 (in at.%) section needs verification because of uncertainties in the primary crystal-
lization fields of the τ1 and μ phases. Vertical sections at 13 mass% P (Fe78.8P21.2-Si88.1P11.9 in
at.%) and at 7 mass% Si, 16 to 26 mass% P (Fe64.3Si11.6P24.1-Fe52.4Si10.9P36.7 in at.%) are
shown in Figs. 4 and 5, respectively.
Thermodynamics
The effect of silicon on the activity coefficient of phosphorus in liquid iron alloys at different
temperatures was investigated by [1979Yam, 1983Yam, 1997Ued]. The Knudsen cell - mass
spectrometer combination measurements carried out at 1600˚C by [1979Yam, 1983Yam]
show a linear increase of the activity coefficient of P with silicon content increasing up to
12.1 mass%. As a result of the calculations, a value of εPSi = 11.9 ± 0.6 was obtained for the
interaction parameter at 1600˚C. Thermodynamics of phosphorus in molten Fe-Si alloys were
studied by [1997Ued] at 1450˚C by equilibrating the alloys in a controlled phosphorus partial
pressure. The phosphorus content of molten Si in a certain phosphorus partial pressure
decreases with the addition of iron, and it shows a minimum value at 23 at.% Fe. Interaction
coefficients between phosphorus and iron in molten silicon were found to be εPFe = 7.43 and
ρPFe = – 16.4 at iron content up to 65 at.%. Thermodynamic considerations using a ternary
regular solution model demonstrated that the obtained results are explained by a strong
interaction between Si and Fe. The possibility of dephosphorization of such alloys by calcium
treatment was also evaluated using these results.
The vapor pressure of phosphorus in liquid Fe-P-Si alloys with silicon content up to 12.1
mass% was measured by [1983Ban] applying the transportation method at the temperature of
1400˚C. The obtained results were treated by the model of interstitial solution proposed by J.
Chipman. The effect of silicon on the activity coefficient of phosphorus in liquid iron was
determined by assuming Si as substitutional element. The interaction parameter value was
obtained as εPSi = 7.68 ± 0.44 for 1400˚C. From the set of experimental data obtained by
[1983Ban], [1995Bou] assessed a thermodynamic dataset, but the experimental and calculated
values show essential discrepancies. In opinion of [1995Bou], the experimental results are
inconsistent at the Fe-P side, at negligible contents of silicon.
[1993Din] thermodynamically calculated the activity interaction parameter between Si
and P in liquid Fe at 1600˚C εPSi = 13.53 that does not differ essentially from the experimental
data obtained by [1979Yam, 1983Yam] and the data cited in [1988The].
The activation energy of crystallization of the Fe82Si2P16 (in at.%) amorphous alloy
was estimated by [1999Vav] using the Kissinger method, in terms of the variation in crystalli-
zation temperature (Tc) as a function of the heating rate in the range 3.75 to 40˚C·min–1.
Fe–P–Si 25 5
The obtained value was 471.5 ± 5.4 kJ·mol–1. After measurements of viscosity of Fe-P-Si melts,
from the slope of Arrhenius plots of kinematic viscosity, [2000Vav1] evaluated the activation
energy for viscous flow: 11.0, 44.0 and 44.0 kJ·mol–1 for the alloys (in at.%) Fe82Si2P16,
Fe78Si2P20 and Fe80Si6P14, respectively.

The Fe-P-Si alloys find practical application in modern technology mainly in two aspects.
Firstly, phosphorus usually serves as dopant in Si-semiconductor technology. In particular, the
semiconducting iron disilicide ζ2, FeSi2 (r), is a potential candidate for practical use in the high
temperature range (up to about 930˚C) because of its low cost of raw materials, its good
resistance to oxidation, and its nontoxicity [2002Ito], with P substitution for Si as an n-type
dopant possess lower thermal conductivity then the nondoped sample. Secondly, a consider-
able research effort has recently been concentrated on nanocrystalline materials produced by
controlled crystallization of amorphous alloys, but its high diffusion mobility and tendency to
nonuniform distribution leads to segregation brittleness [1999Vav]. In this aspect, a study of
the influence of silicon additions on the segregation of phosphorus atoms in iron is desirable.
The applied experimental techniques and investigated types of properties of Fe-P-Si alloys
are presented in Table 4.
[1981Yan] established that the addition of phosphorus to Fe-3 w/o Si alloys enhances the
sinterability but decreases the maximum permeability (mumax) and increases the coercive
force (Hc). These phenomena were discussed in terms of pore distribution, the formation of
secondary phases in the grain and the formation of amorphous phase in the grain boundary.
The resistivities of sintered compacts increase with the increase of the amount of phosphorus.
The γ, Fe2P (I) phase with additions of Si was reported by [1983And] to be ferromagnetic or
possibly ferrimagnetic; the Curie temperature of Fe2Si0.25P0.75 was reported as 570 K (297˚C).
Later the Curie temperature of Fe2SixP1–x alloys was found by [1984Jer] to increase with
increasing substitution by silicon - from 216 K (–57˚C) at x = 0 to 660 K (387˚C) at x = 0.35.
[1988Liu] reported that addition of 0.5 mass% Si reduces the ductile-brittle transition
temperature determined by small scale Charpy impact test by about 100 K, and the fracture
mode becomes transgranular. Addition of more Si increases the transition temperature, but
the fracture mode remains to be transgranular.
Mechanical, electrical, magnetic and other physical properties of Fe-P-Si amorphous alloys
were studied by [1993Bal, 1997Vav, 1998Vav, 1999Vav, 2000Vav1, 2003Bal, 2004Vav]. In
particular, it was concluded that the embrittlement of these alloys is governed by the amount
of (αFe) precipitating during crystallization [1998Vav, 1999Vav]. The effects of P substitution
for Si as n type dopant on the thermoelectric properties of hot-pressed ζ2, FeSi2 phase were
reported by [2002Ito]. The Seebeck coefficient, electrical resistivity and thermal conductivity
were measured from room temperature up to 1100 K (827˚C), and then the power factor and
figure of merit were evaluated. The Seebeck coefficient of the hot-pressed specimens is
negative, indicating that P atoms are definitely substituted for Si atoms as an n-type dopant
in the ζ2 phase. The electrical resistivity is significantly reduced by P doping, especially in the
lower temperature range, and slightly decreases with increasing P content. The thermal
conductivity of the P-doped sample is smaller than that of the nondoped sample in spite of
the larger amount of metallic λ, FeSi phase, and this fact indicates that P solution into the ζ2
phase is effective for reducing the thermal conductivity.
6 25 Fe–P–Si
Miscellaneous
A high-resolution scanning Auger microprobe analysis was carried out by [1991Men] on

matching fracture surfaces of symmetrical ∑ = 5 (013) bicrystals of Fe-3 mass% Si doped with
270 ppm phosphorus which were grown from seeds by floating-zone melting. Phosphorus
distribution on some regions of a fracture surface was found to alternate between high and low
concentrations. These alternations were often associated with deformation bands, such as
mechanical twins. The reverse pattern was found on the matching region on the opposite
fracture surface.
Investigations of thermo-diffusion processes in Fe-P-Si alloys were carried out by
[1973Wan]. A measuring arrangement for studies of thermo-diffusion in molten iron alloys
was described, the Soret coefficients of silicon and phosphorus in the Fe-P-Si heats were
determined. The lattice and grain boundary tracer diffusion coefficients D*PL and P*P of
phosphorus in the Fe98.91Si0.96P0.13 (at.%) alloy were measured by [1983Mat] in the tempera-
ture range from 710 to 882˚C. The effect of Si additions on D*PL and P*P was concluded to be
small. The sintering and alloying behavior of ferrous metal powder ternary compact Fe-3 mass
% Si-3 mass% Fe3P (Fe90.06Si5.21P4.73 in at.%) was studied by [1990Qu] using dilatometry and
SEM. It was found that phosphorus and silicon behave synergetically; phosphorus enhances
alloying between Fe and Si at temperatures in the range 900-1100˚C. The concentration of
interstitially dissolved Fe atoms in a Si crystal doped with a rather high concentration of P was
found by [1994Tak] to depend on the cooling rate of the crystal. It was measured to decrease
with an increase in the concentration of P and a decrease in the cooling rate. It was reported by
[1990Reb, 1998Vav] that Fe-P-Si alloys have a tendency to amorphization in the concentration
range between 12 and 20 at.% P and 2 to 10 at.% Si, but later this range was precised by
[1997Vav, 1999Vav, 2000Vav1] as between 14 and 20 at.% P and 10 at.% Si at cooling rates of
105 to 106 K·sec–1. Annealing was shown by [2000Vav2, 2003Bal] to give a rise to nanoscale
crystallization of amorphous Fe-P-Si alloys. The process occurs in one, two or three steps, and
the annealed alloys contain crystallites 30 to 140 nm in size. Later the crystallization behavior
of amorphous Fe-P-Si alloys was studied by [2003Bal] applying Mössbauer spectroscopy and
physico-chemical analysis. The resulting materials are found to contain nanocrystalline
particles of a complex composition, characterized by a doublet and several sextets in the
Mössbauer spectrum. The amorphous alloys containing 6 or 10 at.% Si were found to possess
the highest thermal stability, while the alloys with 2 at.% Si have a tendency toward nanoscale
crystallization, accompanied by hardening.
. Table 1
Investigations of the Fe-P-Si Phase Relations, Structures and Thermodynamics
[1930Hum] Melting in vacuum furnace, optical microscopy, The Fe-Fe2P-FeSi region

thermal analysis, chemical analysis, heating in
vacuum
[1933Sau] Melting in vacuum furnace, heating in vacuum, 1000˚C, the Fe-Fe2P-FeSi region
X-ray diffraction (Debye technique)

Fe–P–Si 25 7
[1959Vog] Melting in Pythagoras crucible (calcium chloride < 1500˚C, the Fe-FeP2-SiP-Si
cover), thermal analysis, optical microscopy, region
chemical analysis
[1962Run] Induction melting, heating, X-ray diffraction 50 at.% Fe, 0 to 25 at.% Si
(Guinier technique)
[1965Kan1] Electrolytical isolation, X-ray diffraction, chemical 1000˚C, 800˚C, 2.5 mass% P in the
analysis alloys
[1965Kan2] X-ray diffraction, chemical analysis 1100-700˚C, ≤ 4 at.% P
[1965Sab] Induction melting, optical microscopy, X-ray 1080˚C, the Fe-FeP2-SiP-Si region
powder diffraction (Debye-Scherrer technique)
[1968Sab] Induction melting, optical microscopy, X-ray 1080˚C, the Fe-FeP2-SiP-Si region
powder diffraction (Debye-Scherrer technique)
[1979Yam] Melting, Knudsen cell-mass spectrometry εPSi in liquid phase, 1600˚C,
≤ 12.1 mass% Si
[1983And] Induction melting, X-ray powder diffraction 66.7 at.% Fe, ≤ 22.3 at.% Si
(Haegg-Guinier camera)
[1983Ban] Transportation method εPSi in liquid phase, 1400˚C,
≤ 12.1 mass% Si
[1983Yam] Melting, Knudsen cell-mass spectrometry εPSi in liquid phase, 1600˚C,
≤ 12.1 mass% Si
[1984Jer] Induction melting, sintering, X-ray powder 66.7 at.% Fe, ≤ 22.3 at.% Si
diffraction (Haegg-Guinier camera), Mössbauer
spectroscopy
57
[1990Reb] Fe Mössbauer spectroscopy 2 to 10 at.% Si, 12 to 20 at.% P
[1991Men] Floating-zone technique, high-resolution Fe rich range
scanning Auger spectroscopy of fracture surfaces
[1993Bal] Arc melting, 57Fe Mössbauer gamma- resonance 2 to 10 at.% Si, 12 to 20 at.% P
spectroscopy, differential thermal analysis, X-ray
diffraction
[1995Per] Solution growth from molten Sn (single crystal 1127-777˚C, FeSi4P4
preparation), powder synthesis, X-ray diffraction
(Guinier technique)
[1997Ued] Equilibration of alloys in controlled P partial 1450˚C, ≤ 63 at.% Fe, ≤ 0.92 at.% P
pressure
[1997Vav] Arc melting, X-ray diffraction, thermal analysis, ≤ 10 at.% Si
TEM, electron diffraction, Mössbauer
spectroscopy
[1998Vav] Mössbauer spectroscopy, differential thermal 2 to 10 at.% Si, 12 to 20 at.% P
analysis, X-ray diffraction

8 25 Fe–P–Si
[1999Vav] Mössbauer spectroscopy, differential thermal 2 to 10 at.% Si, 12 to 20 at.% P

analysis
[2002Ito] Arc melting, mechanical alloying, X-ray Hot pressing at 900˚C (3.6 ks, 25
diffraction, SEM, EDX MPa); ≤ 33.3 at.% Fe, ≤ 6.67 at.% P
[2003Bal] Arc melting, liquid quenching, X-ray diffraction, 2 to 10 at.% Si, 12 to 20 at.% P
DTA
. Table 2
Pearson
Symbol/
Phase/ Space
α, (αδFe) cI2 dissolves 4.55 at.% P at 1048˚C, 4 at.%

P at 1000˚C [2002Per]

Im3m dissolves 19.5 at.% Si at ~1280˚C [Mas2]
W dissolves 2.2 at.% P at 7.6 at.% Si,
1000˚C [1965Kan2]
(δFe) (h2) a = 293.15 pure Fe, T = 1360˚C [V-C2]
1538 - 1394
(αFe) (r) (ferrite) a = 286.65 pure Fe, T = 25˚C [V-C2]
< 912
(γFe) (h1) (austenite) cF4 a = 364.68 pure Fe, T = 912˚C [V-C2]
1394 - 912 Fm3m dissolves 0.56 at.% P and 3.19 at.% Si
Cu at 1150˚C [Mas2]
at 1 at.% Si dissolves 3.9 at.% P at
1000˚C, 1.9 at.% P at 800˚C [1965Kan2]
dissolves 0.8 at.% P at 1.2 mass% Si,
1000˚C; 0.6 at.% P at 3.5 mass% Si
1000˚C [1965Kan2]
(P) (red) c*66 a = 1131 sublimation at 1 bar. Stable form of P.
< 417 Triple point at 576˚C, > 36.3 bar; triple
point at 589.6˚C at 1 atm [Mas2, V-C2]
(P) (white) c** a = 718 common form of P [Mas2, V-C2]
< 44.14 -
P (white)

Fe–P–Si 25 9
Pearson
Symbol/
Phase/ Space
(P) (black) oC8 a = 331.36 T = 25˚C [Mas2, V-C2]

Cmca b = 1047.8
P (black) c = 437.63
(αSi) cF8 a = 543.06 T = 25˚C [Mas2, V-C2]
< 1414 Fm3m
C (diamond)
(βSi) (II) tI4 a = 468.6 T = 25˚C, p > 9.624 bar [Mas2, V-C2]
I41/amd c = 258.5
βSn
(γSi) (III) cI16 a = 663.6 T = 25˚C, p > 16.208 bar [Mas2, V-C2]
Im3m
γSi
(δSi) (I) hP4 a = 380 T = 25˚C, p = 16.208-1.013 bar
P63/mmc c = 628 [Mas2, V-C2]
αLa
β, Fe3P tI32 a = 910.8 at 25 at.% P [V-C2]
< 1166 I4 c = 445.5
Ni3P a = 917.4 T = 678˚C [1990Oka]
c = 452.99
γ, Fe2P (I) hP9 at 33.3 at.% P
< 1370 at 1.013 kbar P62m [Mas2, V-C2]
Fe2P a = 586.4 at 33.3 at.% P [1984Jer]
c = 346.0
γ, Fe2SixP1–x a = 586.75 x = 0 to 0.17 at room temperature
c = 345.81 [1984Jer]
a = 592.12 x = 0.10, room temperature [1984Jer]
c = 342.26
Fe2P (II) oP12 a = 577.5 T = 800˚C, 80 kbar
high pressure phase Pnma b = 357.1 [Mas2, V-C2]
Co2Si c = 664.1

10 25 Fe–P–Si
Pearson
Symbol/
Phase/ Space
δ, FeP oP8 50 at.% P [Mas2]

≲ 1370 Pnma a = 519.1 [1962Run]
MnP b = 309.9
c = 579.2
a = 519.3 at 20˚C [1972Sel], symmetry
b = 309.9 diminished to space group Pn21a by
c = 579.3 slight shift of the P atoms
δ, FeSixP1–x x = 0 to 0.5 [1962Run]
a = 524.2 x = 0.5 [1962Run]
b = 305.9
c = 585.3
ε, FeP2 oP6 66 to 67 at.% P [Mas2]
Pnnm a = 497.29 at 66.7 at.% P [1969Dah, 1990Oka]
FeS2 b = 565.68
(marcasite)
c = 272.30
π, FeP4 (I) mP30 80 at.% P [Mas2]
P21/c a = 461.9 [1978Jei]
FeP4 b = 1367.0
c = 700.2
β = 101.48˚
FeP4 (II) oC20 a = 500.5 T = 1100˚C, 60 kbar
high pressure phase C2221 b = 1021.3 [Mas2, V-C2]
FeP4 c = 553.0
α2, Fe4Si or Fe2Si (h) cP2 B2, ~ 10 to 22 at.% Si [Mas2]
≲ 1280 Pm3m a = 281 consecutive annealing of a Fe66.3Si33.7
CsCl (at.%) button at 1100˚C for 18 h and
of powder at 1150˚C for 7 min
[1974Koe, V-C2]
α1, Fe3Si cF16 D03, 11 to 30 at.% Si [1982Kub, Mas2]
≲ 1235 Fm3m a = 565.0 [V-C2]
BiF3
κ, Fe2Si hP6 ~33.0 to ~34.3 at.% Si [1982Kub]
1212 - ~1040 P
3m1 a = 405.2 ± 0.2 [V-C2]
Fe2Si c = 508.55 ± 0.03
η, Fe5Si3 hP16 37.5 at.% Si [1982Kub]
1060 - 825 P63/mcm a = 675.9 ± 0.5 [V-C2]
Mn5Si3 c = 472.0 ± 0.5

Fe–P–Si 25 11
Pearson
Symbol/
Phase/ Space
λ, FeSi cP8 ~ 49.6 to ~ 50.8 at.% Si [Mas2]

< 1410 P213 dissolves 2.1 mass% P at 1080˚C
FeSi [1965Sab]
a = 451.7 ± 0.5 [V-C2]
a = 448.61 to 447.64 0 to 4.56 mass% P (0 to 6 at.% P) at
33.8 mass% Si, annealing at 1000˚C for
100 h [1965Sab]
ζ1, FeSi2(h) tP3 69.5 to 73.5 at.% Si [Mas2]
1220 - 937 P4/mmm a = 268.72 to 269.37 69.6 to 72.1 at.% Si, annealing at
FeSi2 (h) c = 512.8 to 513.9 1080˚C for 100 h [V-C2]
a = 269.09 at 5 mass% P, annealing at 1080˚C for
c = 513.08 100 h [1965Sab]
ζ2, FeSi2(r) oC48 66.7 at.% Si [1982Kub]
< 982 Cmca a = 986.3 ± 0.7 [V-C2]
FeSi2 (r) b = 779.1 ± 0.6
c = 783.3 ± 0.6
μ, SiP oC48 50 at.% P [Mas2]
≲ 1131 Cmc21 a = 351.18 single crystal studies [V-C2]
SiP b = 2048.8
c = 1360.7
ω (Si-P) amorphous - metastable; amorphous phase forming
≲ 1131 from a gaseous mixture of SiH4 and PH3
at 450˚C. Decomposed at 600˚C into
(Si) and the μ phase [Mas2]
SiP2 cP12 a = 570.5 studies of a single crystal Si33.6P66.4
Pa
3 (at.%) heated in an evacuated silica
FeS2 (pyrite) tube at 900˚C [V-C2]
τ1, FeSi4P4 aP9 [1959Vog, 1965Sab, 1968Sab]
≲ 1210 P1 a = 487.61 single crystal annealed at T = 927˚C
FeSi4P4 b = 554.52 [1995Per]
c = 606.43
α = 85.33˚
β = 68.40˚
γ = 70.43˚
τ2, Fe2SixP1–x oI* - 0.20 < x < 0.36, T = 997˚C [1984Jer]
?
Fe2SixP1–x

12 25 Fe–P–Si
Pearson
Symbol/
Phase/ Space
ψ (Fe-Si-P) amorphous - metastable; in alloys (in at.%) Fe82Si2P16

and Fe78Si10P12, rapidly quenched and
then annealed at 500˚C for 10 min; in
alloys Fe80Si6P14, Fe78Si10P12 and
Fe78Si2P20, rapidly quenched and
then annealed at 600˚C for 10 min
[1997Vav, 1998Vav, 1999Vav]
. Table 3
Composition (at.%)
Reaction T [˚C] Type Phase Fe P Si
LÐδ+λ 1223 e2 L 50.0 22.7 27.3

L+κÐα+λ - U1 L ~ 68 ~2 ~ 30
LÐγ+λ 1183 e7 L 58.6 17.2 24.2
LÐγ+δ+λ 1166 E1 L 56.4 21.5 22.1
L Ð (Si) + τ1 1123 e9 L 6.8 28.1 65.1
L Ð μ + τ1 - e10 - - - -
L Ð μ + (Si) + τ1 1116 E2 L 3.2 31.4 65.4
L Ð Ð ζ1 + τ1 1115 e11 L 21.3 19.3 59.4
L Ð ζ1 + (Si) + τ1 1113 E3 L 20.6 19.2 60.2
L+γÐβ+λ 1110 U2 L 68.1 9.1 22.8
L Ð λ + τ1 1105 e12 L 31.1 21.7 47.2
L Ð δ + τ1 - e13 - - - -
L Ð λ + ζ 1 + τ1 1096 E4 L 30.7 21.1 48.2
L Ð λ + δ + τ1 1095 E5 L 31.7 22.9 45.4
LÐλ+β+α 1018 E6 L 76.8 12.0 11.2

Fe–P–Si 25 13
. Table 4
Investigations of the Fe-P-Si Materials Properties
[1965Sab] PMT-3 mechanical testing, picnometry Microhardness, density

[1981Yan] Hysteresigraph tracer technique Maximum permeability, coercive force
[1983And] Mössbauer spectroscopy Curie temperature
[1983Mat] Residual activity method Curie temperature
[1984Jer] Mössbauer spectroscopy Curie temperature
[1988Liu] Small scale Charpy impact test Ductile-brittle transition temperature
57
[1993Bal] Fe Mössbauer gamma-resonance Effective magnetic field acting upon the
spectroscopy, mechanical tests nucleus, microhardness, plasticity of foils
[1994Tak] ESR spectroscopy Magnetic susceptibility versus magnetic
field
[1997Vav] Electrical resistance and magnetic Electrical resistance, effective magnetic
measurements field
[1998Vav] Mechanical properties tests, electrical Brittle temperature, electrical resistivity
resistivity measurements
[1999Vav] Mechanical properties tests, magnetic Microhardness, plasticity, effective
measurements magnetic field, chemical shift
[2000Vav1] Rapid quenching, X-ray diffraction, thermal Kinematic viscosity
analysis, Mössbauer spectroscopy;
viscosity measurements (rotational
oscillations of a quartz beaker filled with
the melt
[2002Ito] Four probe dc method (computer- Seebeck coefficient, electrical resistivity,
controlled equipment); laser flash method thermal diffusivity, specific heat, density,
(thermal contact analyzer ULVAC TC-7000) thermal conductivity
[2003Bal] Mechanical properties tests, Mössbauer Electrical resistance, microhardness
spectroscopy
[2004Vav] Thermal annealing, pulsed photon Size of particles; microhardness
processing
[2006Jan] Mechanical properties tests, Auger Energy of intergranular fracture
electron spectroscopy

14 25
Fe-P-Si. Reaction scheme, part 1
. Fig. 1a
Fe–P–Si

Fe-P-Si. Reaction scheme, part 2
. Fig. 1b
Fe–P–Si 25 15

16 25 Fe–P–Si
. Fig. 2
Fe-P-Si. Partial liquidus surface projection

Fe–P–Si 25 17
. Fig. 3
Fe-P-Si. Temperature - composition section at 5 mass% P, plotted in at.%

18 25 Fe–P–Si
. Fig. 4
Fe-P-Si. Temperature - composition section at 13 mass% P, plotted in at.%

Fe–P–Si 25 19
. Fig. 5
Fe-P-Si. Temperature - composition section at 7 mass% Si, plotted in at.%

20 25 Fe–P–Si
References
[1930Hum] Hummitzsch, W., Sauerwald, F., “The Iron-Phosphorus-Silicon System” (in German), Z. Anorg. Allg.
Chem., 194, 113–138 (1930) (Morphology, Phase Diagram, Phase Relations, Experimental, *, 9)
[1933Sau] Sauerwald, F., Teske, W., Lempert, G., “X-Ray Studies of the Cr-C and Fe-Si-P Systems” (in German),
Z. Anorg. Chem., 210, 21–25 (1933) (Crys. Structure, Morphology, Experimental, *, 5)
[1949Jae] Jaenecke, E., “Si-Fe-P” (in German), Kurzgefasstes Handbuch aller Legierungen, Winter Verlag,
Heidelberg, 625–627 (1949) (Phase Diagram, Phase Relations, Review, *, 16)
[1959Vog] Vogel, R., Giessen, B., “The Iron-Phosphorus-Silicon System” (in German), Arch. Eisenhuettenwes.,
30(10), 619–626 (1959) (Crys. Structure, Morphology, Phase Diagram, Experimental, #, 9)
[1962Run] Rundqvist, S., “Phosphides of the B31 (MnP) Structure Type”, Acta Chem. Scand., 16(2), 287–292
[1965Kan1] Kaneko, H., Nishizawa, T., Tamaki, K., “Phosphide-Phases in Ternary Alloys of Iron, Phosphorus and
Other Elements” (in Japanese), Nippon Kinzoku Gakkai-shi, 29(2), 159–165 (1965) (Morphology, Phase
Diagram, Phase Relations, Experimental, Review, *, 24)
[1965Kan2] Kaneko, H., Nishizawa, T., Tamaki, K., Tanifuji, A., “Solubility of Phosphorus in α- and γ-Iron” (in
Japanese), Nippon Kinzoku Gakkai-shi, 29(2), 166–170 (1965) (Phase Relations, Experimental, Review,
*, 20)
[1965Sab] Sabirzyanov, A.V., Shumilov, M.A., “The Solubility of Aluminium and Phosphorus in Constituents of
High-Silicon Ferrosilicon” (in Russian), Tr. Ural’sk. Politekh. Ins., (144), 35–40 (1965) (Crys. Structure,
Morphology, Phase Diagram, Phase Relations, Experimental, Phys. Prop., 14)
[1968Sab] Sabirzyanov, A.V., Gel’d, P.V., “Some Features of the Peritectoid Transformation in β-Leboite (FeSi2)
Alloys Alloyed with Al, Ca and P” (in Russian), Tr. Ural’sk. Politekh. Inst., (167), 75–80 (1968)
(Morphology, Phase Relations, Experimental, 6) as quoted by [1988Rag]
[1969Dah] Dahl, E., “Refined Crystal Structures of PtP2 and FeP2”, Acta Chem. Scand., 23(8), 2677–2684 (1969)
(Crys. Structure, Experimental) as quoted by [1990Oka]
[1972Sel] Selte, K., Kjekshus, A., “Structural and Magnetic Properties of FeP”, Acta Chem. Scand., Ser. A, 26(3),
1276–1277 (1972) (Crys. Structure, Experimental, Magn. Prop., 17)
[1973Wan] Wanibe, Y., Sakao, H., Sugiyama, T., Maiwa, K., “Investigations into Thermo-Diffusion with Iron-
Silicon, Iron-Phosphorus and Iron-Silicon-Phosphorus Alloys”, Arch. Eisenhuettenwes., 44(8), 579–583
(1973) (Morphology, Experimental, Interface Phenomena) cited from abstract
[1974Koe] Koester, W., “Micro- and Crystal-Structure of Iron-Silicon Alloys Containing up to 40 at.% Si”, Trans.
Iron Steel Inst. Jpn., 14(6), 387–394 (1974) (Crys. Structure, Morphology, Phase Diagram, Phase
[1978Jei] Jeitschko, W., Braun, D.J., “Synthesis and Crystal Structure of the Iron Polyphosphide FeP4”, Acta Cryst.
B, 34, 3196–3201 (1978) (Crys. Structure, Experimental, 30)
[1979Yam] Yamada, K., Kato, E., “Mass Spectrometric Determination of Activities of Phosphorus in Liquid
Fe-P-Si, Al, Ti, V, Cr, Co, Ni, Nb and Mo Alloys” (in Japanese), Tetsu to Hagane (J. Iron Steel Inst. Jpn.),
65(2), 273–280 (1979) (Thermodyn., Calculation, Experimental, Review, 40)
[1981Yan] Yang, H.K., Lee, H.G., Im, H.B., “The Magnetic Properties of Sintered Fe-P and Fe-3 w/o Si-P Alloys”,
J. Korean Inst. Met., 19(6), 471–479 (1981) (Morphology, Experimental, Electr. Prop., Magn. Prop.)
cited from abstract
[1983And] Andersson, Y., “A New Ternary Phase in the Fe-P-Si System: Fe2P1–uSiu, 0.20 < u < 0.36”, VII Interna-
tional Conference on Solid Compounds and Transition Elements, Proc. CNRS, Grenoble (France), IIIA13/
1-IIIA13/3 (1983) (Crys. Structure, Experimental, Magn. Prop.) cited from abstract
[1983Ban] Ban-ya, S., Maruyama, N., Fujino, S., “The Effect of C, Si, Al and B on the Activity of Phosphorus in
Liquid Iron”, Tetsu to Hagane, 69, 921–928 (1983) (Thermodyn., Calculation, Experimental, Review, 32)
[1983Mat] Matsuyama, T., Hosokawa, H., Suto, H., “Tracer Diffusion of P in Iron and Iron Alloys”, Trans. Jpn.
Inst. Met., 24(8), 589–594 (1983) (Morphology, Experimental, Interface Phenomena, Kinetics, Magn.
Prop., 14)
Activity Coefficient of P in Liquid Iron”, Trans. Iron Steel Inst. Jpn., 23(1), 51–55 (1983) (Thermodyn.,
Calculation, Experimental, 16)

Fe–P–Si 25 21
[1984Jer] Jernberg, P., Yousif, A.A., Haeggstroem, L., Andersson, Y., “A Mössbauer Study of Fe2P1–xSix (x ≤ 0.35)”,
J. Solid State Chem., 53, 313–322 (1984) (Crys. Structure, Experimental, Theory, Electronic Structure,
Magn. Prop., 13)
[1988Liu] Liu, C.M., Abiko, K., Kimura, H., “Effect of Silicon on the Grain Boundary Segregation of Phosphorus
and the Phosphorus Induced Intergranular Fracture in High Purity Fe-Si-P Alloys” in “Strength of
Metals and Alloys (ICSMA8)”, Proc. of the 8th International Conference, Pergamon, 1101–1106 (1988)
(Morphology, Experimental, Mechan. Prop.) cited from abstract
[1988Rag] Raghavan, V., “The Fe-P-Si (Iron-Phosphorus-Silicon) System” in “Phase Diagrams of Ternary Iron
Alloys”, Indian Inst. Met., Calcutta, 3, 162–171 (1988) (Crys. Structure, Phase Diagram, Phase Relations,
Review, #, 11)
[1988The] “The 19th Committee on Steelmaking, The Japan Society for the Promotion of Science” in “Steelmaking
Data Sourcebook”, Gordon and Bresch Science Publishers, 280 (1988) (Morphology, Thermodyn.,
Review) as quoted by [1993Din]
[1990Oka] Okamoto, H., “The Fe-P (Iron-Phosphorus) System”, Bull. Alloy Phase Diagrams, 11(4), 404–412
(1990) (Crys. Structure, Phase Diagram, Phase Relations, Thermodyn., Assessment, Review, Magn.
Prop., *, 88)
[1990Qu] Qu, X., Lund, J.A., Gowri, S., “Synergistic Alloying-Sintering Effects in Iron-Silicon-Phosphorus
Compacts”, Diffusion and Defect Data - Solid State Data, Part B (Solid State Phenomena), B8-9, 319–329
(1990) (Morphology, Experimental, Interface Phenomena) cited from abstract
[1990Reb] Rebrikova, L.K., Kovneristyi, Yu.K., Vavilova, V.V., Levintov, B.L., “Phase Equilibria and Susceptibility
to Amorphization of Fe-P-Si Alloys” (in Russian), Konferenciya po Fizicheskoi Chimii i Tekhnologii
Fosfidov i Fosforsoderzhaschikh Splavov (Conf. on the Physical Chemistry and Technology of
Phosphides and Phosphorus-Containing Alloys), Alma-Ata, (1990) (Morphology, Phase Diagram,
Phase Relations, Experimental) as quoted by [1998Vav]
[1991Men] Menyhard, M., Rothman, B., McMahon, C.J., Jr., Lejcek, P., Paidar, V., “On the Fracture Path and the
Intergranular Phosphorus Distribution in Phosphorus-Doped Fe-Si Symmetrical Bicrystals”, Acta
Metall. Mater., 39(6), 1289–1295 (1991) (Crys. Structure, Morphology, Experimental, Mechan. Prop., 4)
[1993Bal] Baldokhin, Yu.V., Vavilova, V.V., Kovneristyi, Ya.K., Kolotyrkin, P.Ya., Rebrikova, L.K., “Mössbauer
Investigation of the Segregation Processes in the Amorphous Alloys of the Systems Fe-P-M (M: Mn, Si,
V)” (in Russian), Dokl. Akad. Nauk, 328(5), 575–579 (1993) (Crys. Structure, Phase Relations, Experi-
mental, Magn. Prop., Mechan. Prop., 7)
(China), 29(12), B527–B532 (1993) (Thermodyn., Calculation, Theory, 7)
[1994Tak] Takahashi, H., Suezawa, M., Sumino, K., “Iron-Phosphorus Interaction in Si”, Mater. Sci. Forum,
143–147, 1257–1262 (1994) (Morphology, Experimental, Kinetics, Magn. Prop., 12)
[1995Bou] Bouchard, D., Bale, C.W., “Simultaneous Optimization of Thermochemical Data for Liquid Iron Alloys
Containing C, N, Ti, Si, Mn, S, and P”, Metall. Mater. Trans. B, 26B, 467–484 (1995) (Phase Relations,
Thermodyn., Calculation, Review, Theory, 85)
[1995Per] Perrier, Ch., Vincent, H., Chaudouet, P., Chenevier, B., Madar, R., “Preparation and Crystal Structure
of a New Family of Transition Metal Phospho-Silicides”, Mater. Res. Bull., 30(3), 357–364 (1995) (Crys.
[1997Ued] Ueda, S., Morita, K., Sano, N., “Thermodynamics of Phosphorus in Molten Si-Fe and Si-Mn Alloys”,
Metall. Mater. Trans. B, 28(6), 1151–1155 (1997) (Thermodyn., Experimental, 15)
Si) Amorphous Alloys”, Inorg. Mater. (Engl. Trans.), 33(3), 275–281 (1997), translated from Neorg.
Mater., 33(3), 333–339 (1997) (Phase Diagram, Phase Relations, Thermodyn., Experimental, Electr.
Prop., Kinetics, Magn. Prop., 15)
[1998Vav] Vavilova, V.V., Kovneristyi, Yu.K., Palii, N.A., “Correlation between the Annealing-induced
Embrittlement of Fe-P-M (M = V, Mn, Si) Amorphous Alloys and the Content of α-Fe Precipitates”,
Inorg. Mater. (Engl. Trans.), 34(6), 566–570 (1998), translated from Neorg. Mater., 34(6), 692–696
(1998) (Crys. Structure, Morphology, Phase Relations, Experimental, Electr. Prop., Mechan. Prop., 17)
[1999Vav] Vavilova, V.V., Baldokhin, Y.V., “Mössbauer Study of Rapidly Quenched Fe-P-E Alloys (E = V, Nb, Mo,
Mn, Si)”, Russ. Metall. (Engl. Transl.), (1), 122–132 (1999) (Crys. Structure, Phase Diagram, Phase
Relations, Thermodyn., Experimental, Review, Kinetics, Magn. Prop., Mechan. Prop., 20)

22 25 Fe–P–Si
[2000Vav1] Vavilova, V.V., Baldokhin, Y.V., Kovneristyi, Yu.K., Matveev, V.M., “Fe-P-M (M = Si, Mn, V) Alloys:
Viscosity in the Liquid State and Tendency to Amorphization”, Inorg. Mater. (Engl. Trans.), 36(7),
703–708 (2000), translated from Neorg. Mater., 36(7), 845–851 (2000) (Morphology, Thermodyn.,
Calculation, Experimental, Kinetics, Phys. Prop., 13)
[2000Vav2] Vavilova, V.V., Palii, N.A., Kovneristyi, Yu.K., Timofeev, V.N., “Nanocrystalline Fe-P-Si Alloys”, Inorg.
Mater. (Engl. Trans.), 36(8), 783–787 (2000), translated from Neorg. Mater., 36(8), 945–949 (2000)
(Morphology, Experimental, Kinetics) as quoted by [2003Bal]
[2002Ito] Ito, M., Nagai, H., Oda, E., Katsuyama, S., Majima, K., “Effects of P Doping on the Thermoelectric
Properties of β-FeSi2”, J. Appl. Phys., 91(4), 2138–2142 (2002) (Crys. Structure, Morphology, Calcula-
tion, Experimental, Electr. Prop., 19)
[2002Per] Perrot, P., Batista, S., Xing, X., “Fe-P (Iron-Phosphorus)”, MSIT Binary Evaluation Program, in MSIT
ment ID: 20.16107.1.20, (2002) (Crys. Structure, Phase Diagram, Phase Relations, Thermodyn., Assess-
ment, Phys. Prop., #, 23)
[2002Tan] Tani, J.-i., Kido, H., “Geometrical and Electronic Structures of β-FeSi1.875X0.125 (X = B, Al, N or P)”, Jpn.
J. Appl. Phys., 41(11A), 6426–6429 (2002) (Crys. Structure, Calculation, Electronic Structure, 21)
[2003Bal] Baldokhin, Yu.V., Vavilova, V.V., Kovneristyi, Yu.K., Kolotyrkin, P.Ya., Palii, N.A., Solomatin, A.S.,
“Mössbauer Study of Nanoscale Crystallization in Amorphous Fe-P-Si Alloys During Annealing”,
Inorg. Mater. (Engl. Trans.), 39(5), 479–484 (2003), translated from Neorg. Mater., 39(5), 576–582
(2003) (Crys. Structure, Morphology, Experimental, Electr. Prop., Kinetics, Magn. Prop., Mechan.
Prop., 8)
[2004Vav] Vavilova, V.V., Ievlev, V.M., Isaenko, A.P., Kovneristyi, Y.K., Palii, N.A., Timofeev, V.N., “Effect of
Thermal Annealing and Pulsed Photon Processing on the Relaxation and Crystallization of
Amorphous Fe-P-Si Alloys”, Inorg. Mater., 40(2), 152–160 (2004) (Morphology, Experimental, Mechan.
[2006Jan] Janovec, J., Pokluda, J., Jenko, M., Lejcek, P., Vlach, B., Hornikov, J., “Influence of Phosphorus on
Energy of Intergranular Fracture in Fe-Si-P Alloys”, Surf. Interface Anal., 38(4), 401–405 (2006)
(Morphology, Experimental, Mechan. Prop.) cited from abstract
(1990)

Fe–S–Ti 26 1
Iron – Sulphur – Titanium

Nataliya Bochvar, Lazar Rokhlin
Introduction
The presence of sulphur in iron and steel leads commonly to decrease of strength, ductility and
corrosion resistance. The steels containing sulphur incline to cracking at high temperatures of
hot working. Therefore, the sulphur content in commercial steels is strictly limited in
steelmaking processes. Titanium additions to the steel melts result in precipitation of disperse
spherical complex sulphides which are modificators of cast structure and decrease the sulphur
danger. For successful control this process, the Fe-S-Ti phase diagram is of a great importance.
There is a number of reports on the ternary sulphides in the Fe-S-Ti system. The ternary
compound Ti2FeS4 was reported by [1968Plo1, 1968Plo2, 1973Mur1, 1973Mur3], who deter-
mined its crystal structure and lattice parameters. The ternary compound TiFe2S4 was studied
by [1973Mur2]. [1970Dan, 1974Dan] reported two ternary compounds Ti4FeS8 and Ti4Fe3S8,
and their crystal structures. There are few reports about the phase equilibria in the Fe-S-Ti
system. The liquidus surface and a number of the vertical sections in the region Fe-FeS-TiS-
TiFe2 were constructed by [1948Vog]. Phase equilibria at 600, 950 and 1300˚C were studied by
[1957Hah], [1963Kan] and [1968Swi], respectively.
The effect of Ti on the solubility and activity of S in liquid Fe at 1550 to 1640˚C was
determined by [1966Sch, 1969Sch, 1973Buz, 1977Eji1, 1977Eji2, 1985Don, 1987Don].
In the review on the Fe-S-Ti phase diagram of [1988Rag], the liquidus surface and reaction
scheme are presented based on data of [1948Vog].
[1995Bou] optimized the thermodynamic data for liquid alloys of iron containing Ti, S
and other elements.
The list of the experimental works on the Fe-S-Ti phase diagram is presented in Table 1.
Binary systems
The Fe-S binary system is accepted after [Mas2] supplemented by [1982Kub1]. The Fe-Ti
binary system is accepted after [1982Kub2]. The S-Ti binary system is accepted after [Mas2]
supplemented by [1986Mur].
Solid Phases
Four ternary compounds found in the Fe-S-Ti system are given in Table 2. These are τ1,
Ti2FeS4; τ2, TiFe2S4; τ3, Ti4FeS8; τ4, Ti4Fe3S8 [1968Plo1, 1970Dan, 1973Mur1, 1973Mur2,
1973Mur3, 1974Dan]. All the ternary compounds were established by preparation in the
direct synthesis from the elements of stoichiometric ratio by heating up to temperatures 900
or 1000˚C. The character of formation, the melting temperatures and the homogeneous ranges

2 26 Fe–S–Ti
of these compounds were not studied. The certain connection between crystal structures of the
ternary phases τ1, τ3 and τ4 was noted [1974Dan].
The binary FeS and TiS compounds dissolve some Ti and Fe, respectively. There is
discrepancy in values of solubility. According to [1934Kle], the compounds FeS and TiS
form continuous solid solution, whereas [1948Vog, 1963Kan, 1976Mal] established the
limited solution between these compounds. According to [1948Vog], the maximum solubility
of Ti in FeS is about 30 mass% whereas [1963Kan] determined these solubility to be about 7
mass%. Absence of the continuous solid solution of FeS and TiS was confirmed by [1957Hah,
1970Kur] with extension of the limited FeS-base solid solution similar to that reported by
[1948Vog]. On the contrary, solubility Fe in TiS was estimated about 22 mass% according to
[1963Kan] and about 10 mass% according to [1948Vog]. Along with them, further investiga-
tions are desirable in order to avoid these discrepancies.
Continuous solid solution between FeS and TiS can be obtained under high pressure.
Thus, [1991Mak] synthesized the alloys along FeS-TiS section at temperatures 2127 to 2227˚C
under pressure about 70 kbar followed by quenching down to 577˚C. Using X-ray analysis,
[1991Mak] established existence of the solid solution Ti1–xFexS at 0.2 ≤ x ≤ 1.0 with the NiAs
type structure. The lattice parameter a decreased from 345.9 to 334.7 pm and the lattice
parameter c increased from 589.1 to 628.9 pm if the alloy composition changed from FeS to
Ti0.8Fe0.2S.
Quasibinary Systems
[1948Vog] and [1963Kan] presented the section FeS-TiS as quasibinary system. However, this
section can be recognized as the quasibinary one only in limits from the FeS side up to ~ 50
mass% Ti because TiS forms from liquid by the peritectic reaction L + Ti8S9 Ð TiS at ~1780˚
C. FeS and TiS interact by invariant peritectic reaction at the temperature 1540˚C [1948Vog]
or ~1370˚C [1963Kan]. The peritectic temperature 1540˚C by [1948Vog] should be assumed
to be more reliable because of more experiments used. Figure 1 shows the FeS-TiS partial
quasibinary section taking into account [1948Vog].
According to [1948Vog] the TiFe2-TiS section is the quasibinary one. This, however, can be
accepted only below ~ 55 mass% Ti. This section is characterized by existence of the liquid
miscibility gap, monotectic and eutectic invariant reactions. The reaction temperatures were
not indicated. Moreover, [1948Vog] showed two maxima (monotectic and eutectic points) on
the double saturation lines in the Fe-corner. These points are located very close to the Fe-TiS
section [1948Vog]. In opinion of [1988Rag], close location of the monotectic and eutectic
points on the double saturation lines to the Fe-TiS section seems to suggest the section to be
quasibinary one. The temperatures of the monotectic and eutectic points are 1500˚C and
~1440˚C, respectively. These values are taken from the vertical sections [1948Vog].
Five four-phase and four three-phase invariant equilibria were established for the Fe-FeS-
TiS-TiFe2 region of the Fe-S-Ti system by [1948Vog]. They are shown in the reaction
scheme (Fig. 2) assumed, in general, after the review [1988Rag]. According to [1948Vog],
temperatures of the points U1, U2, E1 are between 1390 and 1400˚C for U1, U2, and 1300˚C
Fe–S–Ti 26 3
for E1. In [1988Rag] these temperatures were corrected to meet the accepted binary systems
and taken as ~ 1360, ~1350, ~1280˚C, respectively. The temperature of U3, p2max, e1max, e2max
points were taken as 1000, 1570, 1500, 1440˚C in this assessment from vertical section
[1948Vog]. The temperatures of points e3min, e5max, U4 were taken by [1988Rag] speculatively.
Liquidus Surface
There is only one article by [1948Vog] in which the liquidus surface in the Fe-FeS-TiS-TiFe2
region of the Fe-S-Ti system was described. [1948Vog] established existence of the miscibility
gap in liquid state extending from Fe-corner to the TiFe2-TiS section. Two liquids, L1
(metallic) and L2 (sulphide) participate in invariant reactions e1max, e2max and U2. There is
one minimum point (c2) on the line bounding the miscibility gap at the composition about
77.2 mass% Fe, 21.2 mass% S, 1.6 mass% Ti. It is reasonable to suppose also the existence of
the maximum point c1 on the line bounding the miscibility gap out of the studied area of the
phase diagram (in the direction of the Ti corner from the section TiS-TiFe2 (Fig. 3). The
liquidus surface is shown in Fig. 3 according to [1948Vog] evaluated in mass%. The liquidus
surface includes the miscibility gap and six regions of primary crystallization: (δFe,αFe), (γFe),
FeS, TiS, Ti8S9 and TiFe2.
Isothermal Sections
The isothermal section at 600˚C was studied by [1957Hah] in the FeS-TiS2-TiS region. The
one-phase ranges of the NiAs and CdI2 type structures are shown approximately. The
isothermal section at 950˚C was constructed by [1963Kan] in the limits of the Fe-FeS-TiS-
TiFe2 region. [1963Kan] drew the tie lines in the two-phase areas joining (δFe,αFe) or (γFe)
with two sulphides FeS and TiS. However, there is considerable disagreement in solubility
limits of Ti and Fe in corresponding sulphides that was discussed earlier. This section and the
section at 600˚C are not shown in this assessment.
The isothermal section at 1300˚C was constructed by [1968Swi] in Fe corner of the Fe-S-Ti
phase diagram. Figure 4 shows this isothermal section with the tie lines in two-phase area
joining (γFe) with the sulphide TiS at various partial pressure of sulphur. Positions of the three
upper tie lines were drawn based on data obtained for the high sulphur partial pressure.
Positions of the two lower tie lines were drawn based on one or two data points only and,
therefore, should be regarded as approximate. The phase boundary between (γFe) and
sulphide TiS was established from the solubility measurements in the range from 0.1 to
0.4 mass% Ti. The Fe contents in the sulphide TiS was not determined by [1968Swi] because
the experimental data yielded only the sulphur to titanium ratio in the sulphide TiS and did
not give the iron contents.
The isotherm of solubility of S and Ti in the Fe rich liquid phase at 1600˚C is shown in
Fig. 5 according to the calculation made by [1995Bou] using the experimental data [1973Buz,
1987Don]. The existence of the minimum solubility on the curve may be explained by
decrease of the sulphur activity resulting from the Ti presence.

4 26 Fe–S–Ti
Seven vertical sections of the Fe-S-Ti phase diagram in limits of the Fe-FeS-TiS-TiFe2 region
were constructed by [1948Vog]. Two of them are reproduced in Figs. 6 and 7 with some
corrections to meet the accepted binary phase diagrams. In accordance with this, temperatures
of the four-phase invariant equilibria U1, U2, E1 are given in the reaction scheme (Fig. 2).
Thermodynamics
The activity coefficient of sulphur was determined by [1966Sch, 1969Ban, 1969Sch, 1973Buz,
1974Sig, 1977Eji1, 1977Eji2, 1985Don, 1987Don]. Titanium decreases the activity coefficient
of sulphur in both liquid and solid iron. The first-order interaction coefficients in liquid iron
at 1600˚C are eSTi = –0.082 [1966Sch, 1969Sch, 1973Buz], –0.072 [1974Sig], –0.18 [1977Eji1,
1977Eji2], –0.2 [1985Don, 1987Don]. According to [1969Ban] eSTi = –0.072 at 1550˚C. The
discrepancies in the reported activity coefficients could be caused by the different methods
used in the experiments.
[2001Sud] determined thermodynamic properties of the Fe-S melts containing different
d- and f- metals (in particular, Ti) by the calorimetric method. The partial mole enthalpies of
the melts were established and taken into account at the desulphurization of steels.

[1973Mur2] reported the results of the magnetization and Mössbauer effect measurements on
TiFe2S compound. The temperature dependence of magnetization was constructed for various
magnetic fields up to 18 kOe between 2 and 340 K. Mössbauer spectra were determined at 291,
276 and 80 K. Magnetic transition temperature was determined at 285 K.
[1973Mur3, 1968Plo2] constructed the temperature dependence of electric resistivity of
Ti2FeS4. The Ti2FeS4 resistivity measured on single crystal sample [1973Mur3] was similar to
the results obtained by [1968Plo2] on polycrystalline samples. However, the kink on the
resistivity curve at Neel temperature of Ti2FeS4 was not observed in the [1968Plo2] results.
Based on the X-ray investigation of quenched samples [1968Plo1] showed the absence of the
temperature-dependent order-disorder transition in this compound. Unlike [1968Plo1], in
[1973Mur1] the transition from vacancy-order state to vacancy-disorder state was observed at
720 K during magnetic measurements of the Ti2FeS4 sample at the temperature between liquid
nitrogen temperature and 1273 K. The sample showed antiferromagnetism with the Neel
temperature at 138 K. This discrepancy of [1968Plo1, 1968Plo2] and [1973Mur1, 1973Mur3]
results may be explained by the difference of heat treatments of the samples during prepara-
tions. [1974Dan] measured electric and magnetic properties of the TiFexS2 alloys at x = 0.25,
0.33, 0.40, 0.50, 0.75 in the temperature range from 7 to 400 K. Measured alloys showed a
competition between ferromagnetism and antiferromagnetism.
The temperature dependence of magnetization and magnetic susceptibility of the alloys
along the FeS-Ti0.8Fe0.2S section were established by [1991Mak]. The experiments were
conducted under high pressure. [1991Mak] determined the temperatures of the magnetic
phase transitions in these alloys and constructed the magnetic phase diagram of the FeS-TiS
solid solution.
Fe–S–Ti 26 5
[2004Kim, 2005Nam] measured Mössbauer spectra of the Ti0.025Fe0.975S alloy at various

temperatures between liquid nitrogen temperature and 600 K. The Neel temperature, crystal-
lographic phase transition temperature and the Morin transition temperature were deter-
mined.
Miscellaneous
[1965Sch] investigated a possibility of the sulphide formation in Fe-S-Ti system at 1600˚C.
They discovered that the sulphide TiS was formed only at the lower than 1600˚C temperature
during crystallization of the Fe-rich liquid phase.
[1976Mal] investigated formation and nature of the sulphide phase in Fe-S-Ti and
C-Fe-S-Ti systems. [1976Mal] showed that the titanium sulphide eutectic was formed between
the branches of the austenite dendrites during the solidification of Fe-S-Ti alloys with low
S and Ti contents. With increasing concentrations of Ti and S the amount of sulphide eutectic
increased and at approximately 0.5 mass% S and 2.5 mass% Ti the alloy possessed a purely
eutectic structure. The titanium sulphide eutectic was formed in C-Fe-S-Ti alloys even at low
Ti content together with a titanium carbide eutectic.
Also, the mechanism of the titanium sulphides formation around the branches of the
austenite dendrites in the Fe-S-Ti alloys during crystallization was studied by [1981Sam], who
gave the mathematical description of this process.
Using an electron microprobe analyzer, [1968Ska] studied the effect of Ti additions on the
morphology, size and mode of precipitation of sulphides in pure iron with high sulphur
content.
In the review [1968Hul] the transition-element compounds with the structure of various
types (pyrite, marcasite, CdI2, NiAs and others) were discussed.
[1995Bou] presented a database of thermochemical parameters for liquid iron-base alloys
containing Ti, S and other elements. Expressions for the interaction parameters of the solutes
and the Gibbs energies of formation of the carbides, nitrides and sulphides of titanium were
simultaneously optimized. It was shown that the resulting thermochemical database repro-
duced the experimental data satisfactorily.

6 26 Fe–S–Ti
. Table 1
Investigations of the Fe-S-Ti Phase Relations, Structures and Thermodynamics
[1934Kle] Alloys were prepared by melting of FeS 1000 to 1600˚C The partial FeS-TiS
with 1, 5, 10, 20, 44% TiS2 at different section from 0 to 40 mass% TiS
temperature from 1360 to 1630˚C.
Chemical, thermal and microstructure
analyses
[1948Vog] Krupp WW Fe, Ti (95%), pure S were At the temperatures from 1500 to 800˚C
melted in alumina crucible in Ar. The in Fe-FeS-TiS-TiFe2 composition range.
thermal analysis, optical microscopy, Liquidus surface and vertical sections.
chemical analysis of the separated layers, Invariant equilibria.
X-ray analysis
[1957Hah] The direct synthesis of elements. 900 to Phase relations at 600˚C in the FeS-TiS2-
1000˚C for 48 hour, then 600˚C for more TiS composition range.
week. X-ray analysis
[1963Kan] Electrolytic isolation of sulphides from 950˚C, Fe-rich alloys with S from 0 to
ternary alloys. Chemical and X-ray 40 mass% and Ti from 0 to 60 mass%. The
analyses isothermal section at 950˚C.
[1965Sch] Alloys were prepared in induction furnace 1600˚C, Fe alloys with 0.6 to 4.3 mass% Ti
in argon atmosphere. Chemical and and 0.1 mass% S
metallographic analyses
[1966Sch] Alloys were prepared in induction furnace Solubility of Ti and S in Fe liquid at
in argon atmosphere at 1600˚C. Chemical 1600˚C, activity coefficient of S in Fe
analysis, thermodynamic liquid
[1968Plo1] Synthesis of stoichiometric ratio Ti Ternary compound Ti2FeS4. Crystal
(99.99%), Fe (99.99%), powder S structure and order-disorder transition.
(99.999%) in evacuated silica tube at 600,
800 and 1000˚C during one week.
Quenching from 1300˚C into ice water,
then annealing at 800, 1000˚C and slow-
cooled at the rate of 10 K·h–1. X-ray
measurement.
[1968Swi] Flat plates (0.03 by 2 by 4) from Fe-Ti alloys with 0.12, 0.24, 0.38,
specimens of Fe-Ti alloys made in 0.54 mass% Ti and 0 to 0.08 mass% S. The
induction furnace were equilibrated at temperature range from 1150 to 1300˚C.
1300˚C in resistance furnace in H2S-H2 Solubility of S in Fe-Ti alloys at 1300˚C
mixture. Chemical analysis, electron
microprobe.
[1969Ban] Electrolytic Fe, pure Ti and pure iron 1550˚C, the effect Ti on the activity
sulphide. Alumina crucibles, resistance coefficient of S in liquid iron
furnace, exposed to a fixed sulphur
potential gas for 4 to 12 hours at 1550˚C,
quenching. Gravimetrical and chemical
analyses, calculation, thermodynamic.

Fe–S–Ti 26 7
[1969Sch] Alloys were prepared in induction furnace Solubility of Ti and S in Fe liquid at

in argon atmosphere at 1600˚C. Chemical 1600˚C, activity coefficient of S in
analysis, thermodynamic Fe liquid
[1970Dan] Synthesis of elements with TiS2 in silica Ternary compounds Ti4FeS8 and Ti4Fe3S8.
tubes at 900˚C for 5 h. X-ray analysis Crystal structure and lattice parameters
[1973Buz] Electron-probe analysis and X-ray Solubility of Ti and S in Fe liquid and
diffraction, thermodynamic. activity coefficient of S in liquid Fe at
1600˚C.
[1973Mur1] Direct reaction of Fe (99.99%), Ti (99.99%), Ternary compound Ti2FeS4. Crystal
powder S (99.999%) in an evacuated silica structure and lattice parameters.
tube at 500˚C for 1 week, then at 900˚C
for 1 week. Chemical and X-ray analyses,
magnetic measurements.
[1973Mur2] Direct reaction of highly pure elements in Ternary compound TiFe2S4. Crystal
an evacuated silica tube at 750˚C for structure and lattice parameters.
2 weeks. Chemical and X-ray analyses,
magnetic measurements on torsion
balance magnetometer.
[1973Mur3] Single crystal of Ti2FeS4 was prepared in Single crystal of Ti2FeS4. Lattice
sealed evacuated tube from powder parameters.
sample with 10–6 MmHg, Cl2 gas as a
growth agency. X-ray diffraction,
measurement of electric resistivity.
[1974Dan] Synthesis of elements with TiS2 in silica Alloys along FexTiS2 at x = 0.25, 0.5, 0.75
tubes at 900˚C for 5 h and 1000˚C for 10 (ternary compounds Ti4FeS8, Ti2FeS4 and
h X-ray analysis, electric and magnetic Ti4Fe3S8). Crystal structure and lattice
measurements parameters.
[1976Mal] Alloys were prepared in vacuum electric Cast alloys in Fe-corner, S varied from
furnace in alundum crucibles from 0.009 to 0.1 mass% and Ti from 0.012 to
carbonyl Fe, metallic Ti and elemental S. 0.53 mass%. The effect of Ti and S
X-ray microanalyser, microprobe and contents on the sulphide formations.
microstructure analyses.
[1977Eji1, Alloys were prepared by melting Fe-S in 1600˚C, solubility S and Ti in Fe liquid,
1977Eji2] induction furnace with addition of Ti interaction parameters, activity
under argon. Thermodynamic properties coefficient
[1987Don] High purity Fe (99.99%) and Ti (99.7%) Series of liquid Fe-Ti-S alloys in
and iron sulphide (powder). High temperature range of 1560 to 1640˚C.
frequency induction furnace, argon gas. The TiS solubility product and sulphur-
Stabilization at 1640˚C for 10 min and titanium interaction parameter at 1600˚C.
quenching. Stabilization at 1560˚C for 10
min and quenching. Optical pyrometer,
chemical analysis, energy dispersive
spectroscopy, thermodynamic.

8 26 Fe–S–Ti
[2004Kim] Alloys were prepared by direct reaction of Alloy FeS with 1.25 at.% Ti (Ti0.025Fe0.975S).
the elements (of high purity, better than Crystal structure and lattice parameters at
99.9%) in evacuated and sealed quartz room temperature
tubes at 1000˚C for 7 days followed by
quenching. X-ray diffraction, Mössbauer
measurements.
[2005Nam] Alloys were prepared by direct reaction of Alloy FeS with 1.25 at.% Ti (Ti0.025Fe0.975S).
the elements (of high purity, better than Crystal structure and lattice parameters at
99.995%) in evacuated quartz ampoules room temperature
at 600˚C for 1 day, then at 1000˚C for 3
days followed by quenching. X-ray
diffraction, Mössbauer measurements.
. Table 2
Pearson
Symbol/
δα, (δFe,αFe) cI2 (δFe) and (αFe) merges and dissolves 9.8 at.% Ti at
Im3m 1290˚C in Fe-Ti system [1982Kub2]
W
(δFe) dissolves ~0.24 at.% S at 1365˚C
1538 - 1394 [Mas2]
a = 293.15 [Mas2]
a = 293.78 at 1480˚C [V-C2]
(αFe) dissolves 0.033 at.% S at 1365˚C [Mas2] and 3.08 at.
< 912 % Ti at 900˚C
[1982Kub2]
a = 286.65 at 25˚C [Mas2]
(γFe) cF4 dissolves 0.09 at.% S at 1365˚C [Mas2] and 0.8 at.%
1394 - 912 Fm3m Ti at 1120˚C [1982Kub2]
Cu a = 364.67 at 915˚C [Mas2]
a = 366.00 at 1167˚C [V-C2]
(βS) mP48 a = 1102 100 at.% S [Mas2]
115.22 - 95.9 P21/a b = 1096
βS c =1090
β = 96.7˚

Fe–S–Ti 26 9
Pearson
Symbol/
(αS) oF128 100 at.% S

< 95.5 Fddd a = 1046.4 at 25˚C [Mas2]
αS b = 1286.60
c = 2448.60
(βTi) cI2 dissolves 0.01 at.% S at 1212˚C [Mas2] and 22 at.%
1670 - 882 Im3m Fe at 1085˚C [1982Kub2]
W a = 330.65 [Mas2]
(αTi) hP2 dissolves 0.02 at.% S at ~885˚C [Mas2] and
< 882 P63/mmc 0.055 at.% Fe at 590˚C [1982Kub2]
Mg a = 295.06 at 25˚C [Mas2]
c = 468.35
γFeS hP4 50 to 55 at.% S
1188 - 315 P63/mmc [Mas2]
NiAs dissolves about 27 at.% Ti along FeS- TiS section
[1948Vog]
a = 344.36 ± 5 [V-C2]
c = 587.59 ± 0.05
βFeS hP24 50 to ~52 at.% S [Mas2], troilite
315 -< 138 P62c a = 599.8 ± 1.1 [V-C2]
βFeS c = 1171 ± 1
a = 596.9 ± 0.2 quenching from 1000˚C, for Ti0.025Fe0.975S
c = 1169 ± 5 [2004Kim, 2005Nam]
αFeS hP6 50 to ~52 at.% S [Mas2]
< 138 P63/mmc a = 345.59 ± 0.05 [V-C2]
αFeS c = 577.89 ± 0.05
βFeS2 cP12 ~66.7 at.% S [Mas2], pyrite
743 - 444.6 Pa3 a = 541.8 ± 0.2 [V-C2]
βFeS2
αFeS2 oP6 ~66.7 at.% S [Mas2], marcasite
< 444.6 Pnnm a = 444.31 ± 0.09 [V-C2]
αFeS2 b = 542.15 ± 0.09
c = 338.71 ± 0.06
TiFe2 hP12 25.8 to 34.4 at.% Ti at 1200˚C
< 1427 P63/mmc [1982Kub2]
MgZn2 a = 478.5 ± 0.2 [V-C2]
c = 779.9 ± 0.3

10 26 Fe–S–Ti
Pearson
Symbol/
TiFe cP2 49.8 to 51.8 at.% Ti at 1080˚C

< 1317 Pm3m [1982Kub2]
ClCs a = 297.89 ± 0.03 [V-C2]
Ti6S h** ~14 at.% S [Mas2]
< 885 - a = 296.7 [1986Mur]
- c = 1450
Ti3S t** 25 at.% S [Mas2]
< 1305 - a = 997.8 [1986Mur]
- c = 490
Ti2S oP 31 to 35 at.% S [Mas2]
< 1410 36 a = 1406 [V-C2]
Pnnm b = 1135
Ta2P c = 332
TiS, (Ti1+xS) hP2 46 to 49.7 at.% S [Mas2]
≲ 1780 - 935 P6m2 dissolves about 8.8 at.% Fe along TiS- FeS section
CW [1948Vog]
a = 327.2 [1986Mur]
c = 643.8
TiS hP4 ~49.7 at.% S [Mas2]
< 935 P63/mmc a = 329.6 [V-C2]
NiAs c = 639.8
Ti8S9 hR18 ~52.6 at.% S [Mas2]
≲ 1975 R3m a = 342.3 [1986Mur]
- c = 2646
Ti8S10 hP18 ~55.6 at.% S [Mas2]
≲ 1850 P63/mmc a = 343.9 [1986Mur]
- c = 2893
Ti16S21 hR37.1 ~56.6 at.% S [Mas2]
R3m a = 344.1 [1986Mur]
- c = 6048
Ti2.67S4 hP6.8 57.9 to 61.4 at.% S [Mas2]
P63mc a = 343.85 [1986Mur]
- c = 1143.22

Fe–S–Ti 26 11
Pearson
Symbol/
(4H)2 mC40.14 Superlattice structure based on Ti2.67S4

Cc 59.8 to 60.3 at.% S [Mas2]
- a = 594.395 [1986Mur]
b = 1029.51
c = 2285.83
(4H)3 mC59.8 Superlattice structure based on Ti2.67S4
Cc [Mas2]
- a = 1030 [1986Mur]
b = 592
c = 3490
Ti7S12 hR19.1 ~62.8 at.% S [Mas2]
R3m a = 342.0 [1986Mur]
Ti7S12 c = 3432.6
TiS2 hP3 64.4 to 66.7 at.% S [Mas2]
P3m1 a = 340.73 [1986Mur]
CdI2 c = 569.53
TiS3 mP8 ~75 at.% S [Mas2]
< 632 P21/m a = 499 [1986Mur]
- b = 338
c = 877.84
β = 97.324˚

12 26 Fe–S–Ti
Pearson
Symbol/
* τ1, Ti2FeS4 mC14 a = 592.7 slowly cooling [1973Mur1]

C2/m b = 342.8
Cr3S4 c = 1145.8
β = 90.1˚
a = 592.8 quenching from 400˚C [1973Mur1]
b = 342.2
c = 1149.1
β = 90.0˚
b = 342.0
c = 1147.9
β = 90.0˚
b = 342.6
c = 1148.2
β = 90.0˚
a = 592.6 single crystal [1973Mur3]
b = 342.8
c = 1145.7
β = 90.1˚
a = 592.9 quenching from 1000˚C [1968Plo1]
b = 342.6
c = 1146
β = 90.1˚
a = 595 [1974Dan]
b = 341.7
c = 1153
β = 90.2˚
* τ2, TiFe2S4 mC14 a = 598 annealing at 750˚C [1973Mur2]
C2/m b = 343
Cr3S4 c = 1116
β = 91.7˚
* τ3, Ti4FeS8 mC52 [V-C2]
C2/m a = 1181 [1970Dan, 1974Dan]
Ti4FeS8 b = 683
c = 1140
β = 90.4˚
* τ4, Ti4Fe3S8 mC120 [V-C2]
C2/m a = 1184 [1970Dan, 1974Dan]
- b = 685
c = 2320
β = 90.3˚

Fe–S–Ti 26 13
. Fig. 1
Fe-S-Ti. Partial quasibinary FeS-TiS section

14
Fe-S-Ti. Partial reaction scheme
26 Fe–S–Ti
. Fig. 2

Fe–S–Ti 26 15
. Fig. 3
Fe-S-Ti. Liquidus surface projection in the Fe-FeS-TiS-TiFe2 region

16 26 Fe–S–Ti
. Fig. 4
Fe-S-Ti. Partial isothermal section at 1300˚C

Fe–S–Ti 26 17
. Fig. 5
Fe-S-Ti. Solubility S and Ti in liquid Fe at 1600˚C

18 26 Fe–S–Ti
. Fig. 6
Fe-S-Ti. Partial vertical section from the binary 94Fe-6S towards the binary 90Ti-10Fe (mass%)
alloys

Fe–S–Ti 26 19
. Fig. 7
Fe-S-Ti. Partial vertical section from Ti-corner towards the binary 70Fe-30S (mass%)

20 26 Fe–S–Ti
References
[1934Kle] Kleffer, J., “The Metallurgy of Titanium Sulphide in the Haglund Process” (in German), Metall Erz,
3(14), 307-320 (1934) (Morphology, Phase Diagram, Phase Relations, Experimental, 59)
[1948Vog] Vogel, R., Kasten, G.-W., “The Iron-Sulphur-Titanium Phase Diagram” (in German), Arch. Eisenhuet-
tenwes., 19, 65-71 (1948) (Experimental, Morphology, Phase Diagram, Phase Relations, 4)
[1957Hah] Hahn, H., Harder, B., Brockmueller, W., “Ternary Chalcogenides. X. The Reaction of Ti Sulphides with
Sulphides of Divalent Transition Metals” (in German), Z. Anorg. Allg. Chem., 288(5-6), 260-268 (1957)
(Crys. Structure, Experimental, Phase Relations, 8)
[1963Kan] Kaneko, H., Nishizawa, T., Tamaki, K., “Study on Phase Diagram of Sulfides in Steel” (in Japanese),
Nippon Kinzoku Gakkai Shi, 27(7), 312-318 (1963) (Phase Diagram, Experimental, Phase Rela-
tions, *, 23)
[1965Sch] Schindlerova, V., Buzek, Z., “The Experimental Investigation of the Possible Formation of Sulphides in
Systems of Fe-S-Al, Fe-S-Ti and Fe-S-Zr at 1600˚C” (in Czech), Sb. Ved. Pr. Vys. Sk. Banske Ostrave,
Rada Hutn., 11(3), 443-447 (1965) (Experimental, Morphology, Phase Relations, 11)
[1966Sch] Schindlerova, V., Buzec, Z., “Effect of Aluminum Titanium, Manganese, Zirconium, and Cerium on
the Solubility and Activity of Sulphur in Molten Iron at 1600˚C” (in Czech), Hutn. Listy, 21(3),
169-175 (1966) (Experimental, Phase Relations, Thermodyn., 14)
[1968Hul] Hulliger, F., “Crystal Chemistry of Chalcogenides and Pnictides of the Transition Elements”, Struc.
Bonding, 4, 83-229 (1968) (Crys. Structure, Review, 532)
[1968Plo1] Plovnick, R.H., Vlasse, M., Wold, A., “Preparation and Structural Properties of Some Ternary
Chalcogenides of Titanium”, Inorg. Chem., 7(1), 127-129 (1968) (Crys. Structure, Experimental, 9)
[1968Plo2] Plovnick, R.H., Perloff, D.S., Vlasse, M., Wold, A., “Electrical and Structural Properties of Some
Ternary Chalcogenides of Titanium”, J. Phys. Chem. Solids, 29, 1935-1940 (1968) (Crys. Structure,
Electr. Prop., Experimental, 8)
[1968Ska] Skala, J., Riman, R., “The Influence of Certain Elements (Al, Mn, Cr and Ti) on the Chemical
Composition of Iron Sulphides” (in Czech), Sb. Ved. Pr. Vys. Sk. Banske Ostrave, Rada Hutn., 14(3),
115-122 (1968) (Crys. Structure, Morphology, Experimental, 2)
[1968Swi] Swisher, J.H., “Sulfur Solubility and Internal Sulfidation of Iron-Titanium Alloys”, Trans. Met. Soc.
AIME, 242, 2433-2439 (1968) (Experimental, Phase Diagram, Phase Relations, Thermodyn., #, 13)
[1969Ban] Ban-ya, S., Chipman, J., “Sulphur in Liquid Iron Alloys: II – Effect of Alloys Elements”, Trans. AIME,
245(1), 133-143 (1969) (Experimental, Thermodyn., 18)
[1969Sch] Schindlerova, V., Buzek, Z., “The Effect of Al, Ti, Mn, Zr and Ce on the Solubility and Activity of S in
Molten Fe at 1600˚C” (in German), Freiberger Forschungshefte, 117B, 43-58 (1969) (Experimental,
Phase Relations, Thermodyn., *, 14)
[1970Dan] Danot, M., Rouxel, J., “MxTiS2 Systems (M = Alkali Metal or Transition Metal of the First Period x =
0 to 1); MTi4S8 and M3Ti4S6 (M = Fe, Co, Ni) Superstructures” (in French), Compt. Rend. Acad. Sci.
Paris, Ser. C, 271, 998-1001 (1970) (Crys. Structure, Experimental, 7)
[1970Kur] Kurihara, J., “Synthetic Products in the Ti-S and Fe-Ti-S Systems” (in Japanese), Denki Kagaku, 38
(11), 842-848 (1970) (Crys. Structure, Experimental) as quoted by [1988Rag]
Iron at 1600˚C”, “Metall. Chem. - Appl. Ferrous Metall.”, Int. Symp., Sheffield, July 1971, Iron Steel Inst,
London, 173-177 (1973) (Crys. Structure, Experimental, *, 8)
[1973Mur1] Muranaka, S., “Order-Disorder Transition of Vacancies in FeTi2S4”, Mater. Res. Bull., 8, 679-686 (1973)
(Crys. Structure, Experimental, Magn. Prop., 3)
[1973Mur2] Muranaka, S., “Magnetic Properties of Fe2TiS4”, J. Phys. Soc. Jpn., 35, 1553 (1973) (Experimental,
Magn. Prop., 3)
[1973Mur3] Muranaka, S., Takada, T., “Growth and Electrical Properties of FeMX4 (M = Ti, V; X = S, Se) Single
Crystals.”, Bull. Inst. Chem. Res., Kyoto Univ., 51(5), 287-294 (1973) (Crys. Structure, Electr. Prop.,
Experimental, 10)
[1974Dan] Danot, M., Rouxel, J., Gorochov, O., “Electrical, Magnetic and Structural Properties of the Phase
MxTiS2 (M = Fe, Co, Ni)” (in French), Mater. Res. Bull., 9, 1383-1392 (1974) (Experimental, Electr.
Prop., Magn. Prop., *, 24)
[1974Sig] Sigworth, G.K., Elliott, J.F., “The Thermodynamics of Liquid Dilute Iron Alloys”, Met. Sci., 8, 298-310

Fe–S–Ti 26 21
[1976Mal] Malinochka, Ya.N., Balakina, N.A., Shmelev, Yu.S., “The Sulphide Phases in Fe-Ti-S and Fe-C-Ti-S
Alloys”, Russ. Metall., (6), 169-174 (1976), translated from Izv. Akad. Nauk SSSR, Met., 6, 212-216
(1976) (Experimental, Kinetics, 15)
[1977Eji1] Ejima, A., Suzuki, K., Harada, N., Sanbongi, K., “Sulphur Equilibria in Molten Fe-La-S, Fe-Ti-S, and
Fe-Zr-S Systems” (in Japanese), Tetsu to Hagane, 63(6), 943-952 (1977) (Experimental, Phase Rela-
tions, Thermodyn., 22)
[1977Eji2] Ejima, A., Suzuki, K., Harada, N., Sanbongi, K., “Sulphur Equilibria in Molten Fe-La-S, Fe-Ti-S, and
Fe-Zr-S Systems”, Trans. Iron Steel Inst. Jpn., 17(6), 349-358 (1977) (Experimental, Morphology,
Thermodyn., 30)
[1981Sam] Samoylovich, Yu.A., Bryksin, V.M., “Rhytmic Growth of Dendritic Branches in Fe-Ti-S Melts”, Russ.
Metall., (5), 170-173 (1981), translated from Izv. Akad. Nauk SSSR, Met., (5), 218-220 (1981) (Experi-
[1982Kub1] Kubaschewski, O., “Iron-Sulphur” in “Iron Binary Phase Diagrams”, Springer-Verlag Berlin/Heidelberg,
and Verlag Stahluesen GmbH, Düsseldorf, Germany, 125-128 (1982) (Phase Diagram, Phase Relations,
Crys. Structure, Thermodyn., Review, 20)
[1982Kub2] Kubaschewski, O., “Iron-Titanium” in “Iron Binary Phase Diagrams”, Springer-Verlag Berlin/Heidel-
berg, and Verlag Stahluesen GmbH, Düsseldorf, Germany, 152-156 (1982) (Phase Diagram, Phase
Relations, Crys. Structure, Thermodyn., Review, 26)
[1986Mur] Murray, J.L., “The S-Ti (Sulphur-Titanium) System”, Bull. Alloy Phase Diagrams, 7(2), 156-163 (1986)
(Crys. Structure, Phase Diagram, Phase Relations, Review, 57)
[1985Don] Donahue, F.M.III, Pehlke, R.D., “Equilibrium between Sulfur and Titanium in Liquid Iron”, J. Met., 37
(11), A96-A96 (1985) (Experimental, Thermodyn., Abstract, 0)
[1987Don] Donahue, F.M.III, Pehlke, R.D., “Equilibrium between Sulfur and Titanium in Liquid Iron”, Metall.
Trans. B, 18(B), 681-685 (1987) (Experimental, Thermodyn., *, 14)
[1988Rag] Raghavan, V., “The Fe-S-Ti (Iron-Sulphur-Titanium) System” in “Phase Diagrams of Ternary Iron
Alloys”, Indian Inst. Metal., Calcutta, 2, 299-306 (1988) (Crys. Structure, Phase Diagram, Phase
Relations, Review, *, #, 22)
[1991Mak] Makovetskii, G.I., Yanushkevich, K.I., “Structure and Magnetic Properties of Solid Solutions of Iron
Sulphide-Titanium Sulphide System” (in Russian), Fiz. Tverd. Tela, 33(11), 3280-3283 (1991) (Exper-
imental, Phase Relations, Magn. Prop., 8)
[1995Bou] Bouchard, D., Bale, C.W., “Simultaneous Optimization of Thermochemical Data for Liquid Iron
Alloys Containing C, N, Ti, Si, Mn, S, and P”, Metall. Mater. Trans. B, 26B, 467-484 (1995) (Phase
Relations, Theory, Thermodyn., #, 85)
[2001Sud] Sudavtsova, V.S., Sharkina, N.O., Kudin, V.G., “Thermodynamic Properties of the Liquid Melts in the
Fe-S and Fe-S-Metals Systems”, Russ. J. Phys. Chem., 75(7), 1061-1064 (2001), translated from Zh. Fiz.
Khim., 75(7), 1178-1181 (2001) (Thermodyn., Experimental, 13)
[2004Kim] Kim, E.C., “Crystallographic and Magnetic Properties of Iron Sulfides Doped with 3d Transition
Metals”, J. Mater. Sci. Letter., 19, 693-694 (2000) (Crys. Structure, Magn. Prop., Experimental, 8)
[2005Nam] Nam, H.D., Kim, E.C., Han, J.S., “Mössbauer Study of Iron Sulfides Doped with 3d-Transition Metals”,
Solid State Commun., 135(5), 327-329 (2005) (Crys. Structure, Magn. Prop., Experimental, 8)
(1990)

Fe–Si–Ti 27 1
Iron – Silicon – Titanium

Wei Xiong, Yong Du, Chao Zhang
Introduction
The major contributions to the determination of the phase equilibria in the Fe-Si-Ti system
are due to [1938Vog, 1956Ben, 1966Mar, 2003Loe]. The phase equilibria of the Fe-Si-Ti
system were first investigated by [1938Vog], whose work was briefly reviewed by [1949Jae].
A liquidus projection was constructed in the Fe-TiFe2-τ2-FeSi region [1938Vog]. [1956Ben]
(and apparently [1954Ben]) determined the austenitic phase transformation temperature to
establish the limit of the austenitic iron region in the Fe-Si-Ti system. The isothermal section
at 800˚C previously constructed by [1966Mar] was recently modified by [2003Loe], who also
presented isothermal sections at 1150 and 1000˚C.
So far, seven stable ternary compounds were reported: τ1 (TiFeSi2) [1966Mar, 1967Mar,
1968Mar, 1982Ste, 1982Yar, 1990Ang, 2005Sai], τ2 (TiFeSi) [1938Vog, 1965Mar, 1966Fre,
1966Mar, 1967Far, 1967Mar, 1968Mar, 1970Jei, 2003Loe, 2005Sai], τ3 (TiFe4Si3) [1966Mar,
1974Ste, 2003Loe], τ4 (TiFe7Si2) [2003Loe], τ5 (Ti46Fe10Si44) [1966Mar], τ6 (Ti45Fe15Si40)
[1966Mar], and τ7 [1993Jud, 1997Boe]. Further work is needed to determine the crystallo-
graphic data of τ5 and τ6. In addition, four metastable ternary phases, TiFe2Si [1970Jac,
1972Jac, 1977Nic1, 1977Nic2], Ti2Fe1–xSix (0.03<x<0.06) [1992Man], Ti68Fe26Si6 [1997Tiw,
2003Man], and Ti68Fe28Si4 [1997Tiw], were observed during rapid solidification. It is recom-
mended to determine the phase relationships above 40 mass% Si, and the liquidus surface over
the whole composition range. Since only [2007Yan] provided a measured enthalpy of forma-
tion of the λ phase, more experiments on thermodynamic properties of the ternary phases are
desirable. Table 1 summarizes the investigations on phase relations, crystal structures and
thermodynamics in the Fe-Si-Ti system.
The previous evaluation of the Fe-Si-Ti system by [1987Rag] was mainly based on the
experimental investigations from [1938Vog, 1956Ben, 1963Bar, 1965Mar, 1966Fre, 1966Mar,
1967Mar, 1968Mar, 1970Jac, 1970Jei, 1974Ste, 1977Nic1, 1977Nic2].
Binary Systems
The binary systems Fe-Ti and Si-Ti are accepted from [Mas2], the Fe-Si is taken from
[1982Kub].
Solid Phases
Crystallographic data of the binary and ternary phases are given in Table 2. Among the ternary
solid solutions, the Laves λ phase (Ti(Fe1–xSix)2) with a large solubility of Si has attracted
considerable attention. By means of X-ray diffraction, [1963Bar] determined the lattice

2 27 Fe–Si–Ti
parameters for the λ Ti(Fe1–xSix)2 phase with x value of 0, 0.074, 0.255, and 0.375, respectively.
Recently, using X-ray diffraction, optical microscopy and first principles calculations,
[2007Yan] performed a systematic crystallographic investigation on the λ phase with x value
of 0.25 and revealed that Si substitution for λ stabilizes the ternary Laves C14 phase with
respect to the corresponding binary Laves phases. The first principles calculations by
[2007Yan] showed that the λ Ti(Fe0.75Si0.25)2 phase is a very weak ferromagnet.
The solubility of Fe in Ti5Si3 is about 4 at.% [1966Mar], and that of Ti in α1 is about 6.25
at.% [1977Nic2]. These measured solubilities [1966Mar, 1977Nic2] were confirmed in the
work of [2003Loe].
[1966Mar] first reported the τ1 phase with an orthorhombic unit cell, and measured a
density of 4.69 g·cm–3. Employing single crystal X-ray diffraction, a comprehensive crystallo-
graphic study on τ1 was carried out by [1982Ste], who predicted the density of τ1 with a value
of 5.078 g·cm–3.
The τ2 ternary compound found by [1938Vog], was firstly considered to have a hexagonal
structure by [1966Mar, 1968Mar], but later corrected to be orthorhombic by [1970Jei],
but often showing pseudohexagonal twinning. [1970Jei] determined the complete crystal
structure of τ2. [1966Mar] measured a density of 5.57 g·cm–3 for τ2, while [1967Far] reported
a lower experimental value of 5.46 g·cm–3 together with the measured melting point at
1760 ± 20˚C for a single-phase τ2 sample. Additionally, in the work of [1966Fre], τ2 was
observed to be resistant against oxidation in air up to 400˚C but oxidizing rapidly at much
higher temperatures.
In the work of [2005Sai], the Curie temperatures and saturation magnetizations of τ1 and
τ2 were studied using a vibrating sample magnetometer. The τ1 phase showed a low saturation
magnetization of 1.72·103 T and a Curie temperature of 644˚C. The τ2 phase exhibits a
saturation magnetization of 3.77·102 T and a Curie temperature of 455˚C.
[1966Mar] found that the τ3 phase has a similar crystal structure as TiCo4Si3. This was
later confirmed by [1974Ste], who reported for the τ3 phase a hexagonal unit cell, which
was confirmed by [2003Loe]. It is worthy to mention that the phase τ3 found at 800˚C by
[1966Mar] was observed by [2003Loe] at the higher temperatures 1000 and 1150˚C only, but
not at 800˚C. This may be because of insufficient annealing after leaving the temperature range
of stability, either by [1966Mar] or by [2003Loe]. Thus, some experiment to clarify the
temperature range of stability of τ3 is desirable.
By X-ray diffraction, [2003Loe] found a new phase, τ4, at 1150˚C, and determined it to be
isotypic to αMn with a mean lattice parameter of 883.7 pm.
Phases τ5 and τ6 were reported by [1966Mar] in the experimental isothermal section at
800˚C, but their crystal structures are still unknown.
[1997Boe] prepared a "ternary intermetallic phase" Ti25Fe60Si15 by sintering powder-
mixtures of the pure elements. The reported mass ratios of the elemental powders correspond
to a formula Ti25Fe56Si19. [2003Loe] at 1150˚C found this composition to be inside the
homogeneity range of the Laves phase λ Ti(Fe1–xSix)2. Also [1997Boe] assumed the C14
Laves phase structure for this phase, thus it must not be treated as an extra ternary phase.
For the composition investigated [1997Boe] determined a melting temperature of 1470˚C and
a Curie temperature of 212 ± 5˚C.
A metastable TiFe2Si phase in a Fe-7Si-1.75Ti (at.%) alloy was reported by [1970Jac,
1972Jac, 1977Nic1, 1977Nic2], appearing as finely dispersed particles inside the λ phase. The
TiFe2Si phase with the L21 structure is a metastable extension of the D03 (Fe3Si) phase with
one of the two different Fe positions occupied by Ti.
Fe–Si–Ti 27 3
[1992Man] found a commensurate phase in a melt-spun Ti2Fe1–xSix (0.03 < x < 0.06)
alloy, which is a metastable CsCl type phase with the lattice parameter close to 298 pm. A bcc
metastable phase was found in the rapidly solidified Fe-4Si-68Ti (at.%) alloy by [1997Tiw],
while [1997Tiw, 2003Man] reported an icosahedral phase in the rapidly solidified Fe-6Si-68Ti
(at.%) alloy. The orientational relationship of the bcc phase with the icosahedral phase has
been discussed by [1997Tiw].
Table 3 lists the experimentally observed invariant equilibria by [1938Vog, 1978Hao].

The liquid compositions are estimated from the liquidus drawing in [1987Rag] and should
be considered as tentative only.
Based on the results of [1938Vog], a reaction scheme (Fig. 1) for the Fe rich alloys was
given by [1987Rag]. [1978Hao] identified a eutectic reaction with the temperature of 1210˚C
and the composition of Fe-4.3Si-9.5Ti (mass%). Regarding the impure Ti used by [1938Vog]
this eutectic may be identical to E1 in Figs. 1, 2 and Table 3.
Liquidus Surface
The only study of the liquidus surface of the Fe-Si-Ti system is that of [1938Vog]. Although the
Ti for alloy preparation was only 95% purity, and the melting losses were nearly 20 mass%,
the experimental data of [1938Vog] still can provide a basis for understanding the solidifica-
tion behavior of the Fe rich alloys of this system. In consequence, the liquidus surface in the
Fe-TiFe2-τ2-FeSi region, which was constructed by [1938Vog] and modified by [1987Rag], is
shown in Fig. 2.
Isothermal Sections
[1956Ben] presented boundaries of the (αFe) range against the (αFe) + (γFe) two-phase field
at seven different temperatures (1100, 1060, 1055, 1032, 1012, 980 and 960˚C). However, this
figure is apparently problematic. Both phases, (αFe) and (γFe) are dilute and Henry’s law is
still approximately valid at the compositions inside this figure. That means, that the kink-like
changes of curvatures of the lines drawn by [1956Ben] are not realistic. They seem to be
artifacts due to limits of the accuracy of the measurements and due to incompatibilities
between the ends of the lines in the accepted binary Fe-Ti system and the ternary measure-
ments. Figure 3 shows the boundaries presented by [1956Ben] modified in the present work in
order to be consistent with Henry’s law.
[2003Loe] measured the partial isothermal sections with less than 35 at.% Si at 1150, 1000,
and 800˚C, which are shown in Figs. 4 to 6, respectively. The isothermal section at 800˚C
(Fig. 6) is merged with the Si rich part reported by [1966Mar] and modified to reduce
artificially large homogeneity ranges of the phases.
All three isothermal sections are corrected slightly in order to agree with the accepted
binary phase diagrams and to remove some violations of the Schreinmaker rule.

4 27 Fe–Si–Ti
Seven of the eight measured vertical sections at Fe rich corner by [1938Vog] are in question,
not only due to the high weight losses during the melting but also because phase relationships
at 1150 and 1000˚C are inconsistent with those measured by [2003Loe]. Since the phase
relationships for the vertical section from Fe94.8Si5.2 to Ti31Fe67.31Si3.69 (mass%) agree with
those reported by [2003Loe], this section is presented in Fig. 7.
Thermodynamics
In the work of [2007Yan], the enthalpy of formation of Ti(Fe0.75Si0.25)2 measured by an

isoperibolic calorimeter is –55.9 ± 1.6 kJ·mol–1 of atoms, which agrees well with the value of
–52.6 kJ·mol–1 of atoms derived by a first principles calculation.
The investigations of Fe-Si-Ti materials properties are summarized in Table 4. Magnetic

properties of the ternary phases are described in the section Solid Phases.
[1978Hao] reported that the eutectic in the Fe rich corner of the Fe-Si-Ti system could be
suitable for development of materials for directionally solidified turbine blades operating up
to 1150˚C, since its good oxidation resistance and attractive low specific gravity could meet
several important criteria associated with the manufacture of the turbine blades.
[1997Boe] reported that the powder-metallurgically produced Laves phase with the
composition TiFeSi is a promising high temperature material. It has high strength and
brittleness at room temperature and a good corrosion resistance against neutral and acidic
aqueous solutions.
[2001Ito] investigated the effect of Ti doping on the thermoelectric performance of hot-
pressed FeSi2(h), and did not find a significant influence on the thermoelectric properties.
[2004Kim] investigated the as quenched amorphous Ti78Fe15Si7 alloy with a large super-
cooled liquid region (61 K). The tensile fracture strength for this amorphous alloy was 1318
MPa and increased up to 1876 MPa for a volume fraction of 15% primary (βTi) phase.
The work of [2003Loe, 2004Loe] found that the Fe-Si-Ti alloys could be strengthened by
precipitation of the stable Laves phase λ, which is a hard and brittle intermetallic phase. The
yield stress as well as the brittle-to-ductile transition temperature increases with the Ti content
[2003Loe, 2004Loe]. Furthermore, [2004Loe] pointed out that a beneficial oxidation behavior
is expected for ternary Fe-Si-Ti alloys with moderate Si and Ti contents.
Miscellaneous
Figure 8 shows the lattice parameter and unit cell volume of the λ phase versus Si content
measured by [1966Mar, 1968Mar], who annealed the alloys at 800˚C for 3 months. The
average magnetization and lattice parameter of the TixFe2–xSi alloys (0 ≤⊊ x ≤⊊ 0.7) by
[1977Nic1] are shown in Figs. 9 and 10, respectively. In the work of [1990Ang], Ti prefers to
concentrate in τ1 during the precipitation when the overall Fe composition (in mass%) of the
Fe–Si–Ti 27 5
synthetic alloys is much higher than that of Ti. Figure 11 shows the thermomagnetic curves of
the τ1 and τ2 phases measured by [2005Sai]. In the work of [2005Ste], some general rules for
the occurrence of the different Laves phase polytypes are derived from a study of experimental
phase diagram of Fe-Si-Ti system. The study showed that the solubility of Si added to the Laves
phase λ cannot simply be explained by size effects.
. Table 1
Investigations of the Fe-Si-Ti Phase Relations, Structures and Thermodynamics
[1938Vog] Thermal analysis, metallography Liquidus projection in the Fe-TiFe2-

τ2-FeSi region
[1956Ben] Dilatation measurement The austenitic iron region
[1963Bar] X-ray diffraction λ, Ti(Fe1–xSix)2 (x = 0, 0.074, 0.255,
0.375)
[1965Mar, X-ray diffraction τ2
1966Fre]
[1966Mar] X-ray single crystal diffraction analysis, Isothermal section at 800˚C, τ1, τ2, τ3,
microstructural analysis τ5, τ6, the solubility of Fe in Ti5Si3
[1967Far] X-ray diffraction, metallography, thermal Reaction temperature, melting
analysis, density measurement. temperature and density of τ2
[1967Mar, X-ray diffraction, microstructural analysis τ1 and τ2
1968Mar]
[1970Jac] Electron microscopy, X-ray diffraction, TiFe2Si
electron probe microscopy
[1970Jei] Metallography, single crystal X-ray diffraction τ2
[1972Jac] Transmission electron microscopy TiFe2Si
[1974Ste] Single crystal X-ray diffraction τ3
[1977Nic1, Vibrating sample magnetometry, X-ray The magnetization and lattice
1977Nic2] diffraction parameter of TiFe2Si
[1978Hao] Differential thermal analysis, energy dispersive The eutectic temperature of the Fe-
X-ray analysis 4.3Si-9.5Ti (mass%) alloy
[1982Ste, Single crystal X-ray diffraction τ1
1982Yar]
[1992Man] X-ray diffraction, transmission electron Ti2Fe1–xSix (0.03<x<0.06)
microscopy, energy dispersive X-ray analysis
[1997Boe] Specific magnetization measurement, Curie temperature of τ7 (212 ± 5˚C),
calorimeter and high temperature dilatometer melting temperature of τ7
[1997Tiw, X-ray diffraction, transmission electron Ti68Fe28Si4 and Ti68Fe26Si6
2003Man] microscopy

6 27 Fe–Si–Ti
[2003Loe] X-ray diffraction, differential thermal analysis, τ2, τ3, τ4, isothermal sections at 800,
metallography, electron microscopy 1000, 1150˚C
[2005Sai] X-ray diffraction, scanning electron Curie temperatures and saturation
microscopy, vibrating sample magnetometer magnetization of τ1 and τ2
[2007Yan] X-ray diffraction, optical microscopy, first Crystal structure and enthalpy of
principles calculation, isoperibolic calorimetry formation of λ, Ti(Fe1–xSix)2 (x = 0.25)
. Table 2
Pearson
Symbol/
(βTi) cI2 a = 330.65 at 900˚C [Mas2]

1670 - 882 Im3m
W
(αTi) hP2 a = 295.06 at 25˚C [Mas2]
< 882 P63/mmc c = 468.35
Mg
1394 - 912 Fm3m
Cu
(αδFe) cI2
(δFe) Im3m a = 293.15 pure Fe at 1390˚C [V-C2, Mas2]
1538 - 1394 W
< 912
(αSi) cF8 a = 543.06 at 25˚C [Mas2]
< 1414 Fd3m
C (diamond)

Fe–Si–Ti 27 7
Pearson
Symbol/
λ, Ti(Fe1–xSix)2 hP12 Laves C14 phase

P63/mmc 0 ≤ x ≤ 0.375 [1963Bar]
MgZn2 a = 479.0 at x = 0 [V-C2]
c = 781.1
TiFe2 a = 478.9 at x = 0.074
< 1427 c = 779.6
a = 479.7 at x = 0.255
c = 775.7
a = 480.3 at x = 0.375
c = 772.5
a = 478.0 [1977Nic2]
c = 765.2
a = 480.45 ± 0.034 at x = 0.25 [2007Yan]
c = 776.86 ± 0.08
a = 479.7 ± 0.2 at 800˚C, 41.0 - 67.0 at.% Fe, 0 - 27.5 at.% Si,
c = 773.8 ± 0.9 24.3 - 35.6 at.% Ti
at 1000˚C, 24.5 - 72.3 at.% Fe, 0 - 26.3 at.% Si,
23.1 - 39.6 at.% Ti
at 1150˚C, 40.8 - 72.3 at.% Fe, 0 - 27.1 at.% Si,
22.4 - 44.9 at.% Ti [2003Loe]
TiFe cP2 [Mas2]
< 1317 Pm3m a = 297.6 [V-C2]
CsCl a = 298.1 ± 0.1 at 800˚C, 46.6 - 50.3 at.% Fe, 0 - 18.4 at.% Si,
49.7 - 52.2 at.% Ti
at 1000˚C, 46.6 - 50.3 at.% Fe, 0 - 1.3 at.% Si,
49.7 - 52.8 at.% Ti
at 1150˚C, 0 - 1.7 at.% Si [2003Loe]
TiSi2 oF24 [Mas2]
< 1500 Fddd a = 826.71 [V-C2]
TiSi2 b = 480.00
c = 855.05
TiSi oP8 [Mas2]
< 1570 Pmm2 or a = 654.4 [V-C2]
Pnma b = 363.8
FeB c = 499.7
Ti5Si4 tP36 [Mas2]
< 1920 P41212 a = 670.2 [V-C2]
Zr5Si4 c = 1217.4

8 27 Fe–Si–Ti
Pearson
Symbol/
Ti5Si3 hP16 [Mas2]

< 2130 P63/mcm a = 746.10 ± 0.3 [V-C2]
Mn5Si3 c = 515.08 ± 0.1
at 800˚C, 0 - 3.1 at.% Fe, 35.8 - 38.7 at.% Si,
61.2 -64.2 at.% Ti
at 1000˚C, 0 - 3.9 at.% Fe, 33.3 - 38.8 at.% Si,
61.2 - 64.2 at.% Ti
at 1150˚C, 0 - 1.7 at.% Fe [2003Loe]
Ti3Si tP32 [Mas2]
< 1170 P42/n a = 1019.6 [V-C2]
Ti3P c = 509.7
α1, Fe3Si cF16 D03, 11.0 to 30.0 at.% Si [1982Kub]
≤ 1235 Fm3m a = 565.0 [V-C2]
BiF3 The solubility of Ti in α1 is not less than 6.25
at.% [1977Nic2]
at 800˚C, 64.2-84.8 at.% Fe, 15.2-27.3 at.% Si,
0-10.8 at.% Ti
at 1000˚C, 68.0-81.2 at.% Fe, 0-7.3 at.% Ti at
1150˚C, 0 - 6.2 at.% Ti [2003Loe]
α2, Fe-Si cP2 B2, 10.0 to 22.0 at.% Si [1982Kub]
≤ 1280 Pm3m a = 281 [V-C2]
CsCl at 800˚C 0 - 0.9 at.% Ti
at 1150˚C 0 - 2.1 at.% Ti [2003Loe]
β, Fe2Si hP6 at 1150˚C, 0 - 2.9 at.% Ti [2003Loe]
1212 - 1040 P3m1 ~33.0 to ~34.3 at.% Si [1982Kub]
Fe2Si a = 405.2 ± 0.2 [V-C2]
c = 508.55 ± 0.03
Fe5Si3 hP16 [1982Kub]
1060 - 825 P63/mcm a = 675.9 ± 0.5 [V-C2]
Mn5Si3 c = 472.0 ± 0.5 at 1000˚C 57.0 - 62.5 at.% Fe, 37.1 - 37.5 at.%
Si, 0 - 5.9 at.% Ti
at 1150˚C 56.5 -57.9 at.% Fe, 37.2 - 37.5 at.%
Si, 2.9 - 4.6 at.% Ti [2003Loe]
< 1410 P213 a = 451.7 ± 0.5 [V-C2]
FeSi
ζα, FeSi2(h) tP3 69.5 to 73.5 at.% Si [1982Kub]
1220 - 937 P4/mmm a = 269.01 [V-C2]
FeSi2 c = 513.4

Fe–Si–Ti 27 9
Pearson
Symbol/
ζβ, FeSi2(r) oC48 66.7 at.% Si [1982Kub]

< 982 Cmca a = 986.3 ± 0.7 [V-C2]
FeSi2 b = 779.1 ± 0.6
c = 783.3 ± 0.6
* τ1, TiFeSi2 oP48 at 800˚C 50 at.% Si, 20-29 at.% Ti
Pbam [1966Mar]
TiMnSi2 a = 861.37 ± 0.08 [1982Ste]
b = 953.4 ± 0.1
c = 763.96 ± 0.04
a = 856.0 [1966Mar, 1967Mar, 1968Mar]
b = 953.0
c = 764.0
a = 858.7 ± 0.3 [1982Yar]
b = 947.9 ± 0.5 Curie temperature is 644˚C [2005Sai]
c = 762.6 ± 0.2
* τ2, TiFeSi oI36 at 1150˚C 30.2 to 37.3 at.% Fe, 32.7 to
< 1760 ± 20 Ima2 33.0 at.% Si, 30.0 to 37.0 at.% Ti
TiFeSi [2003Loe]
at 1000˚C 30.3 to 35.3 at.% Fe, 32.3 to 37.2
at.% Si, 29.9 to 37.2 at.% Ti [2003Loe]
a = 699.7 ± 0.2 at 800˚C 30.3 to 35.7 at.% Fe, 32.6 to 32.8 at.%
b = 1083.0 ± 0.5 Si, 31.6 to 37.0 at.% Ti [2003Loe]
c = 628.7 ± 0.2 [1970Jei]
a = 699.9 ± 0.4
b = 1073.0 ± 0.6
c = 628.8 ± 0.6 [2003Loe]
Curie temperature is 455˚C [2005Sai]
* τ3, TiFe4Si3 hP168 [1966Mar]
> 800 P6/mmm a = 1720.6 [1974Ste]
c = 798.1
a = 1708.9 [2003Loe]
c = 797.1
* τ4, TiFe7Si2 cI58 at 1150˚C 67.4 to 68.4 at.% Fe, 20.9 to 21.7
1233 - ~1000 I43m at.% Si, 10.7 to 10.9 at.% Ti;
αMn at 1000˚C 68.9-69.0 at.% Fe, 19.8 to 20.0 at.%
Si, 11.1 to 11.2 at.% Ti [2003Loe]
a = 883.7 [2003Loe]
* τ5, Ti46Fe10Si44 - - [1966Mar]
* τ6, Ti45Fe15Si40 - - [1966Mar]

10 27 Fe–Si–Ti
Pearson
Symbol/
TiFe2Si (m) cF16 Metastable extension of the D03 α1 phase,

Fm3m a = 570.9 [1977Nic2]
Fe3Si
Ti68Fe28Si4 (m) c* a = 1130.0 [1997Tiw], metastable bcc phase
Ti68Fe26Si6 (m) - - [1997Tiw, 2003Man], metastable icosahedral
phase
Ti2Fe1–xSix (m) cP2 a = 298.0 0.03<x<0.06 [1992Man], metastable phase
Pm3m c = 2682.0
CsCl
. Table 3
Composition (at.%)*
Reaction T [˚C] Type Phase Fe Si Ti
L Ð λ + τ2 ~ 1500 e1 L 50.0 29.50 20.5

L Ð FeSi + τ2 ? e2 L 50.0 41.0 9.0
L Ð α1 + λ ? e3 L 67.3 25.7 7.0
L Ð α + α1 ? e4 L 74.7 22.3 3.0
L Ð α + α1 + λ 1205 E1 L 71.27 22.46 6.27
L + FeSi + τ2 Ð Fe5Si3 1200 P L 54.84 37.52 7.64
L + λ Ð α 1 + τ2 1185 U1 L 63.06 29.38 7.56
L + Fe2Si Ð FeSi + α1 ? U2 L 66.16 33.48 0.36
L + FeSi Ð α1 + Fe5Si3 1180 U3 L 65.69 33.32 0.99
L Ð α1 + Fe5Si3 + τ2 1145 E2 L 61.18 32.04 6.78
* compositions are read from the figure

Fe–Si–Ti 27 11
. Table 4
Investigations of the Fe-Si-Ti Materials Properties
[1978Hao] Oxidation measurement water oxidation resistance, density

displacement method
[1997Boe] Archimedes technique, hardness and Density, mechanical properties of τ7 (up to
fracture toughness measurement, 600˚C). The elastic constants, Young’s
indentation crack length method, modulus, Shear modulus, and Poisson’s
ultrasonic measurement, ratio, corrosion resistance of τ7 against
potentiodynamic measurement neutral and acidic aqueous solutions
[2001Ito] Ordinary DC method and laser flash The electrical resistivity, thermoelectric
thermal constant analyzer power, and thermal conductivity from
room temperature to 900˚C
[2003Loe, Vickers hardness and microhardness Hardness, yield stress, oxidation
2004Loe] testing, uniaxial compression, weighting, resistance, ductility and brittle-to-ductile
four-point bending test transition temperature
[2004Kim] Tensile testing Tensile fracture strength of the
amorphous alloy Ti78Fe15Si7

12 27 Fe–Si–Ti
. Fig. 1
Fe-Si-Ti. Partial reaction scheme of the Fe corner

Fe–Si–Ti 27 13
. Fig. 2
Fe-Si-Ti. Partial liquidus surface projection in the Fe corner

14 27 Fe–Si–Ti
. Fig. 3
Fe-Si-Ti. Joint solubility of both Ti and Si in (αFe) at different temperatures

Fe–Si–Ti 27 15
. Fig. 4
Fe-Si-Ti. Partial isothermal section at 1150˚C

16 27 Fe–Si–Ti
. Fig. 5

Fe–Si–Ti 27 17
. Fig. 6

18 27 Fe–Si–Ti
. Fig. 7
Fe-Si-Ti. Vertical section from Fe94.8Si5.2 to Ti31Fe67.31Si3.69 (mass%), plotted in at.%

Fe–Si–Ti 27 19
. Fig. 8
Fe-Si-Ti. Lattice parameters and unit cell volume of the λ Ti(Fe1–xSix)2 phase vs Si content

20 27 Fe–Si–Ti
. Fig. 9
Fe-Si-Ti. The average magnetization of the TixFe3–xSi alloys (0≤x≤0.7) vs outer electron
concentration

Fe–Si–Ti 27 21
. Fig. 10
Fe-Si-Ti. The lattice parameter of the TixFe3–xSi alloys (0≤x≤0.7) vs outer electron concentration

22 27 Fe–Si–Ti
. Fig. 11
Fe-Si-Ti. Thermomagnetic curves of τ2 and τ1

Fe–Si–Ti 27 23
References
[1938Vog] Vogel, R., Schlueter, W., “The Iron Corner of the Iron-Silicon-Titanium System” (in German), Arch.
Eisenhuettenwes., 12(4), 207–212 (1938) (Phase Diagram, Experimental, #, *, 10)
[1949Jae] Jaenecke, E., “Fe-Si-Ti” (in German), Kurzgefasstes Handbuch aller Legierungen, Winter Verlag, Heidel-
berg, 622–623 (1949) (Phase Diagram, Review, 1)
[1954Ben] Bentle, G.G., “γ-loop Studies in the Fe-Si and Fe-Si-Ti Systems”, Ph.D. Thesis, Vanderbilt Univ., U.S.A.,
(1954) (Phase Diagram, Experimental)
[1956Ben] Bentle, G.G., Fishel, W.P., “γ-Loop Studies in the Fe-Si and Fe-Si-Ti Systems”, Trans. AIME, 206,
1345–1348 (1956) (Phase Diagram, Experimental, #, 5)
[1963Bar] Bardos, A.M., Bardos, D.I., Beck, P.A., “The Effective Atomic Radius of Silicon in Ternary Laves Phase
Alloys”, Trans. Metall. Soc. AIME, 227, 991–993 (1963) (Crys. Structure, Experimental, 12)
[1965Mar] Markiv, V.Y., Voroshilov, Y.V., Gladyshevskii, E.I., “Ternary Laves Phases in the Systems Ti-Co-Si(Ge)
and Zr-Fe-Si(Ge)”, Inorg. Mater., 1(6), 818–821 (1965), translated from Izv. Akad. Nauk SSSR, Neorg.
Mater., 1(6), 890–893 (1965) (Crys. Structure, Experimental, 5)
[1966Fre] Freundlich, W., Farrokhi-Mochai, N., “Two Intermetallic Ternary Phases-ZrFeSi and TiFeSi” (in
French), Compt. Rend. Acad. Sci. Paris, 262, 1000–1001 (1966) (Crys. Structure, Experimental, 0)
[1966Mar] Markiv, V.Ya., Lysenko, L.A., Gladyshevskii, E.I., “Titanium-Iron-Silicon System”, Russ. J. Inorg. Chem.,
2(11), 1713–1716 (1966), translated from Izv. Akad. Nauk SSSR, Neorg. Mater., 2(11) 1980–1984 (1966)
(Crys. Structure, Phase Diagram, Phase Relations, Experimental, #, *, 15)
[1967Far] Farrokhi-Mochai, N., “A Study of the Solid Phases in the Fe-Si-Ti, Fe-Si-Zr, and Fe-Si-V Systems”
(in French), Rev. Chim. Miner., 4, 1–25 (1967) (Crys. Structure, Phase Diagram, Experimental, Phys.
Prop., 0)
[1967Mar] Markiv, V.Y., Gladyshevskii, E.I., Skolozdra, R.V., Kripyakevich, P.I., “Ternary Compounds of the RXX2
Type in the Ti-V(Fe, Co, Ni)-Si and Similar Systems”, Dop. Akad. Nauk Ukrain. SSR, (A)3, 266–269
[1968Mar] Markiv, V.Y., Gladyshevskii, E.I., Kripyakevich, P.I., Fedoruk, T.I., Lysenko, L.A., “A Study of the Phase
Equilibria and Crystal Structures of Compounds in the Ti-Fe(Co,Ni)-Si Systems” (in Russian), Dia-
grammy Sostoyaniya Metallich. Sistem, Nauka, Moscow, 137–145 (1968) (Crys. Structure, Phase Dia-
gram, Phase Relations, Experimental, 29)
[1970Jac] Jack, D.H., “Intermetallic Precipitate in an Fe-Ti-Si Alloy”, Met. Sci. J., 4, 22–24 (1970) (Crys. Structure,
Experimental, 6)
[1970Jei] Jeitschko, W., “The Crystal Structure of TiFeSi and Related Compounds”, Acta Crystallogr., Sect. B:
Struct. Crystallogr. Crys. Chem., B26, 815–822 (1970) (Crys. Structure, Experimental, 24)
[1972Jac] Jack, D.H., Honeycombe, R.W.K., “Age Hardening of an Fe-Ti-Si Alloy”, Acta Metall., 20, 787–796
(1972) (Phase Relations, Experimental, Mechan. Prop., 30)
[1974Ste] Steinmetz, J., Albrecht, J.M., Malaman, B., “A New Family of Ternary Silicides of the General Formula
TT4Si3 (T = Ti, Nb, Ta; T = Fe, Co, Ni)” (in French), Compt. Rend. Acad. Sci. Paris, 279C, 1119–1120
[1977Nic1] Niculescu, V., Budnick, J.I., “Limits of Solubility, Magnetic Properties and Electron Concentration in
Fe3–xTxSi System”, Solid State Commun., 24(9), 631–634 (1977) (Crys. Structure, Experimental, Theory,
Magn. Prop., 17)
[1977Nic2] Niculescu, V., Burch, T.J., Raj K., Budnick, J.I., “Properties of Heusler-Type Materials Fe2TiSi and
FeCo2Si”, J. Mag. Mag. Mater., 5(1), 60–66 (1977) (Crys. Structure, Experimental, 12)
[1978Hao] Haour, G., Mollard, F., Lux, B., Wright, G., “New Eutectics Based on Fe, Co or Ni”, Z. Metallkd., 69(1),
26–32 (1978) (Phase Relations, Experimental, Interface Phenomena, Mechan. Prop., Morphology, Phys.
Prop., 24)
(1982) (Phase Diagram, Review, #, *, 23)
[1982Ste] Steinmetz, J., Venturini, G., Roques, B., Engel, N., Chabot, B., Parthe, E., “TiMnSi2 and TiFeSi2 with
New Orthorhombic-Type Structure”, Acta Crystallogr., Sect. B: Struct. Crystallogr. Crys. Chem., B38,
[1982Yar] Yarmolyuk, Y.P., Sikiritsa, M., Akselrud, L.G., Lysenko, L.A., Gladyshevskii, E.I., “The Crystal Structure
of ZrCrSi2”, Sov. Phys. Crystallogr., 27(6), 652–653 (1982), translated from Kristallografiya, 27,

24 27 Fe–Si–Ti
[1987Rag] Raghavan, V., “The Fe-Si-Ti (Iron-Silicon-Titanium) System” in “Phase Diagrams of Ternary Iron Alloys”,
Ind. Inst. Techn., Delhi, Vol. 1, 65–72 (1987) (Crys. Structure, Phase Diagram, Phase Relations, Review,
#, *, 14)
[1990Ang] Anglezio, J.C., Servant, C., “Characterization of Metallurgical Grade Silicon”, J. Mater. Res., 5,
[1992Man] Mandal, P., Mandal, R.K., Tiwari, R.S., Srivastava, O.N., “Commensurate Ordering in Rapidly
Solidified Ti-Fe-Si Alloys”, Phys. Rev. B, Condens. Matter, 45(13), 7521–7524 (1992) (Crys. Structure,
Experimental, 19)
[1993Jud] Juda, T. (in German), Thesis, Technical Univ. Dresden (1990) as quoted by [1997Boe]
[1997Boe] Boehm, A., Pischang, K., Kieback, B., “Processing and Properties of the New Intermetallic Phase
Fe12Ti5Si3”, Metall, 51(10), 554–556 (1997) (Crys. Structure, Experimental, Magn. Prop., Phys. Prop., 5)
[1997Tiw] Tiwari, R.S., Mandal, P., Srivastava, O.N., “Quasicrystalline and Related Phases in Titanium Based Alloy
Systems”, Prog. Cryst. Growth Charact., 34, 271–285 (1997) (Crys. Structure, Experimental, 28)
Performance of β-FeSi2”, J. Alloys Compd., 315, 251–258 (2001) (Crys. Structure, Experimental, Electr.
Prop., 18)
[2003Loe] Loeffler, F., “Investigation of the Ternary Systems Fe-Si-Mg and Fe-Si-Ti: Phase Equilibria and Mechani-
cal Properties of the Alloys” (in German), Ph.D. Thesis, RWTH Achen, Germany (2003) (Crys. Structure,
Morphology, Phase Diagram, Experimental, Mechan. Prop., #, *, 95)
[2003Man] Mandal, P., “Structural Disorder in Ti-Fe-Si Icosahedral Quasicrystal”, J. Alloys Compd., 361, 96–101
(2003) (Crys. Structure, Morphology, Experimental, 23)
[2004Kim] Kim, K.B., Ko, B.C., Pak, S.J., “Formation of Nanocrystals in Ti78Fe15Si7 Amorphous Alloy with a Wide
Supercooled Liquid Region”, Mater. Sci. Eng. A, 366(2), 421–425 (2004) (Crys. Structure, Morphology,
Experimental, Mechan. Prop., 14)
[2004Loe] Loeffler, F., Palm, M., Sauthoff, G., “Iron-Rich Iron-Titanium-Silicon Alloys with Strengthening
Intermetallic Laves Phase Precipitates”, Steel Res. Int., 75(11), 766–772 (2004) (Phase Relations, Mor-
phology, Experimental, Mechan. Prop., Phys. Prop., 38)
[2005Sai] Saito, T., Wakabayashi, K., Yamashita, S., Sasabe, M., “Production of Fe-Ti-Si Alloys From the
Ilmenite Ore and Their Magnetic Properties”, J. Alloys Compd., 388, 258–261 (2005) (Experimental,
Magn. Prop., 7)
[2005Ste] Stein, F., Palm, M., Sauthoff, G., “Structure and Stability of Laves Phases Part II – Structure Type
Variations in Binary and Ternary Systems”, Intermetallics, 13(10), 1056–1074 (2005) (Crys. Structure,
Phase Relations, Theory, 249)
[2007Yan] Yan, X.L., Chen, X.Q., Grytsiv, A., Witusiewicz, V.T., Rogl, P., Podloucky, R., Giester, G., “On the
Ternary Laves Phases {Sc,Ti}2M3Si (M = Cr, Mn, Fe, Co, Ni) with MgZn2-Type”, J. Alloys Compd., 429,
10–18 (2007) (Cry. Structure, Thermodyn., Calculation, Experimental, Review, Electronic Structure,
Magn. Prop., 53)
(1990)

Fe–Si–V 28 1
Iron – Silicon – Vanadium

Honghui Xu, Yong Du, Weihua Sun, Lijun Zhang
Introduction
A critical evaluation of the Fe-Si-V system was first performed by [1982Ray], and subsequently
abridged in [1988Ray]. The experimental data reviewed by both [1982Ray] and [1988Ray]
on this system include: (1) a liquidus projection in the Fe-FeSi-VSi2-V region by [1940Vog];
(2) the isothermal section at 1000˚C for the entire composition range by [1965Gla] and that at
1100˚C for Si poor alloys (up to 40 at.% Si) by [1966Bar]; and (3) the homogeneity range of
the Fe-V σ phase into the Fe-V-Si ternary system at 1175˚C by [1960Gup]. Later, the Fe-Si-V
system was partially updated by [1994Rag, 2002Rag]. [1994Rag] presented two partial iso-
thermal sections in the order-disorder region of Fe rich alloys at 800 and 700˚C that had been
originally presented by [1989Koz]. [2002Rag] reproduced a vertical section at 5 at.% V and
0-25 at.% Si for temperatures between 1200-600˚C that was based on the results of [1994Koz].
The first investigation of the phase equilibria in the Fe-Si-V system was carried out by
[1940Vog], who examined the liquidus surface in the region of Fe-FeSi-VSi2-V by thermal
analysis, and a limited metallographic observation of the solid alloys. 20 g samples were
prepared from Krupp WW iron, silicon (described as “technical”) from Kallbaum and
ferrovanadium alloys containing 60 and 53 mass% V, respectively. No specific details with
regard to purity were given. Some 80 ternary alloys were examined, the compositions of which
lay on composition lines from the silicon corner to the compositions 10, 20, 30, 40, 50 and 60
mass% V on the Fe-V axis. The vertical section through FeSi to VSi2 was also investigated by
[1940Vog]. A ternary compound T (Fe4V5Si4) was reported for the first time, and its
incongruent formation was established. [1940Vog] presented the liquidus surface in the region
of Fe-FeSi-VSi2-V and seven vertical sections.
It should be noted that the liquidus projection proposed by [1982Ray] based on [1940Vog]
that had been corrected in accordance with later versions of the binary phase diagrams must be
further modified in order to bring the phase relationships into agreement with the currently
accepted binary phase diagrams, especially with regard to the Si-V system. The V3Si phase,
which melts congruently according to the currently accepted V-Si phase diagram, was assumed
by [1982Ray] to form through a peritectic reaction of V5Si3 + L Ð V3Si. The V6Si5 phase,
which is a stable compound and forms through the peritectic reaction V5Si3 + L Ð V6Si5, was
not indicated on the liquidus surface proposed by [1982Ray].
The first investigation of the solid-state equilibria was carried out by [1960Gup], who
determined the homogeneity range of the σ phase at 1175˚C. The σ phase was found to be
strongly stabilized by Si, and the σ homogeneity range increased markedly with increasing
silicon content up to about 4 mass%, after which it decreased with further silicon addition.
[1965Gla] determined the isothermal section of the Fe-Si-V system at 1000˚C over the
entire composition range. The Fe-Si-V alloys were prepared from silicon (99.96% Si), carbonyl
iron (≥99.99% Fe) and vanadium (99.62% V). Alloy samples in the as cast and annealed
condition (annealed at 1000˚C for 100 h, at 1200˚C for 30 h and at 800˚C for 500 h) were

2 28 Fe–Si–V
examined by metallography and X-ray analysis. Three ternary compounds were shown to exist
at 1000˚C. Nevertheless, it should be noted that the V6Si5 phase, which is stable at 1000˚C
according to the recently accepted Si-V phase diagram [Mas2], was not present on the
isothermal section at 1000˚C given by [1965Gla]. The VSi2 phase, which is regarded as
approximately stoichiometric, was shown to have some homogeneity.
[1966Bar] established a partial isothermal section at 1100˚C up to a silicon content of
40 at.% Si. The same three ternary phases were reported to exist at 1100˚C.
The three ternary compounds mentioned above were reported by [1960Gup, 1961Bar,
1961Gla, 1962Gla, 1965Gla, 1966Bar, 1971Sho, 1976Sho]. These phases were given as the
R-, χ-, and D- or δ phases. By comparing the composition of D- or δ phase with that of the T
phase proposed by [1940Vog], it would seem that they are one and the same. For convenience,
the first reported ternary compound, originally called T by [1940Vog] is designated τ1 here.
Similarly, the remaining two ternary compounds R and χ are referred to as τ2 and τ3,
respectively.
The influence of V on the order-disorder transitions in the Fe-Si bcc phase and the phase
transformation of the Fe rich Fe-Si-V alloys were studied by [1976Nic, 1985Wan, 1988Fuk,
1989Koz, 1990Zha, 1994Koz, 2004Doi, 2004Nis, 2006Doi]. The phase equilibria involving Fe
rich alloys were investigated at 800˚C by [1989Koz, 1994Koz], 700˚C by [1989Koz], and 600˚C
by [1994Koz]. [1994Koz] also determined a vertical section at 5 at.% in the temperature range
1200-600˚C, where the (α + α1) field dominates at lower temperatures and the α2 phase field is
stable only above 1050˚C.
[1974Bur, 1975Pic] measured the site occupancy of V in substituted Fe3Si, using neutron
diffraction studies. [1976Ber, 1977Nic, 1983Bus, 1991Kud, 2003Kaw, 2004Nas, 2004Nis,
2006Cui] studied the crystal structures and various physical properties of ternary Fe3–xVxSi
(0 ≤ x ≤ 1) alloys having the Heusler structure because of their interesting electronic and
magnetic properties.
[1983Roz] measured the mixing enthalpies and component activities of ternary melts at
1627˚C.
Information on the investigation of phase equilibria and thermodynamics of the Fe-Si-V
system are summarized in Table 1.
Binary Systems
The Fe-V binary system is accepted from [Mas2]. The Fe-Si phase diagram is taken from
[1982Kub]. The V-Si phase diagram is taken from [Mas2] but with a slight modification owing
to the work of [2007Zha]. [2007Zha] reinvestigated the stability of V6Si5 via a hybrid approach
of Calphad, XRD and first principle methods. According to [2007Zha], the decomposition
temperature for the reaction V6Si5 Ð V5Si3 + VSi2 is 460˚C, which is significantly lower than
the temperature of 1160 ± 100˚C recommended in [Mas2]. Figure 1 presents the Si-V phase
diagram from [2007Zha].
Solid Phases
The crystallographic data of the phases in the Fe-Si-V system and their temperature ranges of
stability are listed in Table 2.
Fe–Si–V 28 3
Three ternary phases have been found in the system. A fourth compound was mentioned
by [1965Gla], however no information on its composition or crystal structure was given.
The τ1 ternary phase was established for the first time by [1940Vog], and later its existence
was confirmed by [1965Gla, 1966Bar] at 1000 and 1100˚C. The τ1 phase is isostructural
with tetragonal Mn5Si2. It exists in a rather wide composition range, from 32 to 45 at.% Fe
at 1100˚C and from 30 to 40 at.% Fe at 1000˚C, according to [1966Bar] and [1965Gla]. Its
lattice parameters at a composition of Fe44V26Si30 were determined by [1971Sho]. Subse-
quently, the structure model for the τ1 phase was refined by [1976Sho] using a full-matrix least
squares analysis and diffractometer data from the isotypic Mn5Si2 phase.
There is good agreement in the studies of the composition and crystal structure of the τ2
phase, which has the rhombohedral structure, and it may be described in terms of a hexagonal
unit cell. The crystal structure of the τ2 phase was determined by [1961Bar] at the composition
of Fe41V37Si22, and by [1965Gla] at the composition of Fe2V2Si. The extent of the homogeneity
range of the τ2 phase changes and shifts as the temperature decreases. At 1000˚C the phase
contains more Si and less Fe than at 1100˚C [1965Gla, 1966Bar]. No information is available
concerning the formation of the τ2 phase.
[1961Gla, 1965Gla, 1966Kim, 1967Far] made contributions to the determination of the
crystal structure of the τ3 phase, Fe5V3Si2, which was established for the first time by
[1961Gla]. There is good agreement over its composition and crystal structure. The τ3 phase
has the αMn type structure and exists in a rather wide composition range, from 33 to 47 at.%
Fe at 1100˚C and from 32 to 44 at.% Fe at 1000˚C, according to [1966Bar] and [1965Gla]. The
τ3 phase and the above-mentioned τ2 phase were observed by [1965Gla] in as-cast alloys
quenched after melting in a resistance furnace, and also in arc-melted specimens. Therefore,
crystallization of both of these phases from the liquid is not improbable.
[1967Far] reported the existence of the ternary phases Fe0.175VSi and Fe3VSi as well as
Fe2V2Si (τ2) and Fe5V3Si2 (τ3). The Fe3VSi which has a structure similar to αMn and a
composition coinciding with that of the τ2 phase, is ferromagnetic with a Curie point at
318˚C. The Fe0.175VSi phase is very likely to be the solid solution of Fe in V6Si5, as its atomic
silicon content is approximately equal to that of the stable V6Si5 phase in the Si-V binary
system.
[1984Sin] reported a ternary phase at 400˚C around the composition of Fe50V25Si25 with
an orthorhombic structure and lattice parameters a = 751.7, b = 721.4, c = 691.7. At higher
temperatures (1000 and 1100˚C), this phase is not stable because of the existence of the solid
solution of V in Fe3Si in this composition range. For the same composition (Fe2VSi),
[1995Kaw] reported the αMn structure type at 300 K (designated here as τ4), which exhibits
a tetragonal deformation at low temperatures. Subsequently, [1998Kaw] suggested that Fe2VSi
phase has a tetragonally distorted Heusler structure below 120 K, with an antiferromagnetic
ordering. [2006Nas] reported that Fe2VSi, which has the Heusler structure (L21) at room
temperature, takes on the αMn structure (A2) above 1100˚C. A single-phase Fe2VSi alloy with
a αMn structure type was produced by [2006Nas] using the single-roller melt-spinning
technique under a purified argon atmosphere. When the sample was annealed at 800˚C, its
structure transformed into the Heusler structure (L21). When annealed again at 1100˚C and
quenched into ice, the structure of the sample almost returned to the αMn structure. This
structural transformation is unusual because the high temperature phase takes more
complex structure than the low temperature phase [2006Nas]. By means of neutron diffrac-
tion study and Rietveld analysis with the RIETAN 2000 program, [2006Nas] refined the
structural parameters of the αMn structured Fe2VSi phase including the site occupancy.
4 28 Fe–Si–V
Further investigations are required in the area of the existence of the τ4 phase in relation to the
phase equilibria with other phases in the region. According to [1965Gla], the solubility of V in
Fe5Si3, FeSi and FeSi2 at 1000 ˚C was measured to be about 37, 14 and 2 at.% V, respectively;
and that of Fe in V3Si and V5Si3 about 22 and 13 at.% Fe, respectively. At 1100 ˚C, according to
[1966Bar], the solubility of Fe in V5Si3 was determined to be about 22 at.% Fe. Though Fe5Si3
is not stable at 1100 ˚C in the Fe-Si binary system, the phase that was denoted as N2 by
[1966Bar] and off the Fe-Si binary side is very likely to be the V-stabilized Fe5Si3 phase because
it had a composition range corresponding to part of the composition range of the (Fe,V)5Si3
solid solution at 1000˚C given by [1965Gla].
Quasibinary Systems
The quasibinary system FeSi-VSi2 reported by [1940Vog] is shown in Fig. 2.

The FeSi2-VSi2 section is also likely to be quasibinary by taking into account the congruent
melting of the binary compounds and the existence of the FeSi-VSi2 quasibinary section
making it impossible for the appearance of alternative equilibria.
Five four-phase and two three-phase invariant equilibria involving the liquid phase have been
detected experimentally [1940Vog] for the Fe-FeSi-VSi2-V region. Later, these experimental
results were reinterpreted by [1982Ray] owing to the publication of revised versions of the
binary Fe-Si and Si-V phase diagrams. In the present evaluation, it is necessary for more
invariant reactions to be added in order to account for six binary silicides, instead of the three
(FeSi, VSi2 and V2Si) known at the time of [1940Vog]. Also, the extensions of their composi-
tion ranges have been taken into account. It is reasonable to replace the reaction V from
[1940Vog] (FeSi + α1 Ð L + τ1) by two reactions U6 (L + FeSi Ð Fe2Si + τ1) and U7 (L + τ1 Ð
Fe2Si + α1) (Table 3). This interpretation correlates better with the experimental data of
[1940Vog]; namely the monovariant curve L Ð FeSi + α falls monotonously to the binary
eutectic (1195˚C in [1940Vog]) on the Fe-Si side.
A monovariant e10(max) should result from the probable quasibinary section FeSi2-VSi2,
as mentioned above. Taking into account the two three-phase invariant reactions (e5(max)
and e10(max)), two four-phase ternary eutectic reactions should be assumed, E1 and E2.
The reaction scheme proposed in the present evaluation is shown in Fig. 3. The invariant
equilibria are listed in Table 3 showing the origin of the reactions.
Liquidus Surface
Only one experimental study of the liquidus surface [1940Vog] is available. It was reported for
the Fe-FeSi-VSi2-V region. It was amended later by [1982Ray]. Further amendments have been
made in this evaluation as the currently accepted Si-V phase diagram shows essential differ-
ences with the older versions used by [1940Vog] and [1982Ray]. Figure 4 presents the
amended liquidus projection based on the experimental data of [1940Vog], reinterpreted by
[1982Ray] and modified in the present evaluation to ensure agreement with the accepted
Fe–Si–V 28 5
binary diagrams. New fields of primary crystallization are added tentatively for the regions not
considered in [1940Vog]. The location and the temperatures of the invariant points estab-
lished by [1940Vog] are retained in the present evaluation (P1, U5, p2(max), e5(max)). The
locations of the monovariant curves are also taken from [1940Vog]. The monovariant lines
after [1940Vog] are shown in Fig. 4 by thick solid lines. The monovariant lines added here are
shown by thick dashed lines.
Isothermal Sections
The isothermal sections at 1100 and 1000˚C have been constructed from the results of
experimental investigations undertaken by [1966Bar] and [1965Gla], respectively.
According to [1966Bar], τ1 and τ2 both enter into equilibrium with the ordered Fe3Si
phase, whereas this does not appear in the diagram presented by [1965Gla]. Consequently, no
equilibrium between τ1 and τ2 was possible in the diagram of [1966Bar].
There are also some other differences between the two isothermal sections given by
[1965Gla] and [1966Bar]. [1965Gla] indicated that the V3Si phase extended into the ternary
system with approximately constant silicon content, whereas [1966Bar] suggested that the
phase extends with approximately constant vanadium content. [1986Kan] confirmed the
conclusions of the review of [1982Ray] relating to the solubility limit of Fe in V3Si and
the variation in lattice parameter. The results of [1965Gla] on the shape of the V3Si phase
field seem to be more reliable. Although the temperature difference is not large, the solubility
of Fe in V3Si at 1100˚C was considerably lower than at 1000˚C. It should be noted that the
solubility of Fe in V5Si3 and the homogeneity ranges of the three ternary phases τ1, τ2 and τ3
reported by [1966Bar] for 1100˚C are visibly larger than those at 1000˚C given by [1965Gla].
The phase denoted as N2 by [1966Bar] has a composition range corresponding to part of
the composition range of the (Fe,V)5Si3 solid solution at 1000˚C given by [1965Gla]. This may
be an indication that Fe5Si3 is stabilized by the addition of V, so that a ternary phase with the
same structure as Fe5Si3 may exist at higher temperatures than in the Fe-Si binary system.
Besides, it should be mentioned that the Fe2Si phase, which is stable at 1100˚C, was missing in
the presented isothermal section.
Figures 5 and 6 show the isothermal sections at 1100 and 1000˚C, respectively, which are
due mainly to [1966Bar] and [1965Gla]. Slight corrections have been made in order to bring
the phase relationships into agreement with the currently accepted binary phase diagrams. The
Fe2Si phase missing in [1966Bar] is added to Fig. 5. For Si contents above 40 at.%, tentative
equilibria are shown similar to those given for 1000˚C. The V6Si5 phase missing in [1965Gla] is
added to Fig. 6. The VSi2 phase is treated as a line compound. The stability ranges of the α, α1,
α2 phases are modified in Figs. 5 and 6 to be in agreement with the data of [1994Koz].
Figures 7 to 9 show partial isothermal sections at 800, 700 and 600˚C as determined by
[1989Koz, 1994Koz]. The isothermal section at 600˚C [1994Koz] is very similar to that at 700˚
C [1989Koz], showing a wide α + α1 two-phase field. It was reported by [1989Koz] that the
extent of the α2 +α1 two-phase field decreases markedly on increasing the temperature from
700 to 800˚C. Using the Bragg-Williams-Gorsky model, [1994Koz] calculated isothermal
sections at 800 and 600˚C, taking into account the atomic and magnetic interaction energies
up to the second nearest neighbor. The calculated sections are in good agreement with
experiment [1994Koz].

6 28 Fe–Si–V
Seven vertical sections through the Si corner were constructed by [1940Vog] based on their
own experimental data. They clearly demonstrate the peritectic formation of the ternary
compound τ1 and a maximum on the liquidus surface of the V5Si3 phase. Nevertheless, they
cannot be accepted in the present evaluation because the interpretation of phase equilibria was
based on older versions of the binary phase diagrams that have since been superseded, and
moreover, they are not in accordance with two isothermal sections reported later by [1966Bar]
and [1965Gla].
Figure 10 shows the vertical section determined by [1994Koz] for silicon contents between
0-25at.% at 5 at.% V. The results of [1988Fuk, 1989Koz, 1990Zha, 1994Koz] show that the
addition of vanadium reduces the stability of the α2 phase, narrowing its homogeneity range
until it disappears at 1040˚C (α /(α + α1)) and at 1050˚C ((α1 + α2)/α1) at a V content of
5 at.%.
Thermodynamics
[1983Roz] measured the mixing enthalpies and component activities in ternary melts at
1627˚C. The Fe-Si-V alloy melts show a negative deviation from Raoult’s law.

Ternary Fe3–xVxSi (0 ⊊ x ⊊ 1) alloys with the Heusler structure (L21) show very interesting
electronic and magnetic properties. These properties were studied by [1976Nic, 1976Ber,
1977Nic, 2003Kaw, 2004Nas, 2006Cui]. Using X-ray, magnetization and spin-echo NMR
techniques, [1976Nic] measured the changes in atomic ordering, their effect on local moment
and internal field distributions in the Fe3–xVxSi (0 ⊊ x ⊊ 1) alloys. [1976Ber] measured the
magnetic properties and superconductivity of Fe3–xVxSi. The role of the outer electrons on
solubility limits and bulk magnetic properties of Fe3–xVxSi alloys was investigated by
[1977Nic]. [2003Kaw] measured thermoelectric properties, such as the thermal diffusivity,
electrical resistivity, and Seebeck coefficient in the temperature range from 300 to 1073 K, of
Fe3–xVxSi (0 ⊊ x ⊊ 1) alloys. [2004Nas] measured the Seebeck coefficient, electrical resistivity,
and magnetization of Fe3–xVxSi alloys with 0.6 ≤ x ≤ 1 and compared the results with those of
Fe3xVxAl. The electronic structures of Fe3–xVxSi in the concentration range between x = 0 and
x = 1 were studied by [2006Cui] using photoemission spectroscopy (PES).
[1978Hao] determined the eutectic temperature and composition as well as the oxidation
resistance of the alloys Fe63V30Si7 and Fe65V29Si6 (in mass%).
[1983Bus] studied the magneto-optical properties of the Fe2VSi compound annealed at
800˚C for 10 d. Using X-ray diffraction, [1995Kaw] and [1998Kaw] measured the tetragonal
deformation of Fe2VSi at low temperatures [1995Kaw], and the thermal expansion of Fe2VSi
compounds below room temperature [1998Kaw]. [2004Nis] investigated the magnetic prop-
erties of Fe2VSi by means of NMR experiments using 51V for two samples that had been
quenched after annealing at 800 and 900˚C, respectively.
Information on the investigation of the materials properties are listed in Table 4.

Fe–Si–V 28 7
Miscellaneous
Figure 11 shows the variation of the lattice parameter a and superconducting transition
temperatures in V3–xFexSi alloys as a function of iron content [1978Soz].
. Table 1
Investigations of the Fe-Si-V Phase Relations, Structures and Thermodynamics
Temperature/ Composition/ Phase Range

Reference Method/ Experimental Technique Studied
[1940Vog] Thermal analysis, X-ray analysis and Fe-FeSi-VSi2-V region, from liquidus to
metallography 1100˚C
[1960Gup] X-ray analysis Around the σ phase at 1175˚C
[1961Gla] X-ray analysis Fe5V3Si2
[1961Bar] X-ray analysis Fe41V37Si22
[1962Gla] X-ray analysis Fe2V2Si (τ2), Fe5V3Si2 (τ3)
[1965Gla] X-ray analysis, metallography 800, 1000, 1200˚C and as-cast state, entire
composition range
[1966Bar] Metallography, X-ray analysis, chemical < 40 at.% Si, 1100˚C
analysis
[1966Kim] X-ray analysis, electrical properties, Fe50V30Si20 at 4, 77 and 300 K
magnetic properties, Mössbauer
[1967Far] X-ray analysis Fe2.5V1.5Si, Fe3VSi
[1971Sho] X-ray analysis Fe44V26Si30
[1974Bur] Neutron diffraction Fe3Si; Site occupation of V in dilutely
substitued Fe3Si
[1975Pic] Neutron diffraction Fe2.948V0.052Si alloy; Site occupation of V in
Fe3Si
[1976Nic] Neutron diffraction Fe3–xVxSi alloys (0≤ x ≤1.0); changes in the
atomic ordering, their effect on local
moment and internal field distributions
[1976Sho] X-ray analysis V26.5Fe44Si29.5
[1978Hao] Thermal analysis, SEM Fe63V30Si7 and Fe65V29Si6 alloys (in mass%);
oxidation resistance
[1978Soz] X-ray analysis Solid solution (V,Fe)3Si, ≤ 10 at.% V
[1983Roz] Measurements of mixing enthalpies and The Fe-Si-V alloy melts, at 1267˚C
activities
[1984Sin] X-ray analysis, metallography Fe3Si - V3Si section, 400 and 1000˚C;
V50Fe25Si25 ternary phase
[1985Wan] Magnetic properties, X-ray analysis, SEM Fe-6.5Si (mass%) alloy; effect of vanadium
on ordering phase separation in Fe-Si alloy

8 28 Fe–Si–V
Temperature/ Composition/ Phase Range

Reference Method/ Experimental Technique Studied
[1986Kan] X-ray analysis (Fe,V)3Si alloys; phase separation of α and

α1 in (Fe1–xVx)3 Si alloys
[1988Kum] Thermodynamic calculation Fe rich ternary alloys, at 950, 1050, 1150,
and 1250˚C; bcc-fcc equilibrium
[1988Fuk] TEM observation of phase separation with α and
α1 in Fe-Si-V alloys
[1989Koz] TEM Fe rich Fe-Si-V alloys, 700, 800˚C; phase
separation of α and α1
[1990Zha] Thermodynamic calculation α2 (B2) +α1 (D03) two phase field; influence
of V on the order-disorder reactions in the
Fe-Si bcc (α) phase,
[1991Kud] Ab initio calculation of electronic Fe3–xVxSi
structures and magnetic moments
[1994Koz] Phase separation of α and α1, ordering, Fe rich ternary alloys, 600˚C, 800˚C, 600-
TEM, thermodynamic calculation 1200˚C
[1995Kaw] X-ray analysis Fe2VSi, at 300 K
[1998Kaw] Thermal expansion, X-ray analysis Fe2VSi, below room temperature, 120 K
[2003Kaw] X-ray analysis, EDX Fe3–xVxSi
[2004Doi] TEM Fe72V13Si15, 1200, 650˚C; aging
precipitation of α1 in α
[2004Nas] X-ray analysis, measurements of Seebeck Fe3–xVxSi (0.6 ≤ x ≤ 1.0)
coefficient, electrical resistivity, and
magnetization
[2004Nis] Neutron diffraction, magnetic Fe2VSi, 800˚C, 900˚C
susceptibility measurement
[2006Cui] electronic structures, photoemission Fe3–xVxSi (0 ≤ x ≤ 1.0) annealed at 850˚C for
spectroscopy (PES) 5 days
[2006Nas] X-ray analysis and neutron diffraction Fe2VSi, 800˚C,1100˚C
[2006Doi] TEM Fe70.5V16.2Si13.3, 1200˚C, 650˚C; phase
separation of α and α1

Fe–Si–V 28 9
. Table 2
Pearson
Symbol/
α, (αδFe,V) cI2
< 1910 Im3m
W
(δFe) a = 293.15 pure Fe at 1390˚C [V-C2, Mas2]
1538 - 1394
(V) a = 302.4 pure V at 25˚C [Mas2]
< 1910
< 912
1394 - 912 Fm3m
Cu
P63/mmc c = 396.0
Mg
(αSi) cF8 a = 543.06 T = 25˚C [Mas2, V-C2]
< 1414 Fm3m
C (diamond)
(βSi) (II) tI4 a = 468.6 T = 25˚C, p > 9.624 bar [Mas2, V-C2]
I41/amd c = 258.5
βSn
(γSi) (III) cI16 a = 663.6 T = 25˚C, p > 16.208 bar [Mas2, V-C2]
Im3m
γSi
(δSi) (I) hP4 a = 380 T = 25˚C, p = 16.208-1.013 bar [Mas2, V-C2]
P63/mmc c = 628
αLa
α1, Fe3Si cF16 D03
< 1235 Fm3m a = 565.0 [V-C2]
BiF3 11.0 to 30.0 at.% Si [1982Kub]
α2, Fe-Si cP2 B2
< 1280 Pm3m a = 281 [V-C2]
CsCl 10.0 to 22.0 at.% Si [1982Kub]
β, Fe2Si hP6 a = 405.2 ± 0.2 [V-C2]
1212 - 1040 P3m1 c = 508.55 ± 0.03 19.93 to 21.31 at.% Si [1982Kub]
Fe2Si

10 28 Fe–Si–V
Pearson
Symbol/
η, Fe5Si3 hP16 [1982Kub]

1060 - 825 P63/mmc a = 675.9 ± 0.5 [V-C2]
Mn5Si3 c = 472.0 ± 0.5
ε, FeSi cP8 a = 451.7 ± 0.5 [V-C2]
< 1410 P213 49.6 to 50.8 at.% Si [1982Kub]
FeSi
ζα, FeSi2(h) tP3 a = 269.01 [V-C2]
1220 - 937 P4/mmm c = 513.4 69.5 to 73.5 at.% Si [1982Kub]
FeSi2
ζβ, FeSi2(r) oC48 [1982Kub]
< 982 Cmca a = 986.3 [V-C2]
FeSi2 b = 779.1
c = 783.3
σ, FeV tP30 a = 896.5 [V-C2]
< 1252 P42/mnm c = 463.3 39.9 to 70.4 at.% Fe [Mas2]
σCrFe
V3Si cP8 a = 472.72 [V-C2]
< 1925 Pm3n 19 to 25.5 at.% Si [Mas2]
Cr3Si
V5Si3 tI32 a = 943 [V-C2]
< 2010 I4/mcm c = 471
Si3W5
V6Si5 oI44 a = 1596.6 [V-C2, Mas2]
1670 - 1160 Ibam b = 750.1
Ti6Ge5 c = 485.8
VSi2 hP9 a = 457.5 [V-C2]
< 1677 P6222 c = 638.5
CrSi2
* τ1, Fe4V5Si4 tP56 30 to 40 at.% Fe
P41212 a = 888 [1965Gla]
Mn5Si2 c = 867 [1965Gla]
a = 883.3
c = 864.6 [1971Sho] at Fe44V26Si30
* τ2, Fe2V2Si hR53 45.5 to 52 at.% Fe
R3 a = 1079.9 [1965Gla]
Co5Cr2Mo3 c = 1924.3 [V-C2]
a = 1079
c = 1924.0 [1961Bar] at Fe41V37Si22

Fe–Si–V 28 11
Pearson
Symbol/
* τ3, Fe5V3Si2 cI58 a = 884.3 [1962Gla, 1965Gla] 32 to 44 at.% Fe

I33m
αMn
* τ4, Fe2VSi cF16 L21 Heusler structure phase
Fm3m a = 567.4 at 300 K [1995Kaw]
AlCu2Mn
t* a = 568.8 at 10 K [1995Kaw].
- c = 562.3 Transition to the tetragonal structure occurs at
120 K [1998Kaw]
. Table 3
Composition (at.%)
Reaction T [˚C] Type Phase Fe Si V Comment
L + V5Si3 Ð τ1 1510 p2 (max) L 38 32 30 [1940Vog]

L + V6Si5 Ð V5Si3 + VSi2 1500 U1 - - - - this work
L + V5Si3 Ð τ1 + V3Si 1450 U2 - - - - this work
L + V3Si Ð α + τ1 1400 U3 L 46.5 12.5 41 [1940Vog]
L + τ1 + α2 Ð α1 1370 P1 L 48 13 39 [1940Vog]
L + α2 + τ1 Ð α1 1350 P2 - - - - this work
L Ð VSi2 + FeSi 1310 e5 (max) - - - - this work
L + V5Si3 Ð VSi2 + τ1 1260 U4 L 27.5 49 23.5 [1940Vog]
L + VSi2 Ð FeSi + τ1 1235 U5 L 60 36 4 [1940Vog]
L + FeSi Ð Fe2Si + τ1 1202 U6 - - - - this work
L + τ1 Ð Fe2Si + α1 1201 U7 L 66 31 3 [1940Vog]
L Ð VSi2 + FeSi2 1200 e10 (max) - - - - this work
L Ð VSi2 + FeSi2 + (Si) 1180 E1 - - - - this work
L Ð VSi2 + FeSi2 + FeSi 1150 E2 - - - - this work

12 28 Fe–Si–V
. Table 4
Investigations of the Fe-Si-V Materials Properties
Reference Method/ Experimental Technique Type of Property
[1976Nic] Magnetometer Magnetic properties

[1983Bus] Saturation moment, Polar Kerr rotation Magnetic properties,
optical properties
[1991Kud] Ab initio calculation Magnetic properties
[2003Kaw] Laser flash, measurements of electrical resistivity, Thermoelectric property
thermoelectric power and density
[2004Nis] Measurements of thermoelectric power, magnetization Magnetic and electric
and electrical resistivity properties

Fe–Si–V 28 13
. Fig. 1
Fe-Si-V. Si-V binary phase diagram

14 28 Fe–Si–V
. Fig. 2
Fe-Si-V. Quasibinary system VSi2-FeSi

Fe–Si–V 28 15
. Fig. 3
Fe-Si-V: Partial reaction scheme

16 28 Fe–Si–V
. Fig. 4
Fe-Si-V. Partial liquidus surface in the Fe-FeSi-VSi2-V region

Fe–Si–V 28 17
. Fig. 5
Fe-Si-V. Isothermal section at 1100˚C

18 28 Fe–Si–V
. Fig. 6
Fe-Si-V. Isothermal section at 1000˚C

Fe–Si–V 28 19
. Fig. 7
Fe-Si-V. Partial isothermal section at 800˚C

20 28 Fe–Si–V
. Fig. 8

Fe–Si–V 28 21
. Fig. 9

22 28 Fe–Si–V
. Fig. 10
Fe-Si-V. Vertical section at 5 at.% V with the silicon content of 0-25 at.%

Fe–Si–V 28 23
. Fig. 11
Fe-Si-V. Variation of the lattice parameter (1) and superconducting transition temperature (2) in
the V3–xFexSi alloys with x

24 28 Fe–Si–V
References
[1940Vog] Vogel, R., Jentzsch-Uschinski, C., “The Iron-Silicon-Vanadium Alloys” (in German), Arch. Eisenhuet-
tenwes., 13, 403–408 (1940) (Phase Diagram, Phase Relations, Morphology, Experimental, *, 9)
[1960Gup] Gupta, K.P., Rajan, N.S., Beck, P.A., “Effect of Si and Al on the Stability of Certain σ Phases”, Trans.
Met. Soc. AIME, 218, 617–624 (1960) (Experimental, Phase Diagram, Phase Relations, 18)
[1961Bar] Bardos, D.I., Gupta, K.P., Beck, P.A., “New Ternary R Phases with Silicon”, Nature, 192, 744 (1961)
[1961Gla] Gladyshevskii, E.I., Kripyakevich, P.I., Teslyuk, M.Yu., Zarechnyuk, O.S., Kuz’ma, Yu.B., “Crystal
Structures of Some Intermetallic Compounds”, Sov. Phys.-Crystallogr., 6, 207–208 (1961), translated
from Kristallografiya, 6(2), 267 (1960) (Crys. Structure, Experimental, 11)
[1962Gla] Gladyshevskii, E.I., “Crystal Structure of Compounds and Phase Equilibria in Ternary Systems of Two
Transition Metals and Silicon”, Sov. Powder Metall. Met. Ceram. (Engl. Transl.), 1(4), 262–265 (1962)
(Crys. Structure, Experimental, Phase Diagram, Phase Relations, 17)
[1965Gla] Gladyshevsky, E.I., Shvets, G.N., “Phase Equilibrium Diagram of Ternary V-Fe-Si Alloys and Crystal
Structure of the Compounds”, Russ. Metall., 2, 63–65 (1965), translated from Izv. Akad. Nauk SSSR,
Met., (2), 120–127 (1965) (Experimental, Phase Diagram, Phase Relations, *, 2)
[1966Bar] Bardos, D.I., Beck, P.A., “Electron Phases in Certain Ternary Alloys of Transition Metals with Silicon”,
Trans. Met. Soc. AIME, 236, 64–69 (1966) (Experimental, Phase Diagram, Phase Relations, *, 16)
[1966Kim] Kimball, C.W., Phillips, W.C., Nevitt, M.V., Preston, R.S., “Magnetic Hyperfine Interactions and
Electric Quadrupolar Coupling in Alloys of Iron with the α-Manganese Structure”, Phys. Rev., 146(2),
375–378 (1966) (Crys. Structure, Electr. Prop., Magn. Prop., Experimental, 18)
[1967Far] Farrokhi-Mochai, N., “A Study of the Solid Phases in the Fe-Si-Ti, Fe-Si-Zr, and Fe-Si-V Systems” (in
French), Rev. Chim. Miner., 4, 1–15 (1967) (Crys. Structure, Phase Relations, Phase Diagram, Experi-
mental, 23)
[1971Sho] Shoemaker, C.B., Shoemaker, D.P., “On Structures of Transition-Metal Phases with Approximately
30 at.% Si”, Metall. Trans., 2, 2296–2299 (1971) (Crys. Structure, Experimental, 11)
[1974Bur] Burch, T.J., Litrenta, T., Budnick, J.I., “Hyperfine Studies of Site Occupation in Ternary Systems”, Phys.
Rev. Letters, 33(7), 421–424 (1974) (Crys. Structure, Experimental, 12)
[1975Pic] Pickart, S., Litrenta, T., Burch, T., Budnick, J.I., “Site Preference of Dilute Transition Metal Solutes in
Fe3Si”, Phys. Lett. A, 53A(4), 321–323 (1975) (Crys. Structure, Experimental, 4)
[1976Ber] Bergner, R.L., Rao, V.U.S., Sanker, S.G., “Superconducting and Magnetic Properties of V3–xFexSi and
V3–xMnxSi”, AIP Conf. Proc., 29, 325–326 (1976) (Experimental, Magn. Prop., Supercond., 4)
[1976Nic] Niculescu, V., Raj, K., Budnick, J.I., Burch, T.J., Hines, W.A., Menotti, A.H., “Relating Structural,
Magnetisation and Hyperfine Field Studies to a Local Environment Model in Fe3–xVxSi and
Fe3–xMnxSi”, Phys. Rev. B, 14(9), 4160 (1976) (Crys. Structure, Magn. Prop., Experimental, 26)
[1976Sho] Shoemaker, C.B., Shoemaker, D.P., “The Crystal Structure of Mn5Si2 and the D phase (V-Fe-Si)”, Acta
Crystallogr., Sect. B: Struct. Crystallogr. Crys. Chem., B32(7), 2306–2313 (1976) (Crys. Structure,
Experimental, 24)
[1977Nic] Niculescu, V., Budnick, J.I., “Limits of Solubility, Magnetic Properties and Electron Concentration in
Fe3–xTixSi System”, Solid State Commun., 24(9), 631–634 (1977) (Crys. Structure, Experimental, Phase
Relations, Magn. Prop., 17)
26–32 (1978) (Experimental, Phase Diagram, Phase Relations, 24)
[1978Soz] Sozontova, G.N., Shtolts, A.K., Geld, P.V., Medvedev, A.I., “Superconducting Solid Solutions of
(V,Fe)3Si, (V,Fe)3Ge and (V,Fe)3Ga”, Russ. Metall., (2), 172–174 (1978), translated from Izv. Akad. Nauk
SSSR, Met., (2), 217–219 (1978) (Experimental, Phase Diagram, Phase Relations, 5)
(1982) (Phase Diagram, Phase Relations, Review, #, *, 23)
[1982Ray] Raynor, G.V., Rivlin, V.G., “8: Critical Evaluation of Constitution of Iron-Silicon-Vanadium System”,
Int. Met. Rev., 27(5), 289–306 (1982) (Phase Diagram, Phase Relations, Review, 32)
[1983Bus] Buschow, K.H.J., van Engen, P.G., Jongebreur, R., “Magneto-Optical Properties of Metallic
Ferromagnetic Materials”, J. Magn. Magn. Mater., 38, 1–22 (1983) (Experimental, Magn. Prop., Optical
Prop., 23)

Fe–Si–V 28 25
[1983Roz] Rozhikhina, I.D., Tolstoguzov, N.V., “Practical Use of Data on the Heat of the Dissolution of Fe-V-Si
Molten Alloys”, Izv. V.U.Z. Chern. Metall., (4), 12–15(1983) (Experimental, Thermodyn., 4)
[1984Sin] Singh, M., Bhan, S., “Structural Studies on V3Si-Fe3Si System”, Cryst. Res. Technol., 19(9), K81–K83
(1984) (Experimental, Morphology, Phase Diagram, Phase Relations, Crys. Structure)
[1985Wan] Wang, S., “Effect of Vanadium on Ordering Phase Separation in Fe-Si Alloy”, Acta Metall. Sin., 21(6),
427–37 (1985) (Phase Relations, Experimental, Crys. Structure, Magn. Prop., 21)
[1986Kan] Kanematsu, K., “Stability of Crystal Structure of (Fe,V)3M and (Fe,Ni)3M (M = Si, Ge, Sn) and Its
Analysis Based on Rigaid Band Model”, Trans. Jpn. Inst. Met., 27(4), 225–234 (1986) (Crys. Structure,
Experimental, 13)
[1988Fuk] Fukaya, M., Kozakai, T., Miyazaki, T., “Phase Separation in Fe-Si-V and Fe-Si-Co Ordered Alloys” (in
Japanese), Nippon Kinzoku Gakkai-Si, 52(4), 369–374, (1988) (Experimental, Phase Diagram, Phase
Relations, 26)
[1988Kum] Kumar, K.C.H., Raghavan, V., “BCC-FCC Equilibrium in Ternary Iron Alloys”, J. Alloy Phase Diagrams,
4(1), 53–71 (1988) (Experimental, Phase Relations, Thermodyn., 27)
[1988Ray] Raynor, G.V., Rivlin, V.G., “Fe-Si-V” in “Phase Equilibria in Iron Ternary Alloys”, Inst. Metals, London,
452–466 (1988) (Phase Diagram, Phase Relations, Crys. Structure, Review, 11)
[1989Koz] Kozakai, T., Zhao, P.Z., Miyazaki, T., “Phase Separations in Fe rich Fe-base Ternary Ordering Alloy
Systems”, Met. Abstr. Light Metals and Alloys, 23, 32–33 (1989/1990) (Crys. Structure, Experimental,
[1990Zha] Zhao, P.Z., Kozaki, T., Miyazaki, T., “Analysis of Ordering and Phase Separation in Alloys of the Ternary
System Fe-Si-V with bcc Structure based on the Model of Bragg-Williams-Gorsky”, J. Jpn. Inst. Met.,
54(2), 139–145 (1990) (Crys. Structure, Phase Relations, Calculation, 27)
[1991Kud] Kudrnovsky, J., Christensen, N.E., Andersen, O.K., “Electronic-Structures and Magnetic-Moments of
Fe3+ySi1–y and Fe3–xVxSi Alloys with D03-Derived Structure”, Phys. Rev. B, 43(7), 5924–5933 (1991)
(Crys. Structure, Electronic Structures, Magn. Prop., Calculation, 33)
[1994Koz] Kozakai, T., Miyazaki, T., “Experimental and Theoretical Investigations on Phase Diagrams of Fe Base
Ternary Ordering Alloys”, ISIJ Int., 34(5), 373–383 (1994) (Phase Diagram, Experimental, Calculation,
[1994Rag] Raghavan, V., “Fe-Si-V (Iron-Silicon-Vanadium)”, J. Phase Equilib., 15(6), 633–634 (1994) (Phase
[1995Kaw] Kawakami, M., Nishizaki, S., Fujita, T., “Tetragonal Deformation in Fe2VSi at Low Temperatures”,
J. Phys. Soc. Jpn., 64(11), 4081–4083 (1995) (Crys. Structure, Experimental, 6)
[1998Kaw] Kawakami, M., Uchimura, T., “Crystal Structure Transformation in Fe2VSi and Its Substituted Com-
pounds”, J. Phys. Soc. Jpn., 67(8), 2758–2760 (1998) (Crys. Structure, Phase Relations, Experimental, 7)
[2002Rag] Raghavan, V., “Fe-Si-V (Iron-Silicon-Vanadium)”, J. Phase Equilib., 23(5), 447 (2002) (Phase Relations,
Review, 6)
[2003Kaw] Kawaharada, Y., Uneda, H., Kurosaki, K., Yamanaka, S., “Thermoelectric Properties of Fe-V-Si
Heusler Type Compounds”, J. Alloys Compd., 359, 216–220 (2003) (Crys. Structure, Phys. Prop.,
Experimental, 21)
[2004Doi] Doi, M., Sakai, D., Koyama, T., Kozakai, T., Moritani, T., “TEM Observations of the Precipitation of A2
Particles in DO3 Precipitates in Fe-Si-V Alloy System”, Trans Tech Publications. Materials Science Forum,
449–452(1), 529–532 (2004) (Crys. Structure, Phase Relations, Experimental, 9)
[2004Nas] Nashima, O., Kanomata, T., Yamaguchi, Y., Abe, S., Harada, T., Suzuki, T., Nishihara, H., Koyama, K.,
Shishido, T., Watanabe, K., Kaneko, T., “Magnetic and Electrical Properties of Fe3–xVxSi”, J. Alloys
Compd., 383(1-2), 298–301 (2004) (Crys. Structure, Electr. Prop., Magn. Prop., Experimental, 12)
[2004Nis] Nishihara, H., Ono, K., Neumann, K.U., Ziebeck, K.R.A., Kanomata, K., “NMR of 51V in a
Heusler Alloy Fe2VSi”, J. Alloys Compd., 383(1-2), 302–307 (2004) (Magn. Prop., Crys. Structure,
Experimental, 11)
[2006Cui] Cui, Y.T., Kimura, A., Miyamoto, K., Sakamoto, K., Xie, T., Qiao, S., Nakatake, M., Shimada, K.,
Taniguchi, M., Fujimori, S.-I., Saitoh, Y., Kobayashi, K., Kanomata, T., Nashima, O., “Electronic
Structures of Fe3–xVxSi Probed by Photoemission Spectroscopy”, Phys. Status Solidi A, 203(11),
2765–2768 (2006) (Crys. Structure, Electronic Structure, Experimental, 5)
[2006Doi] Doi, M., Moritani, T., Kozakai, T., Wakano, M., “Transmission Electron Microscopy Observations of
the Phase Separation of D03 Precipitates in an Elastically Constrained Fe-Si-V Alloy”, ISIJ Int., 46(1),
155–160 (2006) (Morphology, Phase Relations, Experimental, 22)

26 28 Fe–Si–V
[2006Nas] Nashima, O., Yamaguchi, Y., Higashi, H., Goto, T., Kaneko, T., Sasamori, S., Kimura, H., Kobayashi, K.,
Kainuma, R., Ishida, K., Kanomata, T., “Unusual Complex High Temperature Structure of Fe2VSi”,
J. Alloys Compd., 417(1-2), 150–154 (2006) (Crys. Structure, Phase Relations, Experimental, 8)
[2007Zha] Zhang, C., Wang, J., Du, Y., Zhang W.J., “An Investigation on the Thermodynamic Stability of V6Si5”,
J. Mater. Sci., 42(16), 7046–7048 (2008) (Phase Diagram, Experimental, Thermodyn., Calculation, 20)
(1990)

Fe–Si–Zr 29 1
Iron – Silicon – Zirconium

Yong Du, Wei Xiong, Weiwei Zhang, Hailin Chen, Weihua Sun
Introduction
The only contribution to the measurement of the Fe-Si-Zr phase diagram is the work by
[1971Lis], who determined the isothermal section at 800˚C using 110 alloys. The existence of
six ternary compounds is reported: τ1, ZrFeSi [1963Spi, 1965Mar, 1966Fre, 1967Far, 1969Jei,
1969Yar, 1971Lis], τ2, Zr2Fe3Si [1965Mar, 1969Tes, 1971Lis, 1978Mit], τ3, Zr4Fe4Si7 [1967Far,
1969Jei, 1971Lis, 1996Eve], τ4, ZrFe2Si2 [1967Vor, 1971Lis], τ5, Zr6Fe16Si7 [1971Lis, 1984Cha],
and τ6, Zr3Fe5Si12 [1974Lys]. The previously reported stoichiometry of ZrFeSi2 [1967Far] for
τ3 was corrected to be Zr4Fe4Si7 by [1996Eve]. So far, there is no information on the melting
behavior of these phases. [1978Hao] identified one eutectic in Fe rich side of the Fe-Si-Zr
system. But the phases participating in the eutectic reaction are not specified [1978Hao].
In the literature, there are two pieces of experimental information on the thermodynamic
properties of Fe-Si-Zr melts. One is the enthalpy of dissolution for Zr in FeSi melt at 1597˚C
[1989Sud1], the other is enthalpies of mixing for the Fe-Si-Zr melt at 1627˚C below 40 at.% Zr
[1989Sud2]. Information on phase relations, crystal structures and thermodynamics is sum-
marized in Table 1.
Further work is necessary to measure the phase relationships over wide composition and
temperature ranges, especially the phase equilibria involving liquid.
Binary Systems
The binary Fe-Si and Si-Zr systems are accepted from [Mas2]. [2002Ste] redetermined the
whole Fe-Zr phase diagram by means of differential thermal analysis (DTA), X-ray diffraction
(XRD), electron probe microanalysis (EPMA), and metallography. This newly established
phase diagram is adopted in the present work.
Solid Phases
The crystallographic data of the phases in the Fe-Si-Zr system and their temperature ranges of
stability are listed in Table 2. Five ternary compounds (τ1, τ3, τ4, τ5 and τ6) are treated as the
stoichiometric ones due to the lack of experiments. The homogeneity range of the τ2 phase at
800˚C given in Table 2 is estimated from the isothermal section drawing in [1971Lis] and
should be considered as tentative only. The τ1 phase was first reported by [1963Spi], who
annealed alloys at 1100˚C for 3 d in argon-filled fused silica capsules. This phase is character-
ized by a rather restricted range of homogeneity around the composition ZrFeSi [1963Spi].
The existence of τ1 is confirmed by subsequent investigators [1965Mar, 1966Fre, 1967Far,
1969Jei, 1969Yar, 1971Lis] using XRD technique. The decomposition temperature of this

2 29 Fe–Si–Zr
ternary phase is determined to be about 1800˚C [1967Far]. [1969Jei] is responsible for the
determination of its space group using XRD.
Using XRD method, four groups of authors [1965Mar, 1969Tes, 1971Lis, 1978Mit] con-
tributed to the crystal structure determination of the τ2 phase. The lattice parameters calcu-
lated by them are consistent with each other within the estimated experimental errors.
The τ3 phase was first reported by [1967Far] and its existence was confirmed by [1969Jei,
1971Lis, 1996Eve]. This phase shows a large homogeneity range with an excess of Fe or a
deficiency of Si, and melts at a temperature of above 2000˚C [1967Far]. Subsequently, the
space group of this phase was determined by [1969Jei] and its stoichiometry was reported to
be Zr4Fe4Si7 [1996Eve].
[1967Vor] published the crystal structure data for τ4 without giving experimental details.
The occurrence of this compound was confirrmed by [1971Lis] using both XRD and optical
microscopy.
Using XRD method, [1971Lis, 1984Cha] reported the existence of τ5. Another ternary
compound τ6 was found by [1974Lys] employing XRD technique. The crystallographic data
for τ5 was established [1971Lis]. For τ6, however, no crystal structure data are available.
Zr2Fe and Zr2Si were found to form a continuous series of solid solution at 800˚C by
[1971Lis], who also reported that the solid solubility of Si in ZrFe2 is about 5 at.%, and that of
Fe in ZrSi2 about 5 at.%. For the other binary compounds, negligible solid solubilities of the
third element were observed [1971Lis]. [1985Tro, 1987Bla] reported the lattice parameters for
the (Zr1–xSix)Fe2 with x = 0.2 and 0.5, respectively.
According to [1985Tro] and [1987Bla], the measured solid solubilities of Si in α, ZrFe2 are
16.7 (in the temperature range of 800-1500˚C) and 6.7 at.% (in the temperature range of 900-
1200˚C), respectively. These authors did not give the specified temperature which corresponds
to the measured solubility.
Based on the literature data, [1981Kot] analyzed the crystal structures and compositions of
the ternary compounds formed in the systems R-M-Si (R = Ce, Hf, Ti, Sc, Y, Zr and M = Fe,
Co, Cu, Ni, Mn) in view of electronegativities and the atomic radii of the components. They
reported that Sc indicates the similar behavior with Zr and Hf when the ternary compound
formation with Si and M is taken into account. This feature found by [1981Kot] can be used
for the investigation of the other systems.
Based on differential thermal analysis and optical microstructure observations of two alloys,
[1978Hao] identified one eutectic with the eutectic temperature of 1310˚C and the eutectic
composition of about 77.9Fe-7.9Si-14.2Zr (mass%). Mentioning (δFe) phase participating in
the eutectic reaction, [1978Hao] did not identify the remaining two solid phases associated
with the eutectic reaction. Based on the information on the invariant equilibria in Fe-rich side
of the Fe-Zr and Fe-Si systems, the remaining two solid phases could be (γFe) and β, ZrFe2.
This invariant equilibrium is given in Table 3.
Isothermal Sections
Figure 1 presents the experimental isothermal section at 800˚C based on [1971Lis]. The
solubility of Si in the Fe2Zr phase was shown by [1971Lis] in the direction of the Si-Zr binary
Fe–Si–Zr 29 3
axis that is in contradiction with [1985Tro] and [1987Bla]. Therefore in Fig. 1 the shape of the
Fe2Zr phase is modified to present the Si solubility in the direction of the Fe-Si binary axis. The
phase borders at the binary sides reported by [1971Lis] are amended slightly in Fig. 1 in order
to bring them into agreement with the accepted binary phase diagrams [Mas2, 2002Ste].
Thermodynamics
[1989Sud1] measured the enthalpy of dissolution of Zr in FeSi melt at 1597˚C by means of
drop calorimetry. These data are reproduced in Table 4 and used to derive the partial and
integral enthalpies of the corresponding compositions by [1989Sud1]. Using a drop calorime-
try, [1989Sud2] determined the enthalpies of mixing for the Fe-Si-Zr melt at 1627˚C below 40
at.% Zr. These experimental results [1989Sud2] are reproduced in Fig. 2. Preliminary thermo-
dynamic calculation of the Fe-Si-Zr system was performed by [1995Gue], who also measured
the solubility of Fe in ZrSi2 at 800˚C. In the modeling of [1995Gue], ternary compounds were
not considered.
[1978Hao] reported that although the eutectic in the Fe rich corner of the Fe-Si-Zr system
could be suitable for development as materials for directionally solidified turbine blades
operating up to 1150˚C, its oxidation resistance should be enhanced in order to meet several
important criteria associated with the manufacture of the turbine blades. Oxidation tests
indicated a rapid attack of the primary silicide phase, starting only after about 20 min of
exposure [1978Hao]. The effects of Zr substitution on thermoelectric power, electrical resis-
tivity, thermal conductivity, Seebeck coefficient, and phase transformation of thermoelectric
materials β-FeSi2 are investigated by [2001Ito, 2002Ito]. It was found that Zr substitution is
quite effective for enhancing the thermoelectric performance of β-FeSi2.
The influence of Si addition on the structure (including short-range order) and stability
of amorphous Fe-Si-Zr alloys was investigated by [1988Bie] using X-ray diffraction and
Mössbauer spectroscopy and by [1991Mic] employing Mössbauer spectroscopy and magneti-
zation measurement. Mössbauer spectroscopy was also utilized to investigate the effect of Si
addition on the mean values of the hyperfine magnetic field for the compounds Zr(Fe1–xSix)2
with x ≤ 0.17 [1990Das, 1992Sar].
Using a metallographic microscope, [1985Tro] measured the microhardness of
Zr0.8Si2Fe0.2. Following the same technique, [1987Bla] determined the microhardness for
several alloys (ZrxSi1–x)Fe2 (x = 0.9, 0.8, 0.7, 0.6, 0.5). It was found [1987Bla] that the
microhardness decreases with increasing Si content. The measured microhardness along the
vertical section ZrFe2 - SiFe2 is presented in Fig. 3 [1987Bla].
Table 5 lists some investigations of the materials properties of the Fe-Si-Zr system.
Miscellaneous
Figure 4 shows lattice parameter variation of the Zr2(Fe,Si)1 phase versus Si content measured
by [1971Lis], who annealed the alloys at 800˚C for 500 h. The measured lattice parameters
4 29 Fe–Si–Zr
along the vertical section ZrFe2 - SiFe2 are presented in Fig. 5 [1987Bla]. A linear dependence
of the lattice parameters measured for the ZrFe2-Zr0.5Si0.5Fe2 system means that 50% Zr in
ZrFe2 can be substituted by Si (16.7 at.% Si) according to [1987Bla]. This experimental
observation seems to be in contradiction with the work of [1971Lis], who reported that the
solubility of Si in ZrFe2 is 5 at.% at 800˚C. In the work due to [1987Bla], temperature of
annealing was given in the range of 800-1500˚C. Therefore, if the annealing temperature was
higher than 800˚C, the results from [1987Bla] could be interpreted in a way that the solubility
of Si increases with temperature. The same solid solution was investigated by [1985Tro] with
annealing temperature 900-1200˚C, and 20% of Zr was found to be substituted by Si (6.7 at.%
Si). This value (6.7 at.% Si) is between the solubility value obtained by [1971Lis] (5 at.% Si)
and by [1987Bla] (16.7 at.% Si). This implies that the temperature of annealing in the work of
[1987Bla] is higher than that in [1985Tro] and thus confirms the idea that the solubility of Si
increases with temperature.
. Table 1
Investigations of the Fe-Si-Zr Phase Relations, Structures and Thermodynamics
Method/Experimental
[1963Spi] X-ray diffracrion (XRD) formation, crystal structure of τ1, (ZrFeSi)

[1965Mar] XRD formations, crystal structures of τ1, and τ2 (Zr2Fe3Si)
[1966Fre] XRD formation, crystal structure of τ1
[1967Far] XRD formations, crystal structures of τ1, and τ3 (Zr4Fe4Si7)
[1967Vor] XRD formation, crystal structure of τ4 (ZrFe2Si2)
[1969Jei] XRD formations, crystal structures of τ1 and τ3
[1969Yar] XRD formation, crystal structure of τ1
[1971Lis] XRD, optical misroscopy formation, crystal structures of τ1, τ2 (Zr2Fe3Si), τ3, τ4, τ5
(OM) (Zr6Fe16Si7) and τ6 (Zr3Fe5Si72); isothermal section at
800˚C
[1978Hao] Differential thermal data on reaction L Ð(δFe) + (γFe) +Zr6Fe23
analysis (DTA), OM
[1978Mit] XRD, OM formation, crystal structure τ2
[1984Cha] XRD formation, crystal structure of τ5
[1985Tro] XRD lattice parameter of Zr0.8Si2Fe0.2 in the temperature
range of 900 to 1200˚C
[1987Bla] XRD lattice parameter of Zr0.8Si2Fe0.2 in the temperature
range of 800 to 1500˚C
[1989Sud1] Drop calorimetry enthalpy of dissolution of Zr in FeSi melt at 1597˚C
[1989Sud2] Drop calorimetry enthalpies of mixing for the Fe-Si-Zr melt at 1627˚C
below 40 at.% Zr

Fe–Si–Zr 29 5
Method/Experimental
[1995Gue] CALPHAD, electron probe Approximate calculation of phase equilibria without

microanalysis (EPMA) including any ternary compounds; experimental
solubility of Fe in ZrSi2 at 800˚C
[1996Eve] XRD formation, crystal structure of τ3
. Table 2
Pearson
Symbol/
α, (αδFe) cI2
< 1910 Im3m
(δFe) W a = 293.15 pure Fe at 1390˚C [V-C2, Mas2]
1538 - 1394
< 912
(γFe) cF4 a = 366.60 [V-C2]
1394 - 912 Fm3m a = 364.67 [Mas2]
Cu
(Si) cF8 a = 543.06 at 25˚C [Mas2]
< 1414 Fd3m a = 542.86 [V-C2]
C (diamond)
(βZr) cI2 a = 360.90 [Mas2]
1855 - 863 Im3m a = 356.8 [V-C2]
W
(αZr) hP2 a = 323.16 at 25˚C [Mas2]
< 863 P63/mmc c = 514.75
Mg a = 323.2 [V-C2]
c = 514.7
α1, Fe3Si cF16 D03
< 1235 Fm3m a = 565 [V-C2]
BiF3 11.0 to 30.0 at.% Si [Mas2]
α2, Fe-Si cP2 B2
≲ 1280 Pm3m 10.0 to 22.0 at.% Si [Mas2]
CsCl a = 281 [V-C2]

6 29 Fe–Si–Zr
Pearson
Symbol/
β, Fe2Si hP6 33.0 to 34.3 at.% Si [Mas2]

1212 - 1040 P3m1 a = 405.2 ± 0.2 [V-C2]
Fe2Si c = 508.55 ± 0.03
η, Fe5Si3 hP16 37.5 at.% Si [Mas2]
1060 - 825 P63/mcm a = 675.9 ± 0.5 [V-C2]
Mn5Si3 c = 472.0 ± 0.5
ε, FeSi cP8 49.6 to 50.8 at.% Si [Mas2]
< 1410 P213 a = 451.7 ± 0.5 [V-C2]
FeSi
ζα, FeSi2(h) tP3 69.5 to 73.5 at.% Si [Mas2]
1220 - 937 P4/mmm a = 269.01 [V-C2]
FeSi2 c = 513.4
ζβ, FeSi2(r) oC48 a = 986.3 ± 0.7 [V-C2]
< 982 Cmca b = 779.1 ± 0.6 66.7 at.% Si [Mas2]
FeSi2 c = 783.3 ± 0.6
Zr3Fe oC16 a = 332 24.6 to 25.2 at.% Fe [2002Ste]
≤ 851 Cmcm b = 1100
Re3B c = 882
α, ZrFe2 cF24 a = 702 to 709 27.5 to 34.4 at.% Zr [2002Ste]
< 1673 Fd3m C15 structure
MgCu2
(Zr1–xSix)Fe2 a = 702.5 x = 0.2 [1985Tro]
a = 694.3 x = 0.5 [1987Bla]
β, ZrFe2 hP24 a = 495 73 to 73.5 at.% Fe [2002Ste]
1345 - 1240 P63/mmc c = 1614 C36 structure
MgNi2
ZrSi2 oC12 a = 372.1 [V-C2]
< 1620 Cmcm b = 1468
ZrSi2 c = 368.3
β, ZrSi oC8 - [Mas2]
2210 - 1460 Cmcm
CrB
α, ZrSi oP8 a = 699.5 [V-C2]
< 1460 Pnma b = 378.6
FeB c = 529.6
β, Zr5Si4 - - [Mas2]
2250 - 1860

Fe–Si–Zr 29 7
Pearson
Symbol/
α, Zr5Si4 tP36 a = 712.25 [V-C2]

< 1860 P41212 c = 1300.0
Zr5Si4
Zr3Si2 tP10 a = 708.2 [V-C2]
< 2215 P4/mbm c = 371.5
Si2U3
Zr5Si3 hP16 a = 788.6 [V-C2]
2180 - 1745 P63/mcm c = 555.8
Mn5Si3
Zr3Si tP32 a = 1101 [V-C2]
< 1650 P42/n c = 545
Ti3P
Zr2FexSi1–x tI12
I4/mcm
Zr2Fe CuAl2 a = 638.0 at x = 1 [2002Ste]
951 - 780 c = 560.0 66.7 to 67.2 at.% Zr [2002Ste]
C16 structure
Zr2Si a = 660.9 at x = 0 [V-C2]
< 1925 c = 529.8
* τ1, ZrFeSi oP12 a = 640.50 Pearson symbol [V-C2]
≲ 1800 Pnma b = 393.50 Space group [1969Jei]
TiNiSi c = 719.90 Lattice parameter [1969Jei]
Decomposition temperature [1967Far]
* τ2, Zr2Fe3Si hP12 Pearson symbol [V-C2]
P63/mmc At 800˚C, from 45 to 51.5 at.% Fe, from 15.5 to
MgZn2 20.65 at.% Si, from 32.95 to 34.36 at.% Zr
[1971Lis].
a = 498.90 [1965Mar]
c = 811.00
a = 498.50 [1978Mit]
c = 809.60
* τ3, Zr4Fe4Si7 tI60 Space group [1969Jei]; Pearson symbol [V-C2]
< above 2000 I4/mmm Stoichiometry [1996Eve]
Zr4Co4Ge7
a = 1298.0 [1967Far]
c = 510.00
a = 1305.6 [1969Jei]
c = 509.00

8 29 Fe–Si–Zr
Pearson
Symbol/
* τ4, ZrFe2Si2 tP10 a = 375.00 [1967Vor]

I4/mmm c = 966.00 Pearson symbol [V-C2]
Al2Ga2Ge
* τ5, cF116 a = 1153.0 [1971Lis]
Zr6Fe16Si7 Fm3m a = 1168.0 [1984Cha]
Mg6Cu16Si7
* τ6, - - [1974Lys]
Zr3Fe5Si72
. Table 3
Composition (at.%)
Reaction T [˚C] Type Phase Fe Si Zr
L Ð(δFe) + (γFe) + β,ZrFe2 1310 E L 76.15 15.35 8.5
. Table 4
Quantity, per mole

Temperature of atoms
Reaction or Transformation [˚C] [kJ, mol, K] Comments
Zr(25˚C)+ L (n = ∞, FeSi at 1597˚C) ⇒ 1597˚C ΔH = –15.3 ± 0.3 (xZr Drop calorimetry
L(xZr, 1597˚C) = 0.05) [1989Sud1]
ΔH = –24.7 ± 0.5 (xZr
= 0.10)
ΔH = –35.0 ± 0.8 (xZr
= 0.15)
ΔH = –49.0 ± 1.0 (xZr
= 0.20)

Fe–Si–Zr 29 9
. Table 5
Investigations of the Fe-Si-Zr Materials Properties
[1978Hao] The specimen were oxidized isothermally at oxidation resistance, density

1150˚C in slowly flowing oxygen under
1.33·104 Pa pressure in a thermobalance.
Density was measured using water
displacement method.
[1985Tro] A PMT-3 metallographic microscope was microhardness
used to determine the microhardness under
a load of 100 or 200 g.
[1987Bla] A PMT-3 metallographic microscope was microhardness
used to determine the microhardness under
a load of 100 g.
[1992Sar] Mössbauer spectroscopy mean value of the hyperfine magnetic
field, isomer shift, and quadrupole
splitting
[2001Ito, dc method in a flowing argon gas using thermoelectric power, electrical
2002Ito] computer-controlled equipment, laser flash resistivity, thermal conductivity,
thermal constant analyzer TC-7000. Seebeck coefficient were measured
from room temperature to 900˚C
[2001Ito] or to 827˚C [2002Ito]

10 29 Fe–Si–Zr
. Fig. 1
Fe-Si-Zr. Isothermal section at 800˚C

Fe–Si–Zr 29 11
. Fig. 2
Fe-Si-Zr. Isolines of the enthalpy of mixing (kJ·mol–1) of liquid at 1627˚C

12 29 Fe–Si–Zr
. Fig. 3
Fe-Si-Zr. Microhardness along the vertical section ZrFe2 - SiFe2

Fe–Si–Zr 29 13
. Fig. 4
Fe-Si-Zr. Lattice parameters of the Zr2FexSi1–x vs Si content

14 29 Fe–Si–Zr
. Fig. 5
Fe-Si-Zr. Lattice parameter along the vertical section ZrFe2 - SiFe2

Fe–Si–Zr 29 15
References
[1963Spi] Spiegel, F.X., Bardos, D., Beck, P.A., “Ternary G and E Silicides and Germanides of Transition
Elements”, Trans. Metall. Soc. AIME, 227, 575–579 (1963) (Crys. Structure, Experimental, 13)
[1965Mar] Markiv, V.Ya., Voroshilov, Yu.V., Gladyshevskii, E.I., “Ternary Laves Phases in the Systems Ti-Co-Si(Ge)
and Zr-Fe-Si(Ge)”, Inorg. Mater., 1(6), 818–821 (1965), translated from Izv. Akad. Nauk SSSR, Neorg.
Mater., 1(6), 890–893 (1965) (Crys. Structure, Experimental, 5)
[1966Fre] Freundlich, W., Farrokhi-Mochai, N., “Two Intermetallic Ternary Phases- ZrFeSi and TiFeSi” (in
French), Compt. Rend. Acad. Sci. Paris, 262C, 1000–1001 (1966) (Crys. Structure, Experimental, 0)
[1967Far] Farrokhi-Mochai, N., “A Study of the Solid Phases in the Fe-Si-Ti, Fe-Si-Zr, and Fe-Si-V Systems” (in
French), Rev. Chim. Miner., 4, 1–25 (1967) (Crys. Structure, Experimental, Phase Relations, 23)
[1967Vor] Voroshilov, Yu.V., Markiv, V.Ya., Gladyshevskii, E.I., “The Zirconium-Nickel-Silicon System”,
(in Russian), Izv. Akad. Nauk SSSR, Neorg. Mater., 3(8) 1404–1408 (1967) (Crys. Structure, Experimen-
tal, 28)
[1969Jei] Jeitschko, W., Jordan, A,G., Beck, P.A., “V and E Phases in Ternary Systems with Transition Metals and
Silicon or Germanium”, Trans. Met. Soc. AIME, 245, 335–339 (1969) (Crys. Structure, Experimental, 27)
[1969Tes] Teslyuk, M.Yu., “Intermetallic Compounds with Structure of Laves Phases” (in Russian), in “Interme-
tallic Compounds with Structure of Laves Phases”, Nauka, Moscow, 1–136 (1969) (Crys. Structure, Phase
Diagram, Review, Theory)
[1969Yar] Yarmolyuk, Y.P., Markiv, V.Y., Hladyshevsky, E.I., “Compounds with the TiNiSi Structure in the
Systems of Two Transition Metals and Either Si or Ge”, Vestn. L’vov. Univ. Khim., 11, 14–17 (1969)
[1971Lis] Lisenko, L.A., Ban, Z., Gladisevskii, E.I., “Investigation of the System Zr-Fe-Si”, Croat. Chem. Acta., 43,
113–118 (1971) (Crys. Structure, Phase Diagram, Experimental, #, *, 20)
[1974Lys] Lysenko, L.A., Ban, Z., Yarmolyuk, Ya.P., Gladisevskii, E.I., “Reaction of Zr with Fe-Group Transition
Metals and Si” in “Struktura Faz. Faz. Prevrashcheniya i Diagrammy Sostoyaniya Metal. Sistem”, Nauka,
Moscow, 21–25 (1974) (Crys. Structure, Review, 20)
26–32 (1978) (Experimental, Mechan. Prop., Interface Phenomena, Phase Relations, Phys. Prop., 24)
[1978Mit] Mittal, R.C., Si, S.K., Gupta, K.P., “Si-Stabilised C14 Laves Phases in the Transaction Metal Systems”,
J. Less-Common Met., 60, 75–82 (1978) (Crys. Structure, Experimental, 12)
[1981Kot] Kotur, B.Ya., Bodak, O.I., “Characteristics of the Reaction of Sc with Si and Transition Metals of Period
IV”, Inorg. Mater., 17(2), 185–188 (1981), translated from Izv. Akad. Nauk SSSR, Neorg. Mater., 17(2),
265–268 (1981) (Phase Diagram, Review, Theory, 27)
[1984Cha] Chaudouet, P., Lambert, B., Madar, R., Fruchart, R., “Existence of a G-type Phase in the Fe-Zr-Si
System“ (in French), Ann. Chim. Fr., 9(2), 119–121 (1984) (Crys. Structure, Experimental, 8)
[1985Tro] Trojko, R., Blazina, Z., “Metal-Metalloid Exchange in Some Friauf-Laves Phases Containing Two
Transition Metals”, J. Less-Common Met., 106, 293–300 (1985) (Crys. Structure, Experimental, 13)
[1987Bla] Blazina, Z., Trojko, R., “On Friauf-Laves Phases in the Zr1–xAlxT2, Zr1–xSixT2 and Zr1–xTixT2 (T = Mn,
Fe, Co) Systems”, J. Less-Common Met., 133(2), 277–286 (1987) (Crys. Structure, Mechan. Prop.,
Experimental, 10)
[1988Bie] Biegel, W., Krebs, H.U., Michaelsen, C., Freyhardt, H.C., “Structure Analyses of Amorphous Melt-Spun
Fe-Zr-(B,Si) Alloys and Mechanically Alloyed Fe-Zr Powders”, Mater. Sci. Eng., 97, 59–62 (1988) (Crys.
[1989Sud1] Sudavtsova, V.S., Zelenina, L.N., Sharkina, N.O., “Reaction in the System FeSi-Nb(Zr)”, Inorg. Mater.,
25(9), 1330–1331 (1989), translated from Izv. Akad. Nauk SSSR, Neorg. Mater., 25(9), 1569–1570 (1989)
[1989Sud2] Sudavtsova, V.S, “Termochemical Properties of Liquid Fe-Zr-Si Alloys”, Russ. Metall., 4, 39–40 (1989),
translated from Izv. Akad. Nauk SSR. Metall., 4, 46–47 (1989) (Experimental, Thermodyn., 5)
[1990Das] Dasilva, C.M., Dacunha, J.B.M., Livi, F.P., Gomes, A.A., “Ferromagnetic Laves Phase Intermetallics
Doped with SP Impurities - A Mössbauer Study of Zr(Fe1–xSix)2”, Hyperfine Interactions, 62(3), 199–206
(1990) (Magn. Prop., Experimental, 21)
[1991Mic] Michaelsen, C., Schultz, L., “Structural Study of Amorphous Zr-Fe-B and Zr-Fe-Si Alloys by 57Fe-
Mössbauer and Magnetization Measurements”, Acta Metall. Mater., 39(5) 987–994 (1991) (Magn. Prop.,
Experimental, 36)

16 29 Fe–Si–Zr
[1992Sar] Sarzynski, J., Budzynski, M., Wasiewicz, R., Wiertel, M., “The Influence of Silicon on Hyperfine
Magnetic Fields in Zr(Fe1–xSix)2 measured for x ≤ 0.17 by Mössbauer Spectroscopy”, J. Phys.: Condens.
Mater., 4, 6473–6478 (1992)
[1995Gue] Gueneau, C., Servant, C., Ansara, I., “Experimental and Thermodynamic Assessments of Substitutions
in the AlFeSi, FeMnSi, FeSiZr and AlCaFeSi Systems”, Appl. Thermodyn. Synth. Process. Mater., Proc.
Symp., 1994 (Pub.1995), Nash, P., Sudman, B. (Eds.), The Mineral. Metal. Mater. Soc., 303–317 (1995)
(Assessment, Experimental, Morphology, Phase Diagram, Phase Relations,Thermodyn., 19)
[1996Eve] Evers, Ch.B.H., Jeitschko, W., “Crystal Structure of Tetrazirconium Tetrairon Heptasilicide, Zr4Fe4Si7”,
Z. Kristallogr., 211, 119 (1996) (Crys. Structure, Experimental, 2)
Performace of β-FeSi2”, J. Alloys Compd., 315, 251–258 (2001) (Electr. Prop., Experimental, 18)
[2002Ito] Ito, M., Nagai, H., Tahata, T., Katsuyama, S., Majima, K., “Effects of Zr Substitution on Phase
Transformation and Thermoelectric Properties of β-FeSi2”, J. Appl. Phys., 92(6), 3217–3222 (2002)
(Electr. Prop., Experimental, Transport Phenomena, 21)
(2002) (Phase Diagram, Crys. Structure, Experimental, #, *, 88)
(1990)

Fe–Sm–Ti 30 1
Iron – Samarium – Titanium

Natalia Kol’chugina
Introduction
The Fe-Sm-Ti system is of interest from the practical viewpoint since the Sm(FeTi)12 (the τ1
ternary phase) compound was found to be a possible candidate for permanent-magnet
materials. The high anisotropy field of the (the τ1 phase with the SmTiFe11 stoichiometry, its
rather high Curie temperature, and reasonable magnetization have determined the necessity of
basic understanding of the phase relations in the Fe-Sm-Ti system, in particular, in the range
of Fe rich alloys.
Earlier investigations into the Fe-Sm-Ti system [1988Oha], [1988Sin], [1988Yan], and
[1989Zha] are related to the preparation and study of the τ1 ternary phase. The Fe rich corner
of the system was studied in [1990Jan] (at 900˚C), [1990Kat], [1991Kim] (at 800 and 1000˚C),
[1991Nei] (at 1000˚C), [1992Rei] (equilibria between 1000 and 800˚C), [1994Iva] and
[1995Iva] (a phase close to the phase denoted subsequently 3:29 (τ2), and [1997Liu] (at
600˚C).
The distinctive feature of the most of studies is the use of melt spinning, mechanical
alloying, cathodic sputtering, powder metallurgy procedures as preparation techniques (thus,
many investigators dealt with both nonequilibrium states and metastable phases) and mag-
netic measurements as procedures, which allow one to find and identify phases along with the
investigation of their magnetic properties.
A review [2000Rag], which summarizes the investigations of the phase equilibria in the
Fe-Sm-Ti system, is available.
A review [1995Cad] considers advances in iron based permanent-magnet materials;
Fe-Sm-Ti compositions are among them.
In a number of works, hydrogenation and nitrogenation (with the formation of hydrides
and nitrides, respectively) techniques are used as procedures that allow the magnetic proper-
ties of Fe-Sm-Ti alloys and compounds to be changed and improved.
Investigations of the Fe-Sm-Ti phase relations, structure identifications are given in
Table 1.
Binary Systems
The Fe-Ti binary phase diagram is taken from the critical assessment of [1987Mur]. The
homogeneity ranges of the TiFe and TiFe2 phases and solubilities of Ti in (γFe) and Fe in (αTi)
are reported using numerous experimental data.
The Fe-Sm binary phase diagram is taken from [Mas2]. The maximum solubility of iron
in (βSm) at the eutectic temperature is shown to be < 0.54 at.% [1982Kub].
The phase diagram of the Sm-Ti binary system is taken from [1991Rei], it is shown
in Fig. 1.

2 30 Fe–Sm–Ti
Solid Phases
There are four ternary phases identified in the system. They are designated in the literature as
1:12 (τ1), 1:11 (τ3), 3:29 (τ2), and 5:17 (τ4). The crystallographic data of the Fe-Sm-Ti phases
are listed in Table 2.
It should be noted that the phases were obtained by both conventional arc and induction
melting (in as-cast and annealed alloys) and rapid quenching (mechanical alloying) followed
by annealing.
The τ1 phase is formed peritectically from (αFe) and liquid at 1300˚C [1992Rei]. Earlier,
[1990Jan] reported that the τ1 phase does not undergo decomposition down to 700˚C. At
1000˚C, τ1 ranges from SmTi0.7Fe11.3 to SmTi1.1Fe10.9 [1992Rei]. [1997Liu] did not find the
compound at 600˚C. However, the phase may be crystallized from the amorphous phase of the
Sm8.3Ti8.3Fe83.4 composition upon annealing at 660˚C [1990Wec]. At 900˚C, τ1 is in equilibri-
um with TiFe2 and Sm(Ti,Fe)2 [1992Rei].
The Sm(Ti,Fe)8.5 phase that subsequently was identified as the τ2 phase is stable above
1000˚C and is not found at 800˚C [1994Iva] and below. The τ2 phase is formed upon vacuum
annealing at 1100˚C for 24 h followed by rapid water quenching. The Ti content, which is
needed to stabilize the τ2 phase may vary from 5.0 to 6.5 in the Sm10TixFe100–x compositions
[1995Yan2]. According to [2000Iva], the τ2 phase may be obtained by annealing of the mixture
Sm2(Ti,Fe)17 + τ1 at 1150˚C for 4 h or at 1000˚C for 48 h. According to [2006Sun], the
structural relationship τ2 Ð Sm2Fe17 + τ1 is valid. In [1991Rei, 1992Rei], this phase is given as
Sm(Ti,Fe)9; it disappears at 800˚C. For this phase, [1991Rei] gives the TbCu7 type structure
and the Curie temperature TC = 209˚C that is close to TC = 200˚C given by [1990Jan] for Sm
(Ti,Fe)7, TC = 197˚C given by [1994Iva] for Sm(Ti,Fe)8.5, and TC = 213˚C and 212˚C given by
[1995Yan2] and [1996Koy] for Sm3(Ti,Fe)29, respectively. According to [1991Rei], the τ2 phase
is formed by a peritectic reaction at 1240˚C and subsequently takes part in the formation of
the τ3 phase.
It is likely that a metastable phase with the TbCu7 structure (space group P6/mmm) that is
discussed in a number of works (since it exhibits interesting magnetic properties) is similar to
the τ2 phase. The phase with the TbCu7 structure was obtained in the SmxTi8Fe92–x (6≤x≤15)
compositions annealed at 600 to 700˚C [1990Din]. At x = 8, 10, 15 at.% Sm, a = 489 pm,
c = 424 pm; at 10, 15 at.% Sm, the phase becomes dominant. According to [1990Jan], as-cast
Sm7.7Ti4.6Fe87.7 contains Sm(Ti,Fe)7 phase. The TbCu7 type structure was found in
Sm10TixFe90–x (x = 4.5 and 6) compositions; for x = 4.5, a = 493.5 pm, c = 420.5 pm and
for x = 6, a = 493.5 pm, c = 422.2 pm [1994Wan]. However, [1994Yan] reported that
Sm20Ti9Fe71 annealed at 810˚C and Sm26Ti9Fe65 annealed at 810 and 900˚C contain (along
with other phases) SmTiFe6 (metastable with a cubic structure, a = 802.3 nm) phase. In
[1995Xia], ribbons with the composition corresponding to τ1 annealed above 740˚C exhibit
the transformation Sm(Ti,Fe)7 (TbCu7 type structure, metastable) Ð SmTiFe11 (ThMn12
type structure). According to [1995Yan1], in SmTixFe7+x (x = 0.2-1.5) melt-spun ribbon,
Sm(Ti,Fe)7 formed is stable even after annealing at 650-750˚C; however, the hexagonal
Sm(Fe,Mo)7 type structure with a = 492.2 pm and c = 424.5 pm, volume of unit cell
8906.2 ·103 pm3 is reported.
The τ3 (with the stoichiometry SmTi1.5Fe9.5) phase is found near the tie line (Sm2Fe17 -
TiFe2) in the isothermal section at 900˚C [1990Jan]. In [1991Kim], τ3 was not found at 800˚C.
τ3 is formed peritectically, is found in the isothermal section at 1000˚C [1992Rei], and is stable

Fe–Sm–Ti 30 3
down to 600˚C [1992Rei], [1997Liu]. According to [1991Rei], the τ3 phase is formed by a

peritectic reaction at 1100˚C.
The τ4 phase is found in [1991Sta] (its X-ray diffraction pattern is analogous to the
Nd5Fe17 phase) and for Sm26TiyFe74–y in the composition range y = 1-17 [1997Yan] in samples
annealed at 810 and 870˚C, i.e., it is stable at these temperatures. However, the τ4 phase was not
identified at 800˚C in [1991Kim]. The lattice parameters first are reported in [1994Yan].
According to [1991Rei], the τ4 phase is formed by a peritectic reaction at 900˚C.
Sm2(Fe,Ti)17 is a solid solution of Ti in Sm2Fe17. According to [1990Kat], the Sm2Fe17
phase with the Th2Zn17 type structure incorporates a small amount of Ti atoms; in this case,
Sm2(Fe,Ti)17 (with the rhombohedral Th2Zn17 type structure, a = 856.0 pm, c = 1247 pm) is
found in Smx(Fe0.875Ti0.125)100–x (x = 10, 15, 20, 25) compositions. [1990Jan] gives the
solubility of Ti in Sm2Fe17 up to 3 at.%. According to [1991Nei], 2.59 at.% Ti are present
in Sm2Fe17. The maximum solubility of Ti in Sm2Fe17 at 1000˚C was found to be 3.7 at.%; at
800˚C, Sm2Fe17 shows a small homogeneity range and dissolves up to 3.5 at.% Ti [1992Rei]. At
600˚C, Sm2Fe17 shows a homogeneity range of about 1 at.% Sm and dissolves up to 3.1 at.% Ti
[1997Liu]. The dependence of the lattice parameter of the solid solution on the Ti content
is considered in [1998Pao] for Sm2TixFe17–x (x = 0-0.85) and in [2000Pao] for Sm2TixFe17–x
(x = 0, 0.4, 0.75) (these compositions cover the aforementioned ranges of solubility of Ti
in Sm2Fe17). [2000Shc] reported the increase in the lattice parameter for the Sm2(TixFe1–x)17
(x = 0.02, 0.03, 0.04) compositions (with the Th2Zn17 type structures) up to x = 0.06;
the existence of the high-temperature modification with the Th2Ni17 type structure is dis-
cussed. The existence of the Sm2(TixFe1–x)17 solid solution up to x = 0.04 is discussed in
[2004Zha].
The Sm2(Ti,Fe)17 phase in the form of low- (Th2Zn17 type) and high- (Th2Ni17 type,
a = 851 pm, c = 838 pm) temperature modifications was found in Sm(TixFe1–x)y, (x = 0.04-
0.065, y = 8.0-9.0) [1995Iva].
The Ti-containing SmFe2 in the form of Sm(Ti,Fe)2 with the Cu2Mg type structure with
a = 742.7 pm in and a = 741.5 pm is reported in [1990Kat] and [1994Yan], respectively. In
[1997Liu], the solubility range of Ti in SmFe2 is up to 4.7 at.%. The content is higher than the
value (1 at.%) determined from the isothermal section at 800˚C [1992Rei]. [1997Liu]
deduces that the Ti content in SmFe2 will be reduced as the annealing temperature decreases.
However, [2006Sun] indicates that, when ingots Sm2Ti1Fe16 are quickly cooled along the
cooling direction, the Sm-rich phase is not Sm(Ti,Fe)2 but SmFe2.
For the SmFe3 phase in the Fe-Sm-Ti system, the Sm solubility range is from 24.0 to 26.8
at.% and the maximum solubility of Ti is up to 4.1 at.% [1997Liu], which essentially agrees
with the result of [1990Jan] who gives 5 at.% solubility in the isothermal section at 900˚C.
The amount of Sm dissolving in TiFe2 is about 0.6 at.% [1997Liu].
The data on the invariant equilibria are available in a partial reaction scheme given in Fig. 2 in
accordance with [1991Rei]. The τ2 phase is included in the scheme instead of the Sm(Ti,Fe)9
phase. The eutectic temperature in the Fe-Ti binary system was corrected in accordance with
the accepted phase diagram.

4 30 Fe–Sm–Ti
A partial liquidus projection is given in Fig. 3. It is available in [1992Rei] and [1991Rei] (where
the liquidus surface was constructed experimentally based on EDX and thermal analyses and
metallographic data) and corresponds to the Fe-Sm-TiFe2 field. The Sm(Ti,Fe)9 phase
reported by the author is denoted here as τ2 phase (Sm3(Ti,Fe)29).
Isothermal Sections
Isothermal sections of the Fe-Sm-Ti system were studied in [1990Jan] (at 900˚C), [1991Kim]
(at 800 and 1000˚C), [1991Nei] (at 1000˚C), [1992Rei] (at 800 and 1000˚C), and [1997Liu] (at
600˚C). All these works show good agreement. The isothermal sections at 1000 and 800˚C are
shown in Figs. 4 and 5 from [1992Rei]. The Sm(Fe,Ti)9 phase of [1992Rei] is denoted here
as τ2, Sm3(Ti,Fe)29. The character of the phase relations at 1000˚C continues down to at least
900˚C [1990Jan], [1992Rei]. Figure 6 presents the isothermal section at 600˚C from [1997Liu].
The homogeneity ranges of the binary phases SmFe3 and SmFe2 along the binary axis are ruled
out since they disagree with the accepted binary diagram Fe-Sm.
Three compounds τ1, τ2, and τ4 (among four ternary phases formed in the Fe-Sm-Ti system)
are magnetic phases; τ3 is a nonmagnetic phase. Their properties and properties of alloys with
close compositions are given in Table 3.
The magnetic properties of the metastable phase with the TbCu7 type structure and
magnetic properties of Sm2(Ti,Fe)17 (that is a solid solution of Ti in the Sm2Fe17 compound)
are also considered in Table 3.
The effect of hydrogenation and nitrogenation on the magnetic properties of ternary
phases also is considered in Table 3 in spite of the fact that these compositions are quaternary.
These procedures allow the Curie temperature to be increased and the magnetocrystalline
anisotropy type, saturation magnetization, coercivity to be changed. The effect of other
alloying additions (B, C, Si, metals) is also discussed.
The possibility of preparation of magnets based on the Fe-Sm-Ti system is discussed in
[1992Rei]. The authors conclude that the preparation of Fe-Sm-Ti-based sintered magnets is
restricted by phase relations in the system.
Miscellaneous
Mössbauer spectra of amorphous compositions close to τ1 and annealed (at 650, 700, 800,
850˚C) Sm10Ti8Fe82 alloys are given in [1990Din]; [1991Qia] performed Mössbauer spectros-
copy for the melt-spun Sm20Ti10Fe70. NMR spectroscopy for τ1 was performed in [1996Kap].
An enthalpy change during crystallization (in Ar) of melt-spun Sm0.17Fe0.83 and
(Sm0.17Fe0.83)94Ti3C3 ribbon alloys was estimated in [1999Shi] based on DTA data; these
were found to be –28.1 J·g–1 and 36.4 J·g–1, respectively. These values are normalized to the
mass of the entire sample (crystalline and amorphous fractions) and not to the amount of
Fe–Sm–Ti 30 5
material actually transforming. Therefore, this value is directly related to the amount of
amorphous fraction in each sample. The higher value for (Sm0.17Fe0.83)94Ti3C3 indicates
that the Ti and C additions increase the amorphous phase content (i.e., improve the glass
formability) as well as its stability that follows from the higher crystallization temperature of
the alloy (596˚C) as compared to that of Sm0.17Fe0.83 (570˚C). The enthalpy change during
crystallization (in Ar) of melt-spun (Sm0.11Fe0.89)94Ti3C3 ribbon is –6.8 J·g–1. The enthalpy
changes determined upon crystallization in N2 are lower.
. Table 1
Investigations of the Fe-Sm-Ti Phase Relations, Structures and Thermodynamics
[1988Oha] TEM, EMPA, X-ray diffraction / Compositions 7.14 (7.32) at.% Sm-7.14
magnetization measurements (7.55) at.% Ti-85.72 (85.13) at.% Fe / τ1
phase.
[1988Sin] Arc melting, melt spinning, annealing (at Ribbon Sm8Ti8Fe84 annealed at 700˚C
700˚C) / DSC, X-ray diffraction, EDXA, contains a phase with the ThMn12 type
TEM, magnetic measurements structure.
(thermomagnetic analysis, hysteresis loop
measurements)
[1988Yan] Arc melting / magnetic measurements SmTiFex with x = 8-11 has the tetragonal
ThMn12 type structure.
[1989Zha] R.f. (radio frequency) induction melting, τ1 (SmTiFe11); lattice parameters
annealing, hydrogenation / X-ray
diffraction, thermomagnetic analysis,
magnetic measurements
[1990Coc] Melt spinning, annealing (at 540, 800˚C) / Ribbons Sm17Ti8 Fe75 annealed at 540 and
X-ray diffraction, DTA, magnetic 800˚C / off-stoichiometric phase with the
measurements ThMn12 type structure.
[1990Din] Melt spinning, annealing (at 600, 650, 700, SmxTi8Fe92–x (6≤x≤15).
750, 800, 850, and 900˚C) / X-ray The compositions with x = 8, 10, 15
diffraction, SEM, EDAX, Mössbauer annealed at 600-700˚C exhibit the
spectroscopy, magnetization presence of the TbCu7 structure
measurements (metastable), that is a dominant phase at
x = 10, 15 at.% Sm.
Ribbons with x = 6, 8 annealed at 800˚C
and above have the ThMn12 type
structure; ribbons with x = 10, 15 have a
cubic structure.

6 30 Fe–Sm–Ti
[1990Jan] 99.9%Sm, 99%Fe, 99.9%Ti (mass%) Arc Isothermal section at 900˚C/

melting, annealing (at 900˚C for 72 h), compositions Sm7.7TixFe92.3–x (x = 2.8, 4.6,
quenching in water/ X-ray diffraction 7.7, 9.2, 18.5).
metallography, electron probe analysis, τ1 does decompose down to 700˚C but it
magnetic and thermomagnetic analyses. is restricted by the coexistence of
Sm2Fe17 and TiFe2.
A new τ3 (SmTi1.5Fe9.5).
As-cast Sm7.7Ti4.6Fe87.7 contains the Sm
(Ti,Fe)7 phase.
[1990Kat] Sm 99.5%, Fe 99.9%, 99.9 mass% purity Section Smx(Ti0.125Fe0.875)100–x (x = 10, 15,
Induction melting, annealing (1000˚C, 1 h 20, 25); samples contain Sm2(Ti,Fe)17, Sm
+ 750˚C, 63 h), water quenching / DTA, (Ti,Fe)2, TiFe2 Samples with x = 15, 20, 25
X-ray diffraction, metallography annealed at 750˚C contain Sm2Fe17+Sm
(Ti,Fe)2; at 855˚C: a peritectic
decomposition of Sm(Ti,Fe)2; with x = 10,
15, 20, 25, a peritectic decomposition of
Sm2(Ti,Fe,)17 into the liquid and τ1 phase
at 1260˚C is observed.
After annealing at 1000˚C for 1 h, τ1 is not
observed.
Sm20Ti10–xFe70+x (x = –2, 0, 2); as-
quenched (at low cooling rates) ribbons
contain the τ1 phase.
Melt spinning, annealing (between 725 In annealed (at 800˚C) ribbons, a phase of
and 900˚C for 15-60 min) / magnetic the Sm20Ti10Fe70 composition is present.
measurements
[1990Sch2] Mechanical alloying, annealing (at 800˚C), SmxTi10Fe90–x (x = 16, 18, 20, 22) annealed
hot pressing (at 725˚C), induction melting at 800˚C exhibits the presence of a new
+ rapid quenching, annealing (at 700- phase of the Sm20Ti10Fe70 composition.
850˚C) /X-ray diffraction, magnetic
measurements
[1991Cad] Sputtering / X-ray diffraction, magnetic In sputtered and subsequently
measurements crystallized films, τ1 (SmTi0.5Fe11.5) phase
is found.
[1991Kim] 99.9% Sm, 99.7%, Ti, 99.98% Fe; Melting & Isothermal sections at 800 and 1000˚C;
casting, annealing (at 800 and 1000˚C), SmxTiyFe100–x–y (3.8<x<11.5, 8.8<y<19.2)
melt spinning + annealing (at 800˚C)/ compositions (around SmFe11Ti) are
optical microscopy, SEM, X-ray diffraction, studied.
magnetic measurements

Fe–Sm–Ti 30 7
[1991Nei] 99.9% Sm, 99.7% Ti, 99.98% Fe Arc Isothermal section at 1000˚C for the
melting, annealing (at 1000˚C for 3 compositions around τ1.
weeks), water quenching/optical A “Sm(Ti,Fe)9” phase of the
metallography, microhardness Sm10.44Ti5.55Fe84.01 composition is found.
measurements, SEM, EDAX, X-ray
diffraction, magnetic measurements
[1991Sta] Cathodic sputtering or mechanical A phase with the hexagonal Nd5Fe17 type
alloying structure
[1992Rei] Sm > 99.5 mass%, Ti > 99.5 mass%, Fe > Projection of the liquidus surface.
99.9 mass%, 5-fold arc melting, annealing Equilibria between 1000 and 800˚C. τ1 is
at 1000˚C for 7 d, at 900˚C for 14 d, and at in equilibrium with (αFe), TiFe2, and a Sm
800˚C for 45 d, water quenching / optical (Ti,Fe)9 phase similar to Sm(Ti,Fe)7.
metallography, EDX, thermal and
[1994Iva] Sm - 99.8%, Ti - 99.95%, Fe - 99.98%. Sm(TixFe1–x)y (0.03≤x≤0.08 and 7.0≤≤9.0)
Induction melting, annealing at 1150- compositions quenched from 1150 and
900˚C / X-ray diffraction, magnetic 1000˚C exhibit the presence of a new
measurements phase Sm(Ti0.065Fe0.935)8.5 with an
orthorhombic structure.
[1994Wan] Arc melting, annealing (at 1200˚C for The TbCu7 type structure is found in
24 h), high-energy milling, annealing at Sm10TixFe90–x (x = 4.5 and 6)
600-900˚C / X-ray diffraction, compositions.
[1994Yan] Mechanical alloying, annealing (at 600- Compositions SmxTi9Fe91–x (x = 15-30)
900˚C for 5 min to 2 h) / X-ray diffraction, and Sm26TiyFe74–y (y = 0-17) are studied.
TEM, SEM, EDAX, magnetic τ4 is found.
measurements Sm20Ti9Fe71 annealed at 810˚C comprises
(Sm,Ti)2Fe (?) + SmTiFe6 (metastable,
cubic) + τ4 (hcp), + Sm(Ti,Fe)2.
Sm26Ti9Fe65 annealed at 810 and 900˚C
exhibits the presence of analogous
phases and (Sm,Ti)2Fe17 (?)
[1995Iva] Sm - 99.8%, Fe - 99.98%, Ti - 99.95% Sm(TixFe1–x)y (0.04≤x≤0.07 and 8.0≤y≤9.0)
Induction melting, annealing at 900- annealed at 1150-1250˚C contains the Sm
1250˚C / X-ray diffraction, magnetic (Ti,Fe)8.5 phase.
measurements
[1995Xia] Induction melting, melt spinning, Ribbons corresponding to the τ1 phase
annealing at 580-880˚C for 5 min / X-ray composition annealed above 740˚C
diffraction, DTA, magnetic measurements exhibit the transformation Sm(Ti,Fe)7
(TbCu7 type structure (metastable) Ð τ1
(ThMn12 type structure).

8 30 Fe–Sm–Ti
[1995Yan1] Induction (repeated) melting, melt In SmTixFe7+x (x = 0.2-1.5) melt-spun

spinning, annealing at 650 to 750˚C / ribbon, Sm(Ti,Fe)7 formed is stable even
X-ray diffraction, SEM, TEM, EMPA, EDX, after annealing. The phase has the
thermomagnetic analysis, magnetic hexagonal Sm(Mo,Fe)7 type structure.
measurements
[1995Yan2] All components at least 99.9% purity, In Sm10TixFe85 (x = 4.2, 4.4, 4.6, 4.8, 5.0,
twice arc melting, annealing at 1000- 6.0, 6.5) annealed at from 1000 to 1200˚C,
1200˚C for 10-60 h, quenching in air or quenched in water, the τ2 compound
water/X-ray diffraction, thermomagnetic (Sm3(Fe0.933Ti0.067)29 stoichiometry)
analysis, magnetic measurements (monoclinic Nd3(Ti,Fe)29 type structure is
found.
[1996Has] R.f. (radio frequency) melting, arc melting, In alloys SmxTiyFe100–x–y (x = 6.9-1.17 and
powder metallurgical process, annealing y = 0-9.7), a nonstoichiometric compound
at 600-1150˚C for 2-100 h / X-ray R2(Ti,Fe)17+δ (δ = 1.0-4.0) with a hexagonal
diffraction, SEM/EDX, electron beam structure (space group P 62m) exists
diffraction, magnetic measurements between Sm2(Ti,Fe)17 and τ1.
[1997Liu] 99.95 at.% Sm, 99.9 at.% Fe, 99.5 at.% Ti Isothermal section at 600˚C
Diffusion triple technique, annealing at (compositions (0.08-33.70 at.%) Sm -
600˚C for 500 h, quenching in icy salt (2.75-85.20 at.%) Ti - (95.98-14.66 at.%)
water/electron microprobe analysis Fe). Detected phase regions:
SmFe2+TiFe2+(αSm); TiFe2+TiFe+(αSm);
TiFe+(βTi)+(αSm); SmFe3+SmFe2+TiFe2;
Sm2Fe17+TiFe2+αFe; SmFe3+TiFe2+(αFe);
SmFe3+Sm2Fe17+τ3; Sm2Fe17+TiFe2+τ3;
(αSm)+(αTi)+(βTi). Stoichiometry of τ3
from SmTi1.2Fe9.8 to SmTi1.4Fe9.6
[1997Yan] Mechanical alloying, annealing at 750- Sm26TiyFe74–y with y = 0, 1, 13, 17
870˚C for 30 min / X-ray diffraction, annealed at 840˚C and with y = 3
magnetic measurements annealed at 870˚C contain the mixture of
phases TiFe2, SmFe2, Sm2(Ti,Fe)17, τ4
[2000Iva] Induction melting, annealing at 1150˚C Virtually complete solid state
for 4 h or 1000˚C for 48 h / X-ray transformation of the Sm2(Ti,Fe)17+τ1
diffraction mixture into τ2.
[2000Shc] Induction melting, annealing at 900- Sm2(TixFe1–x)17 (x≤0.06) with x = 0.02,
1450˚C, quenching in water / X-ray annealed at 1200-1250˚C is a mixture of
diffraction, magnetic measurements Th2Zn17 and Th2Ni17 structures; annealed
at 1200˚C with x = 0.03 and 0.04, both
structures are observed; after annealing
at 1250˚C, only the Th2Ni17 type structure.
Monotonic increase in the lattice
parameters is observed up to x = 0.04.

Fe–Sm–Ti 30 9
[2004Zha] Arc melting, annealing (at 1100˚C for In Sm2(TixFe1–x)17 (x = 0, 0.02, 0.04, 0.06,
24 h) / X-ray diffraction, scanning electron 0.08, 0.1) annealed at 1100˚C with
microscopy, magnetic measurements x = 0-0.04 Sm2(Ti,Fe)17 (Th2Zn17 type
structure) is found; with x = 0.06, - τ2
(monoclinic, Nd3(Ti,Fe)29 type structure;
with x = 0.08-0.1 - τ1 (ThMn12 type
structure); with x = 0.08, τ1 coexists with
τ2 and Sm(Ti,Fe)2
[2006Sun] Arc melting, annealing (at 1000˚C for As-cast Sm2Ti1Fe16 consists of τ2 (the
48 h), water quenching, HDDR process / main phase) and secondary phases τ1, τ3,
X-ray diffraction, scanning electron Sm(Ti,Fe)2, αFe(Ti) phases; the annealed
microscopy, magnetic measurements alloy consists of τ2, τ1, τ3, and a few Sm
rich phases (that depending on the
cooling direction may be SmFe2 rather
than Sm(Ti,Fe)2).
Structural relationship τ2 Ð Sm2Fe17 + τ1
is valid.
The τ3 phase (SmTi1.5Fe9.5)
. Table 2

(δSm) hP4 a = 361.8 at 25˚C, 4.0 GPa [Mas2]

P63/mmc c = 1166
αLa
(γSm) cI2 - [Mas2]
1074 - 922 Im3m
W
(βSm) hP2 a = 366.30 [Mas2]
922 - 734 P63/mmc c = 584.48
Mg
(αSm) hR9 a = 362.90 at 25˚C [Mas2]
< 734 R3m c = 2620.7
αSm

10 30 Fe–Sm–Ti

(ωTi) hP3 a = 462.5 at 25˚C, HP → 1 atm [Mas2]
P6/mmm c = 281.3
ωTi
(βTi) cI2 a = 330.65 [Mas2]
1670 - 882 Im3m
W
(αTi) hP2 a = 295.06 at 25˚C [Mas2]
< 882 P63/mmc c = 468.35
Mg
(αδFe) cI2
Im3m
(δFe) W a = 293.15 at 1390˚C [V-C2, Mas2]
1538 - 1394
(αFe) a = 286.65 at 25˚C [Mas2]
< 912
(γFe) cF4 a = 364.67 at 915˚C [V-C2, Mas2]
1394 - 912 Fm3m
Cu
Sm2Fe17 hR57 [Mas2]
< 1280 R3m a = 857.0 [V-C2]
Th2Zn17 c = 1244.0
SmFe3 hR36 [Mas2]
< 1010 R3m a = 518.7 [V-C2]
NbB3 c = 2491.0
SmFe2 cF24 (C15) [Mas2]
< 900 Fd3m a = 741.6 [V-C2]
Cu2Mg
TiFe2 hP12 64.5-72.4 at.% Fe [1987Mur]
< 1427 P63/mmc a = 477.7 at 64.6 at.% Fe
MgZn2 c = 780.7
a = 478.1 at 71.4 at.% Fe
c = 779.5
TiFe cP2 a = 297.8 ± 0.2 at 50 at.%
< 1317 Pm3m 47.5-50.3 at.% Fe at 1317˚C
CsCl [1987Mur]

Fe–Sm–Ti 30 11

* τ1, Sm(Ti,Fe)12 tI26 a = 856 for compositions 7.14 (7.32) at.%
(SmTiFe11 I4/mmm c = 479 Sm-7.14 (7.55) at.% Ti-85.72 (85.13)
stoichiometry) ThMn12 at.% Fe [1988Oha]
1300 - 700
a = 858 in Sm8Fe84Ti8 annealed at 700˚C
c = 479 [1988Sin]
or
a = 854
c = 477
a = 853.4 for SmTiFe11
c = 477.6 V = 347.832·106 pm3 [1989Zha]
b = 480.0 V = 351.4·106 pm3 [1991Yan]
a = 854 for SmTiFe11 [1996Kim]
c = 478
c = 479.8 V = 352·106 pm3 [1998Isn]
a = 843.8 SmFe11.5Ti05 crystallized in
c = 480.5 sputtered films [1991Cad]
a = 856.3 for Sm(Fe0.917Ti0.082)12
c = 480.2 V = 352·106 pm3 [1996Koy]
V = 351.1·106 pm3
a = 856.0 [2001Nik]
c = 479.2
* τ2, Sm3(Ti,Fe)29 mP* a = 1065 annealing at 1000-1200˚C,
1240 - 900 P21/c b = 858 quenching from high
Nd3(Fe,Ti)29 c = 972 temperatures, for
β = 96.98˚ Sm3(Ti0.067Fe0.933)29 [1995Yan2]
a = 1063 Sm3(Ti0.06Fe0.94)29 stoichiometry
b = 857 V = 881·106 pm3
c = 974 [1996Koy]
β = 97˚
a = 1061 [2000Iva]
b = 856
c = 970
β = 96.9˚
a superstructure based on a = 972 1150-1250˚C / Sm(Tix Fe1–x)y
the CaCu5 type structure b = 856 (0.04≤x≤0.07 and 8.0≤y≤9.0) / Sm
with a monoclinic cell c = 1063 (Ti,Fe)8.5 [1995Iva]
β = 96˚50’

12 30 Fe–Sm–Ti

* τ3, Sm(Ti,Fe)11 tP24 a = 825.3 SmFe9.5Ti1.5 [1990Jan]
1100 - 600 P4/mbm c = 482.5
CeMn6Ni5
or
t* [2006Sun]
Sm(Ti,Fe)11
* τ4, Sm5(Ti,Fe)17 hP264 a = 2017.2 in SmxFe91–xTi9 (x = 15-30) and
870 - 800 P63/mcm c = 1237.4 Sm26Fe74–yTiy (y = 0-18) annealed
Nd5Fe17 at 810 to 870˚C [1994Yan]
. Table 3
Investigations of the Fe-Sm-Ti Materials Properties
[1987Had] Thermomagnetic analysis / vibrating- For as-cast, melt-spun, crystallized

sample magnetometer ribbons, aligned powders, and sintered
magnets SmxTizFey (3≤x≤15, 78≤y≤87,
3≤z≤13), hysteresis loops are measured;
the maximum anisotropy field is more
than 18 kOe (14.328 kA·m–1).
Room temperature coercive force
(0.2-2.5 kOe (0.159 -1.99 kA·m–1)) and
hysteresis loops determined for as-cast
materials, melt-spun ribbons, aligned
powders, and sintered magnets are given
[1988Oha] Magnetization measurements in Magnetization curve for τ1; c axis is the
magnetic field applied parallel and easy axis of magnetization.
perpendicular to the c axis
[1988Sin] Thermomagnetic analysis / vibrating- Room-temperature coercivity of melt-
sample magnetometer spun ribbons Sm8Ti8Fe84 crystallized with
the formation of τ1 is 2 kOe
(1.592 kA·m–1).
[1988Yan] cited from abstract (no experimental τ1 exhibits unusual uniaxial
details are available) magnetocrystalline anisotropy, c-axis is
the easy magnetization direction, TC =
337˚C.
[1989Had] cited from abstract (no experimental The τ1 phase coercivity is 7.7 kOe
details are available) (6.13 kA·m–1).

Fe–Sm–Ti 30 13
[1989Str] Thermomagnetic measurements For Fe-Sm-Ti compositions (with the

ThMn12 type structure) alloyed with B and
Si+Al, the possible coercive force is
> 6.5 kOe (5.174 kA·m–1).
[1989Zha] Faraday balance, vibrating sample Increase in the Curie temperature and
magnetometer anisotropy field for τ1 by hydrogenation:
TC from 311 to 354˚C and anisotropy field
HA from 140 (111.44) to 170 kOe
(135.32 kA·m–1).
[1990Din] Vibriting sample magnetometer The magnetization of Sm10Ti8Fe82
annealed at 600-700˚C containing the
metastable phase with the TbCu7
structure is 110 Am2·kg–1.
[1990Jan] Thermomagnetic analysis, magnetization Curie temperature of Sm(Ti,Fe)7 is 200˚C;
measurements TC of τ1 is 305˚C. τ3 has no magnetic
moment.
Magnetization curves for Sm7.7Ti9.2Fe83.1
are given.
[1990Kat] Vibriting sample magnetometer Magnetization (vs melt-spinning
parameters), hysteresis loop, coercivity (vs
annealing temperature of melt-spun
ribbons), remanence for Sm20Ti10Fe70
quenched from 1400˚C + annealed at
800˚C for 15 min are given; iHc= 44.5 kOe
(35.422 kA·m–1).
For Sm25Ti9.4Fe65.6 annealed at 850˚C,
iHc= 58 kOe (46.168 kA·m ), Br = 2.4 kG.
-1
[1990Sch1] magnetic hysteresis loop measurements For Sm20Ti10Fe70 mechanically alloyed

and sintered at 725˚C for 30 min, Hc =
50.3 kOe (40.04 kA·m–1), Br = 3.0 kG,
(BH)max = 2.2 MG Oe (17.5 kJ·m–3), TC =
380˚C.
For Sm10Ti10Fe80-based compositions, the
effect of B, Mo, Co, V, Si, Ga additions is
discussed.
[1990Sch2] Vibrating-sample magnetometer Demagnetization curves and Br vs
composition for SmxTi10Fe90–x (x = 16-22)
mechanically alloyed (or rapidly
quenched) and annealed at 800˚C for 30
min (or hot pressed) are given. TC = 380˚
C, Hc = 50.3 kOe (40.038 kA·m–1), Br = 3.0
kG, Ms = 6-7 kG, (BH)max = 2.2 MG Oe (17.5
kJ·m–3); temperature dependence of
coercivity is given.

14 30 Fe–Sm–Ti
[1990Wan] Thermomagnetic analysis / vibrating- For Sm8Ti9Fe83 ribbons annealed at 800˚

sample magnetometer C, iHc = 5.6 kOe (4.46 kA·m–1), Ms = 806 G.
V-containing compositions have the
higher Hc, decrease in Hc for Nb-, Mo-, W-
containing compositions, increase in Hc
by Zr (small content) and Ga additions are
observed; all the additions decrease Ms.
Preparation of sintered magnets is
discussed, measured hysteresis loop
shows Hc = 2 kOe (1.592 kA·m–1).
[1990Wec] Vibrating-sample magnetometer For Sm8.3Ti8.3Fe83.4 and Sm7.7Ti15.4Fe76.9
crystallized ribbons, iHc = 3.4 kA·cm–1
(0.034 kA·m–1).
iHc = 40 (0.40) and 33 kA·cm
–1
(0.33
kA·m–1) is observed for a new phase
found in Sm20Ti10Fe70 mechanically
alloyed (followed by solid-state reaction
at 725˚C) and rapidly quenched followed
by annealing at 800˚C), respectively; TC =
380˚C.
Improving properties (coercivity) and
increase in TC by Zr and Co additions;
decrease in the anisotropy field, change
of the anisotropy type from axial to planar
are observed.
[1991Kim] Ac-susceptibility, measurements / Magnetization, isocoercivity lines of Fe-
Vibrating-sample magnetometer Sm-Ti (around τ1) melt-spun samples are
given.
SmFe9Ti2 (τ3) is non-magnetic or weakly
magnetic.
[1991Sta] Cathodic sputtering or mechanical The possibility to synthesize a
alloying magnetically hard phase in Fe-Sm-Ti
compositions is shown; the phase has the
hexagonal Nd5Fe17 type structure.
[1991Yan] Extracting-sample magnetometer Nitrogenation of τ1 at 500˚C for 2 h
changes the c-axis plane anisotropy to
basal-plane one.
[1991Wec] Rapid solidification The high coercivity more than 40 kA·cm–1
(0.40 kA·m–1) can be reached for Fe-Sm-Ti
compositions with the Sm5(Ti,Fe)17 phase
(named A2).
[1994Iva] Vibrating-sample magnetometer, ac- Magnetization curves, specific
susceptibility measurements magnetization vs temperature for Sm(Ti,
Fe)8.5 are given; it is highly anisotropic
ferromagnet with TC = 197˚C.

Fe–Sm–Ti 30 15
[1994Wan] Vibrating-sample magnetometer, Thermomagnetic analysis for

extracting-sample magnetometer Sm10Ti4.5Fe85.5 is performed.
Nitrogenation increases the Curie
temperature; magnetization curves,
hysteresis loop, dependence of the Curie
temperature of nitrides on the annealing
temperature are given.
[1994Yan] Pulsed magnetometer, ac-susceptibility Ac-susceptibility, Curie temperature,
measurements magnetization curves, coercive force,
remanence, energy product for
SmxTi9Fe91–x mechanical alloyed,
annealed at 810-840˚C for 30 min are
given.
TC = 160-180˚C.
At x = 26, room-temperature iHc = 69.09
kOe (54.995 kA·m–1) (annealing at 840˚C
for 50 min); the high coercivity is due to
the Sm5(Ti,Fe)17 phase.
At x = 15, 4πMr =2.98 kG, (BH)max = 2.228
MG Oe (17.735 kJ·m–3).
[1995Cad] review, no experimental details given A SmFe5 phase stabilized by Ti has iHc =
6.2 kOe (4.935 kA·m–1), (BH)max = 5.4 MG
Oe (42.984 kJ·m–3), TC = 400˚C.
Crystal phase connections and
transformations between 2:17, 1:12, 1:7
structures that are derivatives from the
CaCu5 structure, magnetization and
anisotropy consideration are discussed.
[1995Iva] Ac-susceptibility measurements / Room temperature magnetization curves
vibrating sample magnetometer for Sm(Ti0.065Fe0.935)8.5 and Sm2(Ti,Fe)17
are given.
[1995Xia] Pulsed magnetometer, ac-susceptibility For τ1 ribbons melt-spun and annealed,
measurements ac-susceptibility vs temperature and
coercivity vs annealing temperature are
given.
The coercivity iHc = 5.8 kOe (4.62 kA·m–1)
is reached for ribbons quenched at 30 m/
s + annealed at 820˚C.

16 30 Fe–Sm–Ti
[1995Yan1] Thermomagnetic analysis / vibrating- Curie temperature, hysteresis loops,

sample magnetometer coercive force, remanence, energy
product are given for SmTixFe7+x (x = 0.2-
2) (repeated induction melting, melt
spinning, annealing at 650-750˚C):
at x = 1.5, iHc = 5 kOe (3.98 kA·m–1),
(BH)max = 3.4 MG Oe (27.064 kJ·m–3);
at x = 0.4-1.0, Br = 6-8 kG; at x = 0.8,
(BH)max = 4.0 MG Oe (31.84 kJ·m–3); at
x = 1.0, TC = 304˚C.
[1995Yan2] Magnetically aligned powder, Curie temperature, magnetization,
thermomagnetic analysis / extracting saturation magnetization, anisotropy field
sample magnetometer, SQUID, high-field are given for Sm3(Fe0.933Ti0.067)29:
installation TC = 213˚C, Ms = 119 Am2·kg–1, uniaxial
anisotropy, Ha = 3.4 T, first-order
magnetization process (FOMP).
Nitrogenation to 5.0 N per formula unit
(powder 15 μm size) at N2 pressure 1 atm,
500-600˚C for 2 h results in increase in
both the Curie temperature to 477˚C, Ms
= 140 Am2·kg–1, uniaxial anisotropy Ha =
12.8 T; μ0iHc = 0.83 T, (BH)max = 105 kJ·m–3
at 293 K
[1996Has] Magnetization measurements Saturation magnetization, Curie
temperature (no values are available) for
SmxTiyFe100–x–y (x = 6.9-1.17 and y = 0-9.7)
for R2Ti,Fe)17+δ (δ = 1.0-4.0)
nonstoichiometric compound are given.
[1996Kim] Thermomagnetic analysis / vibrating- For τ1, magnetization vs temperature,
sample magnetometer, SQUID, / anisotropy constants K1 = 9.2 MJ·m–3, K2 =
computer calculations 0.40 MJ·m–3, anisotropy field μ0HA = 19.8
T, TC = 314˚C, c-axis magnetization
direction are given. Substitution of other
rare-earth metals for Sm decreases
substantially the anisotropy field.

Fe–Sm–Ti 30 17
[1996Koy] Thermomagnetic analysis / vibrating- For Sm3(Fe0.94Ti0.06)29, magnetization

sample magnetometer (FOMP), anisotropy field, Curie
temperature are Ms = 98.3-103 Am2·kg–1,
μ0HA = 4 T, TC = 212˚C.
Schematic diagram of the formation of τ2
structure from CaCu5 structure is given.
The use of hydrogenation (cooling to
room temperature in hydrogen
atmosphere after heating to 500˚C) and
nitrogenation (at 475-500˚C for 10-24 h at
0.1-1 MPa) results in the increase in the
lattice parameters, TC.
[1997Yan] Pulsed magnetometer, ac-susceptibility For Sm26TiyFe74–y, with y = 0, 1, 3, 17,
measurements temperature dependences of ac-
susceptibility, demagnetization curves
are given.
[1998Isn] Thermomagnetic analysis / High Field For τ1, Curie temperature magnetization
Magnet Facility curves are given: Ms = 17.5 μB/f.u,
anisotropy constants K1 = 3.9 MJ·m–3,
K2 = 0.1 MJ·m–3; hydrogenation to about
1 H per f.u., (initial thermal activation and
20 bar H2 pressure) results in the increase
in the lattice parameters, Curie
temperature, saturation magnetization.
[1998Pao] Thermomagnetic analysis / Singular point For Sm2TixFe17–x (x = 0-0.85), Curie
detection technique temperature increases with increasing Ti
content, anisotropy constant and
anisotropy field decrease; compositional
dependence of lattice parameters on Ti
content is shown.
[1998Ter] Thermomagnetic analysis / vibrating- Compositional dependences of the Curie
sample magnetometer, torque temperature, saturation magnetization,
magnetometer and anisotropy constants are given.
Effect of Co substitution for Fe on the
parameters is discussed.
[1999Hu] Thermomagnetic analysis / vibrating- Compositions Sm10Fe85.5Ti4.5 and
sample magnetometer, extracting- Sm10Fe84Ti6 (with TbCu7 type structure)
sample magnetometer are discussed.
Nitrogenation (at 450˚C for 2 h) increases
the lattice parameters, Curie temperature
and saturation magnetization.
[1999Shi] X-ray diffraction, DTA, TEM Compositions Sm-Fe-Ti-C and effect of C
and Ti on the glassy stability are
discussed.

18 30 Fe–Sm–Ti
[2000Pao] Thermomagnetic analysis / Singular point For Sm2TixFe17–x (x = 0, 0.4, 0.75)

detection technique anisotropy constant, anisotropy field (that
decreases with increasing x) are given, the
Sm contribution to the anisotropy is
analyzed.
[2000Shc] Extraction magnetometer, SQUID, For Sm2(TixFe1–x)17 (x = 0.02, 0.03, 0.04),
ac-susceptibility measurements magnetization curves and ac
susceptibility vs temperature for samples
with different (Th2Zn17 and Th2Ni17)
structures, Curie temperature,
magnetization curves, anisotropy
constants; increase in TC up to x = 0.04 are
discussed. The type of structure affects
the magnetic properties. For both
structure types, the easy magnetization
direction lies in the basal plane.
Nitrogenation (at 450-500˚C for 4-12 h)
allows one to obtain highly anisotropic
uniaxial ferromagnets.
[2004Zha] Ac-susceptibility / pulsed magnetometer For Sm2(TixFe1–x)17 (x = 0.0, 0.02, 0.04,
0.06, 0.08, 0.1), the Curie temperature,
temperature dependence of ac-
susceptibility is given:
x = 0, TC = 125˚C; x = 0.02, TC = 139˚C; x =
0.04, TC = 174˚C; x = 0.06, τ2, TC = 210˚C; x
= 0.08 and 0.1, τ1, TC = 314˚C.
Hydrogenation at 300˚C and 800˚C, 1 atm
for 1 h and nitrogenation at 500˚C for 3h,
1 atm increase the Curie temperature. iHc,
Br, (BH)max of hydrides and nitrides,
hysteresis loops of nitrides are given.
[2001Che] Theoretical estimation Stabilization of the τ1 compound
[2001Wan] structure by different transition metals
(T = Ti, V, Cr, Co, Sc, Mn); calculated lattice
parameters are given.
[2001Nik] Pendulum and torque magnetometer For τ1, TC = 325˚C, σs = 18.5 μ0/f.u.,
HA = 102 kOe (81.192 kA·m–1).
Transformation of the magnetic structure
of τ1 upon hydrogenation and
nitrogenation is discussed.

Fe–Sm–Ti 30 19
[2002Sko] Extraction magnetometer, a pulsed field Anisotropy constants of τ1 and effect of

facility hydrogenation on the constants are
discussed.
[2006Sun] Vibrating sample magnetometer For Sm2Fe16Ti1, hydrogenation at 800˚C
for 2 h at 0.12 MPa and nitrogenation at
500˚C for different time at 0.13 MPa,
effect of the lattice parameters, coercivity,
magnetization, remanence.

20 30 Fe–Sm–Ti
. Fig. 1
Fe-Sm-Ti. The Sm-Ti binary phase diagram

Fe-Sm-Ti. Reaction scheme
Fe–Sm–Ti 30 21
. Fig. 2

22 30 Fe–Sm–Ti
. Fig. 3
Fe-Sm-Ti. Partial liquidus surface projection

Fe–Sm–Ti 30 23
. Fig. 4
Fe-Sm-Ti. Isothermal section at 1000˚C

24 30 Fe–Sm–Ti
. Fig. 5

Fe–Sm–Ti 30 25
. Fig. 6

26 30 Fe–Sm–Ti
References
[1982Kub] Kubaschewski, O., Iron Binary Phase Diagrams, Springer Verlag, Berlin, Verlag Stahleisen, Düsseldorf,
152–156 (1982) (Phase Diagram, Review, 26)
[1987Had] Hadjipanayis, G.C., Aly, S.H., Cheng, S.-F., “Hard Magnetic Properties of R-Fe-Ti”, Appl. Phys. Lett., 51
(24), 2048–2050 (1987) (Crys. Structure, Magn. Prop., Experimental, 7)
[1987Mur] Murray, J.L., “The Fe-Ti (Iron-Titanium) System”, Phase Diagrams of Binary Titanium Alloys, ASM
Inter., Metal Park, Ohio, Murray, J.L. (Ed.), 99–111 (1987) (Experimental, Phase Diagram, Phase
[1988Oha] Ohashi, K., Tawara, Y., Osugi, R., “Identification of the Intermetallic Compound Consisting of Sm, Ti,
Fe”, J. Less-Comm. Met., 139, L1–L5 (1988) (Crys. Structure, Magn. Prop., Experimental, 2)
[1988Sin] Singleton, E.W., Strzeszewski, J., Hadjipanayis, G.C., “Magnetic and Structural Properties of Melt-Spun
Rare-Earth Transition-Metal Intermetallics with ThMn12 Structure”, J. Appl. Phys., 64(10), 5717–5719
(Crys. Structure, Magn. Prop., Experimental, 9)
[1988Yan] Yang, Y.-C., Kong, L.-S., Cheng, B.-P., “Structural and Magnetic Properties of Sm(Ti,Fe)12 Intermetallic
Compounds”, Acta Phys. Sin., 37(9), 1534–1539 (1988) (Crys. Structure, Magn. Prop., Experimental, 5)
cited from abstract
[1989Had] Hadjipanayis, G.S., “A Search for New Phases and Processing Techniques for Permanent Magnet
Development”, Mater. Sci. Eng. B, B3(4), 431–434 (1989) (Magn. Prop., Experimental, 19) cited from
abstract
[1989Str] Strzeszewski, J., Wang, Y.Z., Singleton, E.W., Hadjipanayis, G.C., “High Coercivity in Sm(FeT)12 Type
Magnets”, IEEE Trans. Magn., 25(5), 3309–3311 (1989) (Crys. Structure, Magn. Prop., Experimental, 10)
cited from abstract
[1989Zha] Zhang, L.Y., Wallace, W.E., “Structural and Magnetic Properties of RTiFe11 and their Hydrides (R = Y,
Sm)”, J. Less-Comm. Met., 149, 371–376 (1989) (Crys. Structure, Magn. Prop., Experimental, 16)
[1990Coc] Cochet-Muchy, D., Paidassi, “Rapidly Quenched Hard Magnetic Alloys with ThMn12 Structure”, J.
Magn. Magn. Mater., 83, 249–250 (1990) (Crys. Structure, Magn. Prop., Experimental, 7)
[1990Din] Ding, J., Rosenberg, M., “Phase Analysis By X-ray and Moessbauer Spectroscopy of Melt-Spun and
Subsequently Annealed Sm-(Fe, Co or Ni)-Ti”, J. Less-Comm. Met., 166, 303–311 (1990) (Crys.
[1990Jan] Jang, T.S., Stadelmaier, H.H., “Phase Equilibria and Magnetic Properties of Iron-Rich Fe-Nd-Ti and Fe-
Sm-Ti Alloys”, J. Appl. Phys., 67(9), 4957–4959 (1990) (Crys. Structure, Phase Relations, Phase Diagram,
Magn., Prop., Experimental, *, 15)
[1990Kat] Katter, M., Wecker, J., Schultz, L., Groessinger, R., “Preparation of Highly Coercive Sm-Fe-Ti by Rapid
Quenching”, Appl. Phys. Lett., 56(14), 1377–1379 (1990) (Crys. Structure, Phase Relations, Magn. Prop.,
Experimental, *, 7)
[1990Sch1] Schultz, L., Schnitzke, K., Wecker, J., “Magnetic Hardering of Sm-Fe-Mo, Sm-Fe-V and Sm-Fe-Ti
Magnets”, J. Magn. Magn. Mater., 83, 254–256 (1990) (Magn. Prop., Experimental, 10)
[1990Sch2] Schnitzke, K., Schultz, L., Wecker, J., Katter, M., “Sm-Fe-Ti Magnets with Room-Temperature
Coercivities above 50 kOe”, Appl. Phys. Lett., 56(6), 587–589 (1990) (Magn. Prop., Experimental, 16)
[1990Wan] Wang, Y., Hadjipanayis, G.C., Kim, A., Liu, N.C., Sellmyer, D.J., “Magnetic and Structural Studies in
Sm-Fe-Ti Magnets”, J. Appl. Phys., 67(9), 4954–4956 (1990) (Crys. Structure, Magn. Prop., Experimen-
tal, 9)
[1990Wec] Wecker, J., Katter, K., Schnitzke, K., Schultz, L., “Magnetic Hardening of Sm-Fe-Ti Alloys”, J. Appl.
Phys., 67(9), 4951–4953 (1990) (Magn., Prop., Experimental, 15)
[1991Cad] Cadieu, F.J., Hegde, H., Navarathna, A., Rani, R., Chen, K., “High-Energy Product ThMn12 Sm-Fe-T
and Sm-Fe Permanent Magnets Synthesized as Oriented Sputtered Films”, Appl. Phys. Lett., 59(7),
[1991Kim] Kim, Y.B., Sugimoto, S., Okada, M., Homma, M., “Phase Relations of the Sm-Fe-Ti System Around the
Compound SmFe11Ti”, J. Alloys Compd., 176(2), 215–224 (1991) (Crys. Structure, Phase Relations,
Phase Diagram, Magn. Prop., Experimental, #, *, 12)
[1991Nei] Neiva, A.C., Messell, F.P., Grieb, B., Henig, E.-Th., Petzow, G., “Phase Equilibria Around SmFe11Ti
at 1000˚C”, J. Less-Common Met., 170(2), 293–299 (1991) (Assessment, Crys. Structure, Phase Dia-
gram, #, *, 23)

Fe–Sm–Ti 30 27
[1991Qia] Qian, X.R., Chen, M.X., Chen, L., Jin, H.J., Chen, L.J., Xu, G.Q., “Moessbauer Study of Melt-Spun
Sm20Fe70Ti10 Alloy”, Hyperfine Interactions, 69, 585–588 (1991) (Crys. Structure, Experimental, 6)
[1991Rei] Reinsch, B., (in German), Constitution of the Fe-Sm-Ti System, Diploma, Uni. Stuttgart, 86 pp. (1991)
(Crys. Structure, Experimental, Morphology, Phase Diagram, Phase Relations, 43)
[1991Sta] Stadelmaier, H.H., Schneider, G., Henig, E.-T., Ellner, M., “Magnetic Fe17R5 in the Fe-Nd and Fe(-Ti)-
Sm Systems, and Other Phases in Fe-Nd”, Mater. Lett., 10(7-8), 303–309 (1991) (Crys. Structure,
Experimental, 30) cited from abstract
[1991Wec] Wecker, J., Katter, M., Schultz, L., “High Coercivity in Sm-Fe-Ti Alloys by Rapid Solidification”, Mater.
Sci. Eng. A, A133, 147–150 (1991) (Magn. Prop., Experimental, 17) cited from abstract
[1991Yan] Yang, Y.-C., Zhang, X.-D., Kong, L.S., Pan, Q., Ge, S.-L., “Magnetocrystalline Anisotropy of RTiFe11Nx
Compounds”, Appl. Phys. Lett., 58(18), 2042–2044 (1991) (Crys. Structure, Magn. Prop., Experimen-
tal, 4)
[1992Rei] Reinsch, B., Grieb, B., Henig, E.-T., Petzow, G., “Phase Relations in the System Sm-Fe-Ti and the
Consequences for the Production of Permanent Magnets”, IEEE Trans. Magn., 28(5), 2832–2834 (1992)
(Phase Relations, Phase Diagram, Experimental, *, 13)
[1994Iva] Ivanova, G.V., Makarova, G.M., Sherbakova, E.V., Belozerov, E.V., Ermolenko, A.S., “Structure and
Magnetic Properties of a Novel Ternary Compound Sm(Fe, Ti)8.5”, Phys. Met. Metallogr., 78(2), 162–166
(1994), translated from Fiz. Met. Metalloved., 78(2), 60–65 (1994) (Crys. Structure, Magn. Prop.,
Experimental, *, 5)
[1994Wan] Wang, K.-Y., Wang, Y.-Z., Hu, B.-P., Lai, W.-Y., “Magnetic Properties of Sm-Fe-Ti and its Nitrides with
TbCu7 Structure”, Physica B, 203, 54–58, (1994) (Crys. Structure, Magn. Prop., Experimental, 14)
[1994Yan] Yang, J., Wang, Q., Sun, X.-K., Zeng, G., Chen, M., Liu, W., Zhao, X., Zhao, T., Zhang, Z., “The
Structure and Magnetic Hardening in Mechanically Alloyed Sm-Fe-Ti Systems”, J. Magn. Magn. Mater.,
132, 197–206 (1994) (Crys. Structure, Magn. Prop., Experimental, 14)
[1995Cad] Cadieu, F.J., “Recent Advances in Pseudobinary Iron Based Permanent Magnets”, Int. Mater. Rev., 40(4),
137–148 (1995) (Crys. Structure, Magn. Prop., Review, 52)
[1995Iva] Ivanova, G.V., Makarova, G.M., Sherbakova, E.V., Belozerov, E.V., “The Formation of Z-Phase Sm(Fe,
Ti)8.5”, J. Alloys Compd., 224, 29–32 (1995) (Crys. Structure, Magn. Prop., Experimental, *, 10)
[1995Xia] Xiao, Q.-F., Sun, X.-K., Geng, D.-Y., Liu, W., Zhang, Z.-D., Chuang, Y.-C., “Structure and Magnetic
Properties of Rapidly Quenched Sm-Fe-Ti Alloys”, J. Magn. Magn. Mater., 140–144, 1093–1094 (1995)
[1995Yan1] Yang, C.J., Park, E.B., Choi, S.D., “Magnetic Hardening of Rapidly Solidified SmFe7+xMx (0.8≤x≤1.5,
M = Mo, V, Ti) Compounds”, Mater. Lett., 24, 347–354 (1995) (Crys. Structure, Magn. Prop., Experi-
mental, 15)
[1995Yan2] Yang, F., Nasunjilegal, B., Wang, J., Zhu, J., Qin, W., Tang, N., Zhao, R., Hu, B., Wang, Y., Li, H.,
“Formation and Magnetic Properties of Sm3(Fe, Ti)29Ny Compounds”, J. Phys.: Condens. Matter, 7,
[1996Has] Hasebe, A., Otsuki, E., “Crystal Structure and Magnetic Properties of R2(Fe, M)17+δ”, Mater. Trans., JIM,
37(4), 870–877 (1996) (Crys. Structure, Phase Relations, Experimental, 12)
[1996Kap] Kapusta, C., Figiel, H., Lord, J.S., Tomka, G.J., Riedi, P.C., Buschow, K.H.J., Kou, X.C., Wiesinger, G.,
“NMR Study of SmTM12–xMx (TM = Fe, Co, M = Ti, Mo)”, J. Magn. Magn. Mater., 157/158, 109–110
[1996Kim] Kim, H.T., Kim, Y.B., Kim, C.S., Kim, T.K., Jin, H., “Magnetocrystalline Anisotropy of (Sm0.5Re0.5)
Fe11Ti Compounds (Re = Ce, Pr, Nd, Sm, Gd, and Tb”, J. Magn. Magn. Mater., 152, 387–390 (1996)
[1996Koy] Koyama, K., Fujii, H., Suzuki, S., “Magnetic Properties of Interstitially Modified Compounds Sm3(Fe,
M)29Zx (M = Ti, V, Cr, and Z = H or N)”, J. Magn. Magn. Mater., 161, 118–126 (1996) (Crys. Structure,
Magn. Prop., Experimental, 38)
[1997Liu] Liu, Z, Jin, Z., “Determination of Phase Equilibria in the Sm-Fe-Ti System at 600˚C”, Z. Metallkd., 88
(2), 174–177 (1997) (Phase Relations, Diagram, Crys. Structure, Experimental, Review, #, *, 9)
[1997Yan] Yang, J., Wang, Q., Sun, X., “The Structures and Magnetic Properties of Mechanically Alloyed Sm-Fe-T
(T = Ti, Ti+V, V) Systems”, J. Magn. Magn. Mater., 166, 216–222 (1997) (Crys. Structure, Magn. Prop.,
Experimental, 11)
[1998Isn] Isnard, O., Miraglia, S., Guillot, M., Fruchart, D., “Hydrogen Effects on the Magnetic Properties of
RFe11Ti Compounds”, J. Alloys Compd., 275–277, 637–641 (1998) (Crys. Structure, Magn. Prop.,
Experimental, 15)

28 30 Fe–Sm–Ti
[1998Pao] Paoluzi, A., Pareti, L., “Magnetocrystalline Anisotropy of Fe and Sm Sublattices in Sm2Fe17: Effects of Ti
Substitution for Fe”, J. Magn. Magn. Mater., 189, 89–95 (1998) (Crys. Structure, Magn. Prop., Experi-
mental, 27)
[1998Ter] Tereshina, I.S., Nikitin, S.A., Ivanova, T.I., Skokov, K.P., “Rare-Earth and Transition Metal Sublattice
Contribution to Magnetization and Magnetic Anisotropy of R(TM, Ti)12 Single Crystals”, J. Alloys
Compd., 275–277, 625–628 (1998) (Crys. Structure, Magn. Prop., Experimental, 14)
[1999Hu] Hu, J., Wang, K., Wang, Y., Hu, B., Wang, Z., “Volume Expansion and Curie Temperature Enhancement
in Rare-Iron Based Nitrides with TbCu7 Structure”, J. Alloys Compd., 292, 233–235 (1999) (Crys.
Structure, Magn. Prop., Experimental, 9)
[1999Shi] Shield, J.E., “Phase Formation and Crystallization Behavior of Melt Spun Sm-Fe-Based Alloys”, J. Alloys
Compd., 291, 222–228 (1999) (Crys. Structure, Thermodyn., Experimental, 7)
[2000Iva] Ivanova, G.V., Makarova, G.M., Sherbakova, E.V., Teitel, E.I., “Mechanism of the Y2(Fe, V)17 → EY3(Fe,
V)29 Phase Transformation”, Phys. Met. Metallogr., 89(5), 501–507 (2000), translated from Fiz. Met.
Metalloved., 89(5), 82–87 (2000) (Crys. Structure, Magn. Prop., Phase Relations, Experimental, *, 14)
[2000Pao] Paoluzi, A., Albertini, F., Pareti, L., “Comparison Among the Second-Order Anisotropy Constants of
RE (Pr, Nd, Sm) and Fe Sublattices in the RE2Fe17 Rhombohedral Structure. Effects of Ti Substitution
for Fe”, J. Magn. Magn. Mater., 212, 183–188 (2000) (Calculation, Magn. Prop., Experimental, 12)
[2000Rag] Raghavan, V., “Fe-Sm-Ti (Iron-Samarium-Titanium)”, J. Phase Equilib., 21(5), 464–466 (2000) (Crys.
Structure, Phase Relations, Phase Diagram, Review, #, *, 15)
[2000Shc] Shcherbakova, Ye.V., Ivanova, G.V., Mushnikov, N.V., Gervasieva, I.V., “Magnetic Properties of Sm2(Fe,
Ti)17 Compounds and their Nitrides with Th2Zn17 and Th2Ni17 Structures”, J. Alloys Compd., 308, 15–20
(2000) (Crys. Structure, Magn. Prop., Experimental, 16)
[2001Che] Chen, N.-X., Hao, S.-Q., Wu, Y., Shen, J., “Phase Stability and Site Preference of Sm(Fe,T)12”, J. Magn.
Magn. Mater., 233, 169–180 (2001) (Calculation, Crys. Structure, Magn. Prop., Experimental, 19)
[2001Nik] Nikitin, S.A., Tereshina, I.S., Verbetsky, V.N., Salamova, A.A., “Transformations of Magnetic Phase
Diagram as a Result of Insertion of Hydrogen and Nitrogen Atoms in Crystalline Lattice of RFe11Ti
Compounds”, J. Alloys Compd., 316, 46–50 (2001) (Crys. Structure, Magn. Prop., Experimental, 14)
[2001Wan] Wang, Y., Shen, J., Chen, N.X., Wang, J.L., “Theoretical Investigation on Site Preference of Foreign
Atoms in Rare-Earth Intermetallics”, J. Alloys Compd., 319, 62–73 (2001) (Crys. Structure, Magn. Prop.,
Calculation, Theory, 33)
[2002Sko] Skourski, Y., Tereshina, I., Wirth, S., Drulis, H., Mattern, N., Eckert, D., Nikitin, S., Mueller, K.-H.,
“Magnetocrystalline Anisotropy of SmFe11–xCoxTiHy”, IEEE Trans. Magn., 38(5), 2931–2933 (2002)
[2004Zha] Zhao, X., Zhang, Z., Sun, X.K., Liu, W., Guo, Z., Xiao, Q., Geng, D., “Structural and Magnetic
Properties of Sm2(Fe1–xTix)17 (x = 0-0.1) Alloys Prepared by Hydrogenation Processes and Their
Nitrides”, J. Magn. Magn. Mater., 208, 231–238 (2004) (Crys. Structure, Magn. Prop., Experimental, 17)
[2006Sun] Sun, J.B., Cui, C.-X., Zhang, Y., Wang, R., Li, L., Yang, W., Liu, Y.-L., “Structural and Nitrogenation of
Sm2Fe16Ti1 Alloy Prepared by HDDR Process”, Mater. Chem. Phys., 97, 116–120 (2006) (Crys. Structure,
Magn. Prop., Experimental, 19)
(1990)

Fe–Sn–Zr 31 1
Iron – Tin – Zirconium

Shuhong Liu, Yong Du, Honghui Xu, Baiyun Huang
Introduction
The ternary system Fe-Sn-Zr system was investigated by [1960Tan, 1968Kud, 1990Kor,
2000Nie, 2001Nie, 2006Nie]. Literature data up to 1990 were reviewed by [1992Rag]. The
phase relations in the Zr rich corner up to βZrFe2 and Zr4Sn have been determined by
[1960Tan] using X-ray diffraction (XRD) and metallography in the temperature range be-
tween 700 and 1100˚C. The alloys were prepared from high purity materials by nonconsum-
able electrode arc melting techniques under an inert atmosphere. Heat treatments were carried
out in Vycor bulbs either evacuated or under a partial pressure of argon. A ternary phase θ
with the composition range of Zr-(11.6-13.1) Fe-19.1Sn (in at.%) was found by [1960Tan].
Subsequently, the investigators [1990Kwo2, 1999Zav, 2007Cos] determined its crystal struc-
ture. They verified that θ is a Zr6Al2Co type compound of hexagonal structure, with a very
narrow homogeneity range and a formula of Zr6Sn2Fe. [1968Kud] analyzed the Zr rich region
of the Fe-Sn-Zr system through microstructure studies and measurements of hardness and
microhardness. Nevertheless, [1968Kud] did not report the presence of the θ phase. By means
of XRD, electron microscope and the X-ray phase microanalyzer of the “Cameca” system,
[1990Kor] gave a phase diagram for the ternary system in the concentration region of
Zr-βZrFe2-Zr5Sn3 and the temperature range from 500 to 1600˚C. The investigation by
[1990Kor] confirmed the existence of the ternary compound θ reported by [1960Tan]. As
many as 15 alloys were melted by [1990Kor] from zirconium iodide (erroneously given as
9.6%), high purity tin (99.9 mass%) and Armco iron in an arc furnace under an argon
atmosphere using an inconsumable tungsten electrode, with preliminary melting of Zr as a
getter. Subsequently, a critical review for the Fe-Sn-Zr system was performed by [1992Rag],
who mainly evaluated the works of [1960Tan], [1968Kud], and [1990Kor]. [1992Rag] pre-
sented two ‘tentative’ isothermal sections (700 and 1100˚C) based on the reaction scheme from
[1990Kor], with no details of the Zr rich region. [2000Nie, 2001Nie] analyzed the region of the
phase diagram located near the composition of a master alloy of Zircaloy-4 [1990Ale,
2007Ahm], and found two new ternary compounds (N phase and X phase) in the central
region of the Fe-Sn-Zr Gibbs triangle. [2006Nie] investigated the reported phases and their
equilibrium relationships at 800 and 900˚C in an extended area of the Gibbs triangle, by
different complementary techniques: quantitative analysis with electron-probe microanalysis
(EPMA), qualitative analysis with electron scanning microscopy and X-ray energy dispersive
spectrometry (EDS), XRD and metallographic examination. The starting materials used for
the preparation of the alloys were: Zr (99.9%-600 ppm wt. Fe-200 ppm wt. O), Sn (99.999
mass%) and Fe (99.95 mass%). [2006Nie] confirmed the existence of the formerly reported θ-,
N- and X phases, and suggested that the θ- and X phases have extended single phase regions.
The Zr4Sn and Zr5Sn3 phases show low solubility of Fe, and the Zr2Fe and Zr3Fe phases show

2 31 Fe–Sn–Zr
low solubility of Sn. A very ‘sluggish’ behavior in the nucleation and growth processes of Zr4Sn
was verified. Information on phase relations, structures and thermodynamics is summarized
in Table 1.
Binary Systems
The Fe-Sn phase diagram is accepted from [1996Kum]. The Fe-Zr phase diagram is taken from
[2002Ste], who experimentally redetermined the Fe-Zr phase diagram over the whole compo-
sition range. The Sn-Zr phase diagram in Fig. 1 is accepted from [1990Kwo1], who con-
structed the phase diagram from their own experimental investigations of the Zr5Sn3-Zr5Sn4
region and for the other regions used evaluated diagram of [1983Abr].
Solid Phases
Table 2 summarizes the crystal structure data for all phases in the ternary Fe-Sn-Zr system.
A ternary compound θ was first identified by [1960Tan]. [1990Kwo2, 1999Zav, 2007Cos]
investigated the crystal structure of the θ compound by XRD. [1990Kor, 2006Nie] confirmed
the existence of the θ compound and suggested that the θ phase has an extended homogeneity
region. Another compound with the same structure as the θ phase was reported by [1998Mel]
as Zr6Fe1.5+xSn1.5–x. [2000Nie, 2001Nie] observed two more ternary compounds: N phase and
X phase at 800˚C and 900˚C by scanning electron microscopy observation (SEM), XRD and
EPMA. [2000Nie] found that the composition of the N phase at 800˚C was: 35.5±0.3 Fe - 36.6
±0.6 Sn - 27.9±0.4 Zr (at.%). At 900˚C, the resulting composition of the compound N was
practically the same. The XRD results by [2006Nie] indicated that some of the peaks that
would correspond to the N phase are located in 2θ equal to 42.3˚, 43.3˚, 44.8˚, 45.8˚, 46.4˚,
47.8˚ and 48.7˚. On the other hand, the main peaks that would correspond to the X phase are
in 2θ equal to 36.6˚, 38.6˚, 39.8˚, 40.8˚, 42.4˚, 43.8˚, 44.3˚, 45.3˚, and 47.3˚. [2000Maz] for the
first time has obtained and investigated the crystal structure and magnetic properties of the
RFe6Sn6 compounds by means of microprobe analysis, 57Fe Mössbauer spectroscopy and
neutron diffraction technique. A slight under-stoichiometry in Zr content was found
corresponding to about 20% of empty Zr sites in the lattice.
Quasibinary Systems
According to [1990Kor], a quasibinary eutectic reaction L Ðaffl βZrFe2 + Zr5Sn3 occurred at

about 1525˚C, but no diagram has been given. However, considering the accepted Sn-Zr phase
diagram, this section can not be quasibinary because below the critical temperature of the
miscibility in Zr5Sn3 the tie lines are not lying in the section plane.
Invariant reactions in the region of Zr-βZrFe2-Zr5Sn3 have been reported by [1960Tan,

1968Kud, 1990Kor, 2006Nie]. Their main discrepancy is that the existence of the Zr rich
Fe–Sn–Zr 31 3
compounds Zr2Fe and Zr3Fe was not recognized by [1960Tan, 1968Kud]. In addition, the
results of [1990Kor] show that the θ phase is in equilibrium with Zr4Sn, being in disagreement
with those [1960Tan]. [1990Kor] presented a reaction scheme based on their own experimen-
tal results and those of the earlier investigations. This scheme is shown in Fig. 2 with minor
modifications in the temperatures for some reactions, compared with the experimental data
after [1990Kor]. The transition reactions U3 and U4 and the ternary eutectic reaction E1 were
first proposed by [1960Tan] and confirmed by [1990Kor]. The ternary peritectic reaction P1
was proposed by [1990Kor] for the formation of the ternary compound θ. The remaining
reactions are essentially those deduced by [1990Kor].
Liquidus Surface
No liquidus surface has been reported for this system. According to the reported invariant
reactions with the participation of liquid [1960Tan, 1990Kor], a schematic liquidus projection
in the region of Zr-βZrFe2-Zr5Sn3 was proposed by [1992Rag]. However in this projection the
position of the liquid phase taking part in the P reaction has been shown incorrectly. It was
located inside the triangle formed by three solid phases. This is corrected in Fig. 3 in the
present evaluation to ensure that the θ phase is located inside the triangle L-Zr5Sn3-βZrFe2.
Also the curvature and the band of the monovariant lines have been drawn to eliminate
violations of the Konovalov rule.
Isothermal Sections
[1968Kud] determined the isothermal sections at 1000, 900 and 700˚C. Their results do not
indicate the existence of the ternary compound θ in contradiction to the earlier and later
works. Five isothermal sections in the Zr-Zr5Sn3-ZrFe2 subsystem at 1100, 1000, 900, 800 and
700˚C were constructed by [1957Tan, 1960Tan, 1962Tan]. Using the starting materials of the
purity of 99.95 mass% Fe, 99.997 mass% Sn and 99.98 mass% Zr, [1960Tan] melted about 170
alloys in an arc furnace under a helium or argon atmosphere. The alloys were annealed at the
above-mentioned temperatures for durations varying from 5 min to 500 h and water
quenched. X-ray powder diffraction and metallographic techniques were used to study the
phase equilibria. The isothermal section at 1100˚C by [1960Tan] is redrawn in Fig. 4, where the
range of the θ phase is accepted from [2006Nie] because the annealing time of the samples in
the later was longer and EPMA has been used in the measurements.
The isothermal sections at 900˚C and 800˚C in the region Zr-Sn-βZrFe2 determined by
[2006Nie] are shown in Figs. 5a, 5b and Figs. 6a, 6b, respectively. According to [2006Nie], the
Zr5Sn4 phase was observed in both as-cast and annealed alloys in the part around the phase,
which is in agreement with the accepted Sn-Zr binary data [1990Kwo1]. The compound
ZrFe6Sn6, investigated by [2000Maz], is also shown in both Figs. 5a, 5b and Fig. 6a, 6b, because
it is studied in the samples annealed at 850˚C for 3 weeks. This temperature is obviously very
close to the solidus, compared with the sections at 800, 900˚C and the Fe-Sn binary system.
Therefore, it can be considered as a thermodynamically stable phase in both isothermal
sections.
Based on the reaction scheme of [1990Kor], a tentative isothermal section at 700˚C has
been constructed in the review of [1992Rag] and is reproduced in Fig. 7, but the range of the
4 31 Fe–Sn–Zr
θ phase is shown the same as that at 800˚C (Fig. 6a). The section shows the existence of the
binary compound Zr3Fe and the equilibrium between θ and SnZr4. These assumed equilibria
are different from the experimental section at 700˚C by [1960Tan].

[1960Tan, 1990Kor] presented vertical sections with the constant Zr contents of 90 mass% and
90 at.%, respectively. Compared with the accepted binary systems, neither of the vertical
sections is accepted, since [1960Tan] interpreted their results based on a Fe-Zr phase diagram
with a single intermetallic compound βZrFe2, and [1990Kor] on a Fe-Zr diagram contra-
dicting to the presently accepted diagram from [2002Ste]. Moreover, the phase relationships in
both vertical sections do not agree with the accepted isothermal sections at 800˚C and 900˚C.
The Zr based alloys possess three main characteristics: good mechanical properties, low cross
section of neutron absorption and good resistance to corrosion. They have gained an extended
application in the nuclear industry. They are used mainly as cladding and structure material in
light and heavy water nuclear reactors. One alloy type frequently employed in the nuclear field
is Zircaloy-4 [1990Ale, 2006Nie], with the chemical composition Zr-(1.2-1.7) Sn-(0.18-0.24)
Fe-(0.07-0.13) Cr-(0.14 max.)O (at.%). In the process of manufacturing, Sn is added by means
of a master alloy of Fe-Sn-Zr, with a high content of Sn in its composition (usually a
composition close to 10Fe-70Sn-20Zr (at.%)).
Zr alloys are also used as a candidate material for the experimental fusion device. In order
to establish the experimental fusion device, it becomes necessary to raise the thermal stability
and reduce the erosion of the inner surface of the first wall of the blanket material. Electron
beam (EB) surface melting of Zircaloy-4, containing SiC, can be carried out to improve the
surface melting temperature, thermal stability and erosion resistance [2007Ahm].
Two ternary compounds of the ternary system present particular properties. Zr6FeSn2
reveals a large hydrogen storage capacity so that it can be used as hydrogen storage or getter
material [1999Zav]. HfFe6Ge6 type ZrFe6Sn6 compound induces a local magnetic disorder due
to the slight under-stoichiometry in Zr element [2000Maz, 2001Maz]. Information on the
investigations of materials properties is summarized in Table 3.
. Table 1
Investigations of the Fe-Sn-Zr Phase Relations, Structures and Thermodynamics
[1960Tan] X-ray analysis, metallography the Zr-rich corner up to βZrFe2

and Zr4Sn, 700˚C to 1100˚C
[1968Kud] Microstructure studies and measurements of the Zr-rich region, 1000, 900,
hardness and micro-hardness 700˚C

Fe–Sn–Zr 31 5
[1990Kor] X-ray analysis, electron microscope and X-ray phase the Zr-Zr5Sn3-βZrFe2 region,
microanalyzer of the “Cameca” system 500 to 1600˚C
[1990Kwo1] X-ray analysis, SEM-EDX method Zr4Sn, Zr5Sn3, Zr5Sn3-Zr5Sn4
regions, as cast, 800-1700˚C
[1990Kwo2] X-ray analysis crystal structure of the
Zr6FeSn2 (θ phase)
[1998Mel] X-ray analysis, Korringa-Kohm-Rostoker (KKR) crystal structure of the
method with the coherent potential approximation Zr6Fe1.5+xSn1.5–x
(CPA)
[1999Zav] X-ray analysis, full profile (Rietveld) refinement crystal structure of the
Zr6FeSn2 (θ phase)
[2000Maz] Microprobe analysis, neutron diffraction technique ZrFe6Sn6, 850˚C
and 57Fe Mössbauer measurements
[2000Nie] SEM, XRD, EPMA, EDX 10Fe-70Sn-20Zr (in at.%); 800,
900˚C
[2001Nie] SEM, XRD, EPMA, EDX X phase
[2006Nie] EPMA, EDX, X-ray analysis and metallographic Zr-βZrFe2-Sn region, 800,
studies 900˚C
[2007Cos] X-ray analysis Zr6Sn2Fe (θ phase)
. Table 2

Temperature Space Group/ Lattice
Range [˚C] Prototype Parameters [pm] Comments/References
(αδFe) cI2
Im3m a = 293.15
W
(δFe) a = 286.65 at 1390˚C [Mas2, V-C2]
1538 - 1394
(αFe) at 25˚C [Mas2, V-C2]
< 912
(γFe) cF24 a = 364.67 at 915˚C [Mas2, V-C2]
1394 - 912 Fm3m
Cu

6 31 Fe–Sn–Zr

(βSn) tI4 a = 583.18 25˚C [Mas2]
232 - 13 I41/amd c = 318.18
βSn
(αSn) cF8 a = 648.92 [Mas2]
< 13 Fd3m
C(diamond)
(βZr) cI2 a = 360.90 [Mas2]
1855 - 863 Im3m 100 to 95.8 at.% Zr at 928˚C,
W 96.0 at.% Zr at 775˚C [2002Ste]
100 to 83 at.% Zr at 1592˚C, 100 to 89.2
at.% Zr at 1327˚C [1983Abr]
(αZr) hP2 a = 323.16 25˚C [Mas2]
< 863 P63/mmc c = 514.75 92.7 at.% Zr at 982˚C [1983Abr]
Mg
Fe5Sn3 hP6 a = 422 [V-C2]
895 - 768 P63/mmc c = 523
Ni2In
Fe3Sn2 hR30 a = 534.4 ± 0.5 [V-C2]
807 - 607 R3m c = 1984.5 ± 0.5
Fe3Sn2
FeSn hP6 a = 530.0 ± 0.1 [V-C2]
< 761 P6/mmm c = 444.9 ± 0.1
CoSn
FeSn2 tI12 a = 653.9 ± 0.4 [V-C2]
< 513 I4/mcm c = 532.5 ± 0.4
Al2Cu
ZrSn2 oF24 a = 957.3 25˚C [V-C2]
< 1139 Fddd b = 564.4
TiSi2 c = 992.7
a = 957.7 ± 0.1 25˚C [1990Kwo1]
b = 564.34 ± 0.06
c = 992.87 ± 0.09

Fe–Sn–Zr 31 7

Zr5Sn3+x a solid solution with a gradually changing
1988 - 1500 structure
0<x<1
[V-C2]
Zr5Sn3 hP16 a = 846.1
< 1590 P63/mcm c = 579.5 25˚C [1990Kwo1]
Mn5Si3 a = 845.6 ± 0.7
c = 577.9 ± 0.1 [V-C2]
Zr5Sn4 hP18 a = 875.9
≲ 1142 P63/mcm c = 591.6 25˚C [1990Kwo1]
Ti5Ga4 a = 876.56 ± 0.07
c = 593.7 ± 0.1
Zr4Sn cP8 a = 563.1 [V-C2]
< 1320 Pm3n a = 562.54 ± 0.07 25˚C [1990Kwo1]
Cr3Si
βZrFe2(h1) cF24 a = 702 to 709 27.5 to 34.4 at.% Zr [2002Ste]
< 1673 Fd3m C15 structure
MgCu2 27.4 to 34.4 at.% Zr at 1150˚C,
28.4 to 34.3 at.% Zr at 1000˚C,
28 to 34.6 at.% Zr at 800˚C [2002Ste]
αZrFe2 hP24 26.5 to 27 at.% Zr [2002Ste]
1345 - 1240 P63/mmc C36 structure in the alloy Zr25Fe75 (at.%)
MgNi2 a = 495.34 annealed at 1290˚C for 7.5 h, together
c = 1614.3 with the (αFe) and Zr6Fe23 phases
[2002Ste]
a = 498.8 at 1100˚C [V-C2]
c = 1632
Zr2Fe tI12 66.7 to 67.2 at.% Zr, C16 structure
951 - 780 I4/mcm a = 638 [2002Ste]
CuAl2 c = 560
Zr3Fe oC16 a = 332.1 ± 0.1 74.8 to 75.4 at.% Zr [2002Ste] in the alloy
≤ 851 Cmcm b = 1096.6 ± 0.3 Zr60Fe40 (at.%) annealed at 700˚C for
BRe3 c = 882.5 ± 0.2 1000 h, together with the βZrFe2 phase
and traces of the Zr2Fe phase [2002Ste]
Zr6Fe23 cF116 20.6 to 21.6 at.% Zr; metastable; an
(metastable) Fm3m oxygen-stabilized phase [2002Ste] in the
Th6Mn23 a = 1172 alloy Zr30Fe70 (at.%) annealed at 1000˚C
for 200 h, together with the αZrFe2 phase
[2002Ste]

8 31 Fe–Sn–Zr

* θ, Zr6Sn2Fe hP9 a = 796.75 ± 0.06 [1990Kwo2]
P6m2 c = 348.63 ± 0.05
Zr6Al2Co a = 795.3 ± 0.2 [1999Zav]
c = 350.2 ± 0.3
a = 799.4 [2007Cos]
c = 346.5
a = 799.3 ± 0.3 at x = 0.15 [1998Mel]
Zr6Fe1.5+xSn1.5–x c = 346.7 ± 0.2
*N - - [2000Nie, 2001Nie, 2006Nie]
*X - - [2000Nie, 2001Nie, 2006Nie]
* ZrFe6Sn6 hP13 a = 532.4 ± 0.1 [2000Maz]
P6/mmm c = 887.0 ± 0.2
HfFe6Ge6
. Table 3
Investigations of the Fe-Sn-Zr Materials Properties
[1990Ale] Mass spectrometry Thermodynamic activities of Sn in

Zircaloy-4
[1999Zav] Measurements of the crystal structure and Hydrogenation of Zr6FeSn2
thermal behavior of the hydrides and the
hydrogen storage capacity of Zr6FeSn2
[2001Maz] Susceptibility and magnetization measurements Magnetic properties of the RFe6Sn6
[2007Ahm] Electron beam surface melting technique, SEM, Surface melting temperature,
EDS, microhardness measurements thermal stability and erosion
resistance

Fe–Sn–Zr 31 9
. Fig. 1
Fe-Sn-Zr. The Sn-Zr binary system

10 31 Fe–Sn–Zr
. Fig. 2
Fe-Sn-Zr. Partial reaction scheme for the βZrFe2-Sn-Zr5Sn3 region

Fe–Sn–Zr 31 11
. Fig. 3
Fe-Sn-Zr. Schematic partial liquidus surface projection

12 31 Fe–Sn–Zr
. Fig. 4
Fe-Sn-Zr. Partial isothermal section at 1100˚C

Fe–Sn–Zr 31 13
. Fig. 5a

14 31 Fe–Sn–Zr
. Fig. 5b
Fe-Sn-Zr. Partial isothermal section at 900˚C. Details of the Zr rich region

Fe–Sn–Zr 31 15
. Fig. 6a

16 31 Fe–Sn–Zr
. Fig. 6b
Fe-Sn-Zr. Partial isothermal section at 800˚C. Details of the Zr rich region

Fe–Sn–Zr 31 17
. Fig. 7

18 31 Fe–Sn–Zr
References
[1957Tan] Tanner, L.E; Levinson, D.W., “The System Zr-Fe-Sn”, U.S. At. Energy Comm. Publ., ARF-2068, (1957)
as quoted by [1992Rag]
[1960Tan] Tanner, L.E., Levinson, D.W., “The System Zr-Fe-Sn”, Trans. ASM, 52, 1115–1136 (1960) (Experimen-
tal, Morphology, Phase Diagram, Phase Relations, Thermodyn., 11)
[1962Tan] Tanner, L.E., Levinson, D.W., “Structures in the Zr-Fe-Sn System”, U.S. At. Energy Comm. Publ., T1D-
7625, (1962) as quoted by [1992Rag]
[1968Kud] Kudryatsev, D.L., Tregubov, I.A., “The Zr corner of the Phase Diagram and Properties of Alloys in the
Zr-Fe-Sn System”, Fiz.-Khim. Splavov Tsirkoniya, 133 (1968) as quoted by [1992Rag]
[1983Abr] Abriata, J.P., Bolcich, J.C., Ari, D., “The Sn-Zr(Tin-Zirconium) System”, Bull. Alloy Phase Diagrams,
4(2), 147–154 (1983) (Crys. Structure, Phase Diagram, Review, Thermodyn., 38)
[1990Kor] Korotkova, N.V., “The Zirconium Corner of the Phase Diagram Zr-Sn-Fe”, Russ. Metall., 5, 201–208
(1990), translated from Izv. Akad. Nauk SSSR, Met., 5, 206-213 (1990) (Experimental, Phase Diagram,
Phase Relations, 6)
[1990Kwo1] Kwon, Y.-U., Corbett, J.D., “The Zirconium-Tin System, with Particular Attention to the Zr5Sn3-
Zr5Sn4 Region and Zr4Sn”, Chem. Matter., 2(1), 27–33 (1990) (Experimental, Crys. Structure, Phase
[1990Kwo2] Kwon, Y.-U; Sevov, S.C., Corbett, J.D., “Substituted W5Si3- and Zr6Al2Co Type Phase Formed in the
Zirconium-Antimony and Zirconium-tin Systems with Iron Group Metals”, Chem. Matter., 2(5),
550–556 (1990) (Crys. Structure, Morphology, 75)
[1990Ale] Alexander, C.A., Ogden, J.S., “Thermodynamic Activities in Zircaloy-4 by Mass-Spectrometry”, J. Nucl.
Mater., 175(3), 197–202 (1990) (Experimental, 9)
Alloy Systems (Zr1–xTix)2Fe and (Zr1–xTix)3Fe in the Range 0 ≤ x ≤ 0.2”, Scripta Metall. Mater., 25(6),
abstract
[1992Rag] Raghavan, V., “The Fe-Sn-Zr (Iron-Tin-Zirconium) System” in “Phase Diagrams of Ternary Iron Alloys”,
Indian Inst. Metals, Calcutta, Vol. 6B, 1199–1204 (1992) (Crys. Structure, Phase Diagram, Phase
[1996Kum] Kumar, K.C. Hari, Wollants, P., Delaey, L., “Thermodynamic Evaluation of Fe-Sn Phase Diagram”,
Calphad, 20(2), 139–149 (1996) (Assessment, Phase Relations, Phase Diagram, Thermodyn., 55)
[1998Mel] Melnyk, G.A., Fruchart, D., Romaka, L.P., Stadnyk, Ju.V., Skolozdra, V., Tobola, J., “Crystal Structure of
New M’6M’’1.5+xX1.5–x Compounds (M’= Zr, Hf; M’’= Fe, Co, Ni; X = Sn, Sb) and Electronic Structure
of Zr6Co1.65Sn1.35”, J. Alloys Compd., 267, L1-L3 (1998) (Crys. Structure, Electronic Structure, Experi-
mental, 6)
[1999Zav] Zavaliy, I.Yu., Pecharsky, V.K., Miler, G.J., Akselrud, L.G., “Hydrogenation of Zr6MeX2 Intermetallic
Compounds (Me=Fe, Co, Ni; X=Al, Ga, Sn): Crystallographic and Theoretical Analysis”, J. Alloys
Compd., 283, 106–116 (1999) (Crys. Structure, Experimental, 31)
[2000Maz] Mazet, T., Malaman, B., “Local Chemical and Magnetic Disorder within the HfFe6Ge6 Type RFe6Sn6
Compounds (R = Sc, Tm, Lu and Zr)”, J. Magn. Magn. Mater., 219, 33–40 (2000) (Crys. Structure,
Experimental, Magn. Prop., 18)
[2000Nie] Nieva, N., Arias, D., “A New Ternary Compound in the Zr-Sn-Fe System”, J. Nucl. Mater., 277, 120–122
(2000) (Crys. Structure, Experimental, Phase Relations, 5)
[2001Maz] Mazet, T., Malaman, B., “Macroscopic Magnetic Properties of the HfFe6Ge6 Type RFe6X6 (X = Ge or
Sn) Compounds Involving a Non-Magnetic R Metal”, J. Alloys Compd., 325, 67–72 (2001) (Experimen-
tal, Magn. Prop., 28)
[2001Nie] Nieva, N., Arias D., presented at CALPHAD XXX, York, England (2001)
(2002) (Experimental, Phase Diagram, Phase Relations, 88)
[2006Nie] Nieva, N., Arias, D., “Experimental Partial Phase Diagram of the Zr-Sn-Fe System”, J. Nucl. Mater., 359
(1-2), 29–40 (2006) (Experimental, Morphology, Phase Diagram, Phase Relations, #, 22)

Fe–Sn–Zr 31 19
[2007Ahm] Ahmad, M., Akhter, J.I., Ali, G., Akhtar, M., Choudhry, M.A., “Erratum to (Characterization of
Electron Beam Modified Surface of Zircaloy-4) {J. Alloys Compd., 426 (2006) 176-179}”, J. Alloys
Compd., 428(1-2), 362 (2007) (Experimental, Morphology, 1)
[2007Cos] Costa, B.F.O., Greneche, J.M., Fruchart, D., Alberto, H.V., Skryabina, N.E., Romaka, L.P., Stadnyk, Yu.
V., “Structural Analysis and 57Fe Mössbauer Spectrometry of Zr6FeSn2 and Related Compounds”,
J. Alloys Compd., 438(1-2), 88–91 (2007) (Crys. Structure, Electronic Structure, Experimental, 11)
(1990)

Fe–Ti–V 32 1
Iron – Titanium – Vanadium

Lesley Cornish, Andy Watson
Introduction
The Fe-Ti-V system is important for steels, both Ti and V forming very stable carbides, and
thus suppressing the stability of cementite. Both Ti-carbides and V-carbides are useful in
controlling grain size. Both Ti and V can also form nitrides and carbonitrides, which can pin
grain boundaries, and hence produce steels with a finer grain size. The control of grain size is
vital in production, especially rolling, and knowledge of the effects of additions to steels is vital
for improved quality and productivity. Vanadium is beneficial in promoting fine, mainly
nitride, precipitates which give dispersion strengthening. The Laves phase is also formed,
and depending on morphology, these can be detrimental to mechanical properties. Some
vanadium alloys, such as V-5Fe-3Ti, show potential as structural materials for fision power
plants because of their resistance to swelling after neutron irradiation. Both the TiFe2 Laves
phase and (βTi,V) have been identified as having potential hydrogenation capability, and work
is ongoing to characterize and enhance this. It has been postulated that alloys based on the
Laves phase could have potential as neutron radiation shielding applications.
Although there are experimental data for the system, they are fairly limited, and mostly
confined to the Fe rich compositions, and the purity of Fe in the earlier work was 99 mass%.
The Fe rich corner was studied by [1954Luc] using samples prepared from Armco iron (99%
purity), sponge titanium and high (although unspecified) purity vanadium.
[1993Rag] cites thermodynamic calculation of (γFe)/((γFe)+(αFe)) and ((γFe)+(αFe))/
(αFe) phase boundaries at 950˚C, 1050˚C, 1150˚C and 1250˚C undertaken by [1988Kum]; they
were found to be linear.
The system has been reviewed by [1987Rag1, 1987Rag2, 1993Rag]. The experimental work
is summarized in Table 1.
There are a number of references that seem to be by the same authors although the name of
the primary author has been spelled in different ways. These are [1959Cin, 1960Tsi, 1961Cin,
1961Chi].
Binary Systems
The Fe-Ti binary system is accepted from [Mas2].

The Fe-V system has been assessed by [1991Hua]. Although [2006Oka] reported recent
experimental work by [2005Ust] who used XRD and electron microscopy to investigate the
extent of the sigma phase in the binary Fe-V system, this is not accepted here. The suggestion
was that the sigma phase decomposes below about 650˚C accompanied by phase separation of
the bcc phase. The phase diagram shown by [2005Ust] shows a narrow strip of single-phase
bcc between the sigma phase and the region of phase separation. As pointed out by [2006Oka],
this feature of the phase diagram would seem to be unlikely, the sigma phase most probably

2 32 Fe–Ti–V
decomposing eutectoidally to give Fe rich and V rich bcc phases, as in the Cr-Fe system. As this
aspect of the phase diagram is uncertain, it has been ignored in the present work.
The Ti-V phase diagram as shown in [Mas2], exhibits a stable miscibility gap with a critical
temperature of 850˚C and a monotectoid reaction taking place at 675˚C. Earlier assessments of
this system (e.g. [1981Mur]) do not show this miscibility gap, which is based on experimental
work by [1981Nak]. However, experimental studies by [1989Wei] would seem to suggest that
the miscibility gap is indeed metastable. Later, the system was assessed by [1998Sau] showing
the low temperature equilibria of the system expressed as a simple two-phase (αFe) + (αTi)
region. It is this version of the phase diagram that is accepted here.
Solid Phases
Table 2 shows details of stability ranges and crystallography of the solid phases. [1960Tsi]
reported the possible presence of a ternary phase in the system, but this was subsequently
confirmed as contiguous with the binary λ,TiFe2 phase [1987Pri, 1987Rag1]. [1954Sto] was
the only other work to report on the presence of a ternary phase occurring in the system; at 14
at.% (14 mass%) V; 28 at.% (31 mass%) Fe. Since only commercial purity Ti was used in the
preparation of the samples and no other workers have reported this phase, it is generally
ignored [1987Rag1, 1987Rag2]. [1987Pri] showed that the solubility of V in FeTi is small,
whereas up to 30 at.% V dissolves in λ (TiFe2) at 1200˚C. The Laves phase is of type C14, with
12 atoms per unit cell [1958Ell].
Quasibinary Systems
In a pair of articles, [1959Cin, 1960Tsi] presented quasibinary sections for TiFe-V and TiFe2-V.
A combination of hardness measurement, thermal analysis, XRD and metallography were
used to determine the phase diagrams. [1987Rag1, 1987Rag2] queried the quasibinary nature
of these sections as the melting points of the TiFe and TiFe2 end members are given as
considerably higher than shown in the accepted Fe-Ti binary system [Mas2]. The large
terminal solubilities of V in the compounds would make the three phase equilibria between
the compounds, α(V) and and liquid in each quasibinary system unlikely to occur at a
single temperature. Moreover, the TiFe compound melts incongruently making it impossible
for the TiFe-V section to be quasibinary. For these reasons, these sections have not been
reproduced here.
[1961Chi] reported a solid state reaction, FeTi + (βTi,V) Ð (αTi) + λ. Using the limited
experimental data available, [1987Rag1, 1987Rag2] postulated a reaction scheme using their
own tentative liquidus, and assumed that the solid state transition reaction from [1961Chi]
occurred at a temperature just below 590˚C, Table 3. They also assumed the presence of a
ternary eutectic reaction, but there has been no experimental evidence of this. The reaction
scheme from [1987Rag1] is reproduced in Fig. 1.

Fe–Ti–V 32 3
No experimental study of the liquidus surface has been undertaken, although [1987Rag1,
1987Rag2] drew a tentative liquidus projection using the adjoining binary phase diagrams and
the two vertical sections of [1959Cin, 1960Tsi]. This is shown in Fig. 2 with amendments to the
isotherms in order to maintain consistency with the accepted binary phase diagrams. It is
speculated that there is a ternary eutectic reaction occurring at about 1350˚C, and each of the
monovariant lines exhibits a maximum. Alternatively, a liquidus projection can be predicted
by thermodynamic calculation by combining the thermodynamic descriptions of the three
binary systems [1998Ran, 1991Hua, 1998Sau]. The resulting liquidus (Fig. 3) shows a transi-
tion reaction taking place at 1164˚C. However, it must be stressed that there is no experimental
justification for either of these liquidus surfaces.
Isothermal Sections
[1961Chi] argon-arc melted 99% Fe and V, and sponge Ti (99.67%) to produce alloys at 93
compositions along sections at a number of different Fe:Ti ratios. The starting materials and
their impurities were: vanadium powder (0.9% O and 0.09% N), Armco iron (0.11% Al,
0.34% Si, 0.22% Mn and a trace of C), and TG-O titanium (0.04% Fe, 0.04% Mg, 0.03% Si,
0.03% Cl, 0.05% C, 0.02% N, 0.11% O and 0.006% H). The resulting alloys were annealed at
1000˚C for 48 h or 800˚C for 248 h before quenching into water, and resulted in the
construction of partial isothermal sections for Fe-V-TiFe for 1000 and 800˚C. A partial section
for 25˚C showing a much restricted solubility of (βTi,V) was produced by [1961Cin]. In each
of these works [1961Chi, 1961Cin], two Laves phases were reported; the binary λ,TiFe2 phase
and a distinct ternary phase of roughly equiatomic stoichiometry, denoted as γ in the article;
although their experimental work was concentrated on Ti-rich alloys. However, [1984Ere]
postulated that these two Laves phase fields were contiguous, and [1987Pri] undertook
experiments to verify this. Using iodide titanium, type VNM-1 vanadium and carbonyl
iron, [1987Pri] prepared samples along vertical sections at 33.3 at.% Ti and 50 at.% Ti by
arc-melting under argon using an oxygen getter. The weight losses after melting were less than
1 mass%. Using metallography, XRD and local X-ray spectral and hardness techniques,
investigations of alloys annealed at 1000 and 1200˚C (for between 50-110 h) lying at composi-
tions along the TiFe2-V section indicated that the binary Laves phase can dissolve V up to
between 30 and 33 at% suggesting that the composition of the ternary Laves phase as given by
[1961Chi] coincides with the solubility limit of V in the binary λ,TiFe2 Laves phase. A plot of
lattice parameter against V content along the TiFe2-V section shows a steady increase on
adding the larger atom, and thus V can replace both Ti and Fe atoms, at least to some extent, as
had been demonstrated earlier by [1958Ell]. In this work, it was shown that slightly more than
half the Fe atoms in TiFe2 can be substituted by V. It is interesting to note that the composition
limit of the λ phase with respect to V lies at the edge of the partial section investigated by
[1961Chi], which goes some way to explaining their erroneous conclusion regarding the
presence of a ternary phase. Through XRD studies of as-cast ternary alloys, [1997Miy] also
confirmed that Vegard’s law was obeyed as V atoms were dissolved into the binary λ phase.
Taking this phase extension into account, and extrapolating from the binary data, as well as
assuming a nominal solubility of 1 at.% Ti in the σ phase (FeV), [1987Rag1, 1987Rag2]
extended the partial isothermal sections to cover the whole composition range, and these form
4 32 Fe–Ti–V
the basis of Figs. 4 to 6. Although a diagram produced by [1997Miy] suggested that the range
of the λ phase was actually greater, this is not reflected in Figs. 4 to 6 as no further details were
given.

The (γFe)-loop in the ternary system was studied by [1954Luc] using dilatometry. 23 alloys
with compositions ranging between 0-1.12 mass% Ti and 0.11-1.34 mass% V were heated over
the (γFe) to (αFe) transformation at a heating rate between 2 and 3˚C per minute. In some of
the samples (especially Fe-V), the furnace temperature was held constant, even for several
hours, until no further transformation occurred. Sudden changes in slope of the heating curve
were taken as the beginning and the end of the transformation, indicating the phase boundary
between the α/α+γ/γ phase regions. In the same work, they report on a study of the γ-loop in
the Fe-V system, but they indicate a minimum in the phase boundaries, which have since been
discounted by other researchers. [1987Rag1] noted that previous work on the Fe-Ti system
was found to disagree with the later versions of the phase diagram [Mas2], and so [1954Luc] is
considered to be unreliable. For this reason, the ternary work is not discussed further here.
The FeTi-V vertical section was studied by [1960Tsi]. 22 alloys of mass of 20 g were used
for thermal analysis studies using a contact method to determine incipient melting, i.e. onset
of melting, for determination of the solidus (the liquidus was not determined). Metallography
was used to study samples in the as-cast, annealed (under vacuum, 800˚C for 100 h, 600˚C for
200 h, or 550˚C for 1000 h, then furnace-cooled) and quenched states. Four groups of water
quenched alloys were studied: heat treated at 1200˚C for 6 h, 1000˚C for 48 h, 800˚C for 200 h
or 600˚C for 548 h. Powder XRD with vanadium radiation was used to investigate the phase
assemblages in annealed samples. [1961Chi] determined vertical sections for TiFe-V and
TiFe2-V, which they maintain were quasibinary; this is dealt with above. However, owing to
errors in the melting points of the TiFe and TiFe2 indicated on the sections they have not been
considered here. A vertical section was determined by [1961Chi] for the 84Ti16Fe-V. This is
not shown here as it includes equilibria with a ternary compound, which they denote as γ, that
has since been correctly identified as the limiting composition of the extension of the binary
TiFe2 compound into the ternary system.
Hardness measurements across the TiFe2-V section showed a maximum of above 800HV,
corresponding to the maximum extent of the λ phase [1959Cin], i.e. the maximum V content
of the phase. A study by [1960Tsi] of the hardness across the TiFe-V section showed the
maximum hardness being obtained for their ‘ternary’ γ phase at about 750HV, without any
apparent effect due to the phase composition. However, the consistency between the hardness
measurements of the binary λ phase and the apparent ternary γ phase was explained by
[1984Ere], and confirmed by [1987Pri], in that the two phases are actually contiguous.
In a study involving different steel additions, [2004Li] showed the beneficial affects of both
Ti and V additions in controlling the grain size, and the increased solution temperature of
carbonitrides in the austenite matrix. However, the amount of Ti addition is limited because it

Fe–Ti–V 32 5
forms nitrides in austenite, and this reduces the V and N available for subsequent precipitation
in ferrite; both effects which can lead to a reduction in yield strength.
The swelling behavior after neutron irradiation was investigated using TEM by [1998Fuk].
The alloys were made from high purity components (99.9% V, 99.999% Fe and 99.99% Ti), arc
melted under argon. TEM foils were prepared from rolled sheet (0.25mm), annealed at 1100˚C
for 2 h, and irradiated at 380˚C, 519˚C and 615˚C up to a neutron fluence of 1.6 · 1026 n·m–2.
The void growth rate was found to be linearly dependent on Fe content, but Ti additions
reduced this effect, and increasing the Ti additions caused precipitation of titanium oxide
precipitates.
[1997Miy] studied the effect of phase structure in the selection of Fe-Ti-V alloys for
hydrogenation. Confirming the phases before hydrogenation studies, [1997Miy] prepared
samples by arc melting of “high purity” components under argon, then pulverizing the ingots
to obtain powders with average particle size of less than 100 μm. X-ray diffraction was
undertaken using CuKα radiation with a carbon monochromator.
The TiFe2 Laves phase was identified as having the potential as a hydrogenation material
owing the suitability of its component atoms for the hydrogenation reaction, and it was
thought that this could be increased by the addition of V. However, experimental results from
a number of alloys showed that the initial hydrogenation of Fe-Ti-V alloys was less than for
rare earth metals, which are usually employed commercially. Maximum hydrogen storage
occurred at a composition of TiFeV0.7 at 60˚C. Further work on this topic was undertaken by
[1999Ver], in an experimental study of the reaction of Fe-Ti-V alloys with hydrogen. [1999Ver]
also predicted that the alloys could have potential for neutron radiation shielding materials.
Another potentially useful phase for hydrogen storage is the bcc vanadium phase. Here
(βTi,V), on absorbing hydrogen, becomes VH or V2H and then VH2. While the first phases are
stable, the last phase undergoes hydrogen desorption and absorption processes at around
room temperature, and so shows potential for hydrogen storage. This was the rationale for
[2004Ito] to undertake comparative work on V alloys with various additions, including Fe and
Ti, up to 1 mol. [1995Sin] evaluated the performance of the V0.85-Fe0.05-Ti0.15 alloy manu-
factured by a powder route (from 99.99% pure components) for hydrogen storage, and found
that good hydrogen absorption and desorption occurred at room temperature.
The Laves phase, λ,TiFe2, is antiferromagnetic with a Néel temperature of about 12˚C.
Using magnetization and V-NMR spin-echo spectra, [2003Yam] demonstrated that V addi-
tions cause a change to ferromagnetism at (0.15 < x < 0.4). The predicted magnetic phase
diagram for Ti(Fe1-xVx)2 was derived and regions of paramagnetism, antiferromagnetism and
ferromagnetism were shown. The transformations were deduced to be due to the changes in
lattice parameter and d-electron number density.
Details relating to properties studied and techniques employed are listed in Table 4.
Miscellaneous
Nuclear magnetic resonance (NMR) experiments were undertaken by [1967Mas] on (βTi,V)
in the Ti-V and Fe-V binary systems, using arc melted samples made from V of 99.8% purity
and Ti and V of 99.9% purity. Nuclear spin-lattice relaxation times, T1, were measured,
together with the low temperature specific heats, and it was found that the T1T product
(T = temperature) was strongly dependent on composition. The relaxation behavior was
correlated with the low temperature specific heat.
6 32 Fe–Ti–V
[2002Boz] undertook calculations for a number of phases, including TiFe, to calculate the
site preferences of a number of alloying additions, including V, using the Bozzolo-Ferrante-
Smith (BFS) calculation method, but as yet, there are no experimental data with which to
compare these results.
. Table 1
Investigations of the Fe-Ti-V System Phase Relations, Structures and Thermodynamics

[1954Luc] Dilatometry, chemical analysis Prior annealing at 950˚C to 1000˚C for 1 or

2 h; experiments at 970 - 1120˚C; 0-
1.12 mass% Ti and 0.11-1.34 mass% V;
(γFe)-loop
[1959Cin] Metallography, thermal analysis, hardness 20 - 1700˚C; across TiFe2-V section
[1960Tsi] Metallography, XRD, thermal analysis, 20 - 1900˚C; across TiFe-V section
hardness
[1961Chi] Metallography, XRD, differential thermal 800˚C and 1000˚C; partial diagram from Ti
analysis using a Kurnakov pyrometer, up to TiFe
manufacture via a TiFe master alloy
[1961Cin] Metallography, XRD Ambient T; partial diagram from Ti up to
TiFe
[1967Mas] Heat pulse method for heat capacities 5-20 K; up to 84 at.% Ti in V, and up to
30 at.% Fe in V; (βTi,V)
[1987Pri] Metallography, XRD, local X-ray 1000 and 1200˚C; 33.3 and 50 at.% Ti
spectroscopy and hardness isoconcentrate lines; λ phase
[1995Sin] XRD 700-900˚C; V0.85-Fe0.05-Ti0.15
[1997Miy] XRD Unspecified; wide range of alloys;
homogeneity range of λ

Fe–Ti–V 32 7
. Table 2
Pearson
Symbol/
α, (δαFe,βTi,V) cI2
(δFe) Im3m a = 293.15 pure Fe at 1390˚C [V-C2, Mas2]
1538 - 1394 W
(αFe) a = 286.65 pure Fe at 25˚C.
< 912 Dissolves 10 at.% Ti at 1289˚C [Mas2]
(βTi) a = 330.65
1670 - 882 pure Ti at 900˚C [Mas].
Dissolves 22 at.% Fe at 1085˚C [Mas2].
(V) a = 302.40
< 1910 [Mas2]
(γFe) cF4 a = 364.67 at 915˚C [V-C2, Mas2].
1394 - 912 Fm3m Dissolves 1.4 at.% V at 1160˚C [1991Hua].
Cu Dissolves 1.3 at.% V at 1150˚C [1998Ran].
(αTi) hP2 a = 295.06 dissolves 2.7 at.% V at 675˚C [Mas2].
P63/mmc c = 468.35 dissolves 1.6 at.% V at 612˚C.
Mg [1998Sau]
λ, Ti(Fe1–xVx)2 hP12 a = 488.0 at x = 0.5, [1960Tsi]. Dissolves 30 at.%
P63/mmc c = 796.0 V at 1200˚C [1987Pri].
MgZn2
TiFe2 a = 479.0 at x = 0
< 1427 c = 781.1 [V-C2] [Mas2]
TiFe cP2 a = 297.6 [V-C2]
< 1317 Pm3m
CsCl
σ, FeV tP30 a = 886.5 to 901.5 [1987Rag1, 1987Rag2]
P42/mnm c = 460.5 to 464.2
σCrFe
a = 896.5 at V0.5Fe0.5 [V-C2].
c = 463.3 29.6 - 60.1 at.% V [Mas2].

8 32 Fe–Ti–V
Pearson
Symbol/
Metastable / high pressure phases

P63/mmc c = 396.0
Mg
Martensite tI4 - [Mas2]
I4/mmm
α’ cP2 - -
Pm3m
CsCl
. Table 3
Composition (at.%)
Reaction T [˚C] Type Phase Fe Ti V
L Ð FeTi + λ + α 1350 E1 L 36 38 28

FeTi + (βTi,Fe) Ð (αTi) + λ > 590 U1 - - - -
. Table 4
Investigations of the Fe-Ti-V Materials Properties
[1959Cin] Hardness Hardness

[1960Tsi] Hardness Hardness
[1967Mas] NMR Nuclear spin-lattice relaxation times, specific heat
measurements
[1987Pri] Hardness Hardness
[1995Sin] XRD, hydrogen adsorption and Hydrogenation characteristics
desorption
[1997Miy] Hydrogen dissociation pressure Hydrogenation characteristics
[1998Fuk] TEM Swelling behavior on neutron irradiation
[1999Ver] Hydrogen absorption Hydrogenation characteristics

Fe–Ti–V 32 9
[2003Yam] Torsion magnetic balance and Magnetic phase diagram of Ti(Fe1–xVx)2, Néel
NMR studies temperature
[2004Ito] Hydrogen absorption Hydrogenation characteristics
[2004Li] TEM and tensile and charpy tests Mechanical properties in relation to
microstructure

10 32 Fe–Ti–V
. Fig. 1
Fe-Ti-V: Tentative reaction scheme

Fe–Ti–V 32 11
. Fig. 2
Fe-Ti-V. Tentative liquidus surface projection

12 32 Fe–Ti–V
. Fig. 3
Fe-Ti-V. Calculated liquidus surface projection

Fe–Ti–V 32 13
. Fig. 4
Fe-Ti-V. Isothermal section at 25˚C

14 32 Fe–Ti–V
. Fig. 5

Fe–Ti–V 32 15
. Fig. 6

16 32 Fe–Ti–V
References
[1954Luc] Lucas, W.R., Fishel, W.P., “γ Loop Studies in the Iron-Vanadium and the Iron-Vanadium-Titanium
Systems”, Trans. ASM, 46, 277–291 (1954) (Phase Relations, Experimental, 9)
[1954Sto] Stone, L., Margolin, H., “The Ti-V-Fe and Ti-Al-Fe Systems”, U.S. At. Energy Comm. Pub. AD-43730,
1–72 (1954), Nucl. Sci. Abst., No. 172, 10, 23–24 (1956) as quoted by [1987Rag1, 1987Rag2]
[1958Ell] Elliott, R.P., Rostoker, W., “The Occurrence of Laves-Type Phases Among Transition Elements”, Trans.
ASM, 50, 617–633 (1958) (Phase Relations, Calculation, Review, 27)
[1959Cin] Cin-Hua, B., Kornilov, I.I., “Phase Diagram of the TiFe2-V System”, Izv. Akad. Nauk SSSR, Otdel. Tekh.
Nauk, Met. i Toplivo, 6, 110–112 (1959) (in Russian) (Phase Diagram, Phase Relations, Experimental,
Mechan. Prop., Morphology, 6)
[1960Tsi] Tsin-Kua, Bi, Kornilov, I.I., “The Phase Diagram of the TiFe-V System”, Russ. J. Inorg. Chem., 5(4),
434–436 (1960) (Phase Diagram, Phase Relations, Experimental, 5)
[1961Chi] Ch’ing-hua, Pi, Kornilov, I.I., “Equilibrium Diagram of the Ti-V-TiFe Ternary System”, Russ. J. Inorg.
Chem., 6(6), 694–696 (1961) translated from Zh. Neorg. Khim., 6(6), 1351–1354 (1961) (Phase Diagram,
Phase Relations, Experimental, 5)
[1961Cin] Cin-Hua, P., Kornilov, I.I., “Phase Diagram of the Ti-V-Fe System”, Trudy. Inst. Metall. A.A. Baikova,
Akad. Nauk SSSR, 8, 54–57 (1961) (in Russian) (Phase Diagram, Phase Relations, Experimental, 12)
[1967Mas] Masuda, Y., Nishioka, M., Watanabe, N., “Nuclear Magnetic Resonance and Specific Heat
Measurements of Transition Metals and Alloys - Ti-V-Fe and Zr-Nb-Mo Systems”, J. Phys. Soc. Jpn.,
22(1), 238– (1967) (Experimental, Magn. Prop., Thermodyn., 33)
[1981Mur] Murray, J.L., “The Ti-V (Titanium-Vanadium) System”, Bull. Alloy Phase Diagrams, 2(1), 48–55 (1981)
(Crys. Structure, Phase Diagram, Phase Relations, Review, Thermodyn., 80)
[1981Nak] Nakano, O., Sasano, H., Suzuki, T., Kimura, H., (in Japanese), Nippon Kinzoku Gakkaishi, 45, 653–660
(1981) (Phase Diagram, Phase Relations) as quoted in [Mas2]
[1984Ere] Eremenko, V.N., Tretiyachenko, L.A., “Ternary Systems with Titanium and Transitions Metals of IV-VIII
Groups of the Periodic Table” (in Russian), Diag. Sost. Mat., Eremenko, V.N. (Ed.), Naukova Dumka,
Kiev, 3–20 (1984) (Experimental, Phase Diagram, Phase Relations, Review, 63)
[1987Pri] Prima, S.B., Tretiyachencko, L.A., “Area of Homogeniety of Laves Phase in the Ti-V-Fe Ternary System”,
Powder Metall. Met. Ceram., 5, 414–415 (1987), translated from Poroshk. Metall., 5(293), 76–77 (1987)
(Phase Relations, Phase Diagram, Experimental, Thermodyn., 3)
[1987Rag1] Raghavan, V., “The Fe-Ti-V (Iron-Titanium-Vanadium) System” in “Equilibria in Iron Ternary Alloys”,
Institute of Metals, London, 73–84 (1988) (Review, Phase Relations, Phase Diagram, #, 10)
[1987Rag2] Raghavan, V., “Section I. The Fe-Ti-V (Iron-Titanium-Vanadium) System” in “Phase Diagrams of
Ternary Iron Alloys”, Ind. Inst. Techn. Delhi, 1, 73–84 (1987) (Crys. Structure, Phase Diagram, Phase
[1988Kum] Kumar, K.C. Hari, Raghavan, V., “Fcc-Bcc Equilibrium in Ternary Iron Alloys”, J. Phase Diagrams, 4(1),
53–71 (1988) (Review, Phase Relations, Calculation) as quoted by [1993Rag]
[1989Wei] Wei, F., Flower, H.M., “Phase Separation Reactions in Ti-50V Alloys”, Mater. Sci. Technol., 5(12),
1172–1177 (1989) (Phase Relations, Experimental, 15)
[1991Hua] Huang, W., “A Thermodynamic Evaluation of the Fe-V-C System”, Z. Metallkd., 82(5), 391–401 (1991)
[1993Rag] Raghavan, V., “Fe-Ti-V (Iron-Titanium-Vanadium)”, J. Phase Equilib., 14(5), 632–633 (1993) (Phase
[1995Sin] Singh, Ar.K., Singh, Aj.K., Srivastava, O.N., “On the Synthesis, Characterisation and Hydrogenation
Behaviour of V-Ti-Fe Alloy”, Int. J. Hydrogen Energy, 20(8), 647–651 (1995) (Experimental, Phys.
Prop., 3)
[1997Miy] Miyamura, H., Sakai, T., Kuriyama, N., Tanaka, H., Uehara, I., Ishikawa, H., “Hydrogenation and Phase
Structure of Ti-Fe-V Alloys”, J. Alloys Compd., 253–254, 232–234 (1997) (Experimental, Phys. Prop., 6)
[1998Fuk] Fukumoto, K., Kimura, A., Matsui, H., “Swelling Behavior of V-Fe Binary and V-Fe-Ti Ternary Alloys”,
J. Nucl. Mater., 258–263(2), 1431–1436 (1998) (Crys. Structure, Experimental, Morphology, Phase
Relations, 8)
[1998Ran] Rand, M.H., “System Fe-Ti” in “Thermochemical Database for Light Metal Alloys”, Ansara, H., Dinsdale,
A.T., Rand, M.H., (Eds.), Vol. 2, European Commission, Brussels and Luxembourg, 205–207 (1998)

Fe–Ti–V 32 17
[1998Sau] Saunders, N., “System Ti-V” in “Thermochemical Database for Light Metal Alloys”, Ansara, H., Dinsdale,
A.T., Rand, M.H., (Eds.), Vol. 2, European Commission, Brussels and Luxembourg, 297–298 (1998)
[1999Ver] Verbetsky, V.N., Mitrokhin, S.V., Movlaev, E.A., “Synthesis and Properties of Multicomponent
Hydrides with High Density”, J. Alloys Compd., 293–295, 421–425 (1999) (Experimental, Phys. Prop., 8)
Intermetallics, 10, 149–159 (2002) (Calculation, Crys. Structure, Theory, 27)
[2003Yam] Yamada, Y., Masuda, M., Ishitani, S., Nakamura, T., “Magnetic Properties of C14 Laves Phase Ti
(Fe1–xVx)2 and Ti(Fe1–xCrx)2 with x < 0.5”, J. Magn. Mag. Mater., 265, 321–330 (2003) (Experimental,
Phys. Prop., 9)
[2004Ito] Ito, S., Yamashita, D., Komiya, K., Yukawa, H., Morinaga, M., “Compositional Dependence of Phase
Stability of γ Phase Formed in Vanadium Alloys”, J. Alloys Compd., 364(1–2), 137–140 (2004) (Crys.
Structure, Experimental, Interface Phenomena, Kinetics, Phase Diagram, Phase Relations, 7)
[2004Li] Li, Z., Wilson, J.A., Crowther, D.N., Mitchell, P.S., Craven, A.J., Baker, T.N., “The Effects of Vanadium,
Niobium, Titanium and Zirconium on the Microstructure and Mechanical Properties of Thin Slab Cast
Steels”, ISIJ Int., 44(6), 1093–1102 (2004) (Crys. Structure, Experimental, Morphology, 35)
[2005Ust] Ustinovshikov, Y., Pushkarev, B., Sapegina, I., “Phase Transformations in Alloys of the Fe-V System”,
J. Alloys Compd., 398, 133–138 (2005) (Crys. Structure, Phase Diagram, Phase Relations, Experi-
mental, 9)
[2006Oka] Okamoto, H., “Fe-V (Iron-Vanadium)”, J. Phase Equilib. Diff., 27(5), 542 (2006) (Review, Phase
(1990)

Fe–Ti–Y 33 1
Iron – Titanium – Yttrium

Natalia Kol’chugina
Introduction
In searching for new materials for permanent magnets, the Fe-Ti-RE systems, and, in particu-
lar, Fe rich rare-earth intermetallic compounds R(Ti,Fe)12 and R3(Ti,Fe)29 are of interest.
Thus, the studies of the systems are focused to the compounds. They are promising materials
for powerful (and relatively cheap because of the low rare-earth content) permanent magnets
and, therefore they have been extensively studied in the last two decades. The aforementioned
compounds have specific features of crystal and magnetic structures and are convenient
subject for the investigation of fundamental problems in the physics of magnetic phenomena.
RTiFe11 (τ1 phase with R = Y) series is of interest as candidates for high-temperature
permanent magnets owing to the high Curie temperatures, saturation magnetization and
magnetocrystalline anisotropy. Recently, the study on R3(Ti,Fe)29 (τ2 phase with R = Y)
intermetallics attract more attention due to the discovery of favorable magnetic properties
of Sm3(Ti,Fe)29Nx. This new family of intermetallic compounds has attracted a special
attention because the introduction of the interstitial atoms H, N and C led to remarkable
improvements in their magnetic properties.
The compounds with Y are of practical importance from the fundamental point of view
since Y being non-magnetic, allows the properties of Fe sublattice to be directly isolated.
A number of studies was performed for single-crystal samples to assess properties, namely, the
anisotropy of iron sublattice. Thus, most works done on the Fe-Ti-Y system concern structural
properties of the alloys motivated by research in magnetic properties.
There are only two articles on the phase equilibria in the Fe-Ti-Y system in which the
isothermal sections at 500˚C [1994Lin] and 600˚C [1997Liu] were constructed. These works
have been reviewed by [2000Rag, 2001Rag].
In a number of works, hydrogenation and nitrogenation (with the formation of hydrides
and nitrides, respectively) techniques are used as procedures that allow the magnetic proper-
ties of Fe-Ti-Y alloys and compounds to be changed and improved.
Investigations of the Fe-Ti-Y phase relations, structure identifications are given in Table 1.
Binary Systems
The binary Fe-Ti, Fe-Y and Ti-Y systems are accepted from [Mas2]. The lattice parameters
were taken from [1987Mur] for the binary Fe-Ti compounds and from [1992Zha] for the
binary Fe-Y compounds.

2 33 Fe–Ti–Y
Solid Phases
There are two ternary phases established in the system. They are designated in the literature
as 1:12 (τ1) and 3:29 (τ2). The crystallographic data of the Fe-Ti-Y phases are listed in Table 2.
Theτ1 phase exists up to 1200˚C [1994Lin]. It exhibits ferromagnetic ordering at TC =
247˚C and uniaxial magnetic anisotropy.
For the τ2 phase, [1994Li] have reported that it crystallizes in the monoclinic symmetry
with alternate staking of Th2Zn17 (rhombohedral) and ThMn12 (tetragonal) type segments.
Based on TC and magnetization measurements, the authors have supposed that the 3 : 29 type
structure is intermediate between 2 : 17 and 1 : 12 type structures. Based on measurements of
magnetic properties, [1996Tel] supposed that the τ2 phase transforms into the τ1 and Y2Fe7
phases with decreasing temperature. In [1997Liu], the τ2 phase was not found at 600˚C.
According to [2000Kim], the phase is formed at a high temperature, above at least 950˚C.
Thus, the τ2 phase exists within a narrow high-temperature range. The compound is ordered
magnetically at 115˚C.
The existence of another ternary phase (YTi1.1Fe8.6) was found in [1993Rev]. The authors
showed that the phase has a defect CeMn6Ni5 type structure; however, this phase displays a
substantial deviation from the stoichiometric 1 : 11 composition.
The substitution of Ti for Fe in Y2Fe17 (to the formation of the Y2TiFe16 stoichiometry)
and in YFe3 (to the formation of the YTi0.5Fe2.5 stoichiometry) is considered in [2001Ell] and
[2006Sor], respectively. According to [1994Lin], the solubility of Ti in Y2Fe17 is 1.5 at.%.
Isothermal Sections
Isothermal sections of the Fe-Ti-Y system were studied in [1997Liu] (at 600˚C) and [1994Lin]
(at 500˚C). The triangulations at 500 and 600˚C are identical. Figure 1 shows the isothermal
section at 600˚C with some corrections according to the accepted binary systems.

Two compounds τ1 and τ2 are magnetic phases; their properties and properties of alloys with
close compositions are given in Table 3.
Compositions subjected to hydrogenation and nitrogenation also indicated in Table 3
since these procedures may be of importance when forming the magnetic properties of
materials based on these compounds.
Miscellaneous
Pure RFe12 compounds do not exist. The substitution of a T element (T = transition metal) for
Fe stabilizes the ThMn12 structure. The stabilizing effect of Ti doping on the formation of the
1:12 phase is considered in [2005Qia]. Calculations and simulation of the YTiFe11 crystal
structure are performed on the basis of interatomic pair potentials (calculated lattice para-
meters are given in Table 2); for the YTi4Fe8 stoichiometry, local magnetic moments for Fe and
Y atoms in different sites were calculated. The site preference of foreign atoms in τ1 and τ2 is
Fe–Ti–Y 33 3
considered in [2000Gir] and [2001Wan1], respectively. According to a thermodynamic model

suggested in [2000Gir] and calculations [2001Wan1] (performed using the cohesive energy
as a criterion), Ti atoms occupy 8i sites; calculated lattice parameters of τ1 are also given in
Table 3. For Ti in τ2, 4i and 4g sites are preferential [2001Wan1].
Substitution of Co for Fe in τ1 increases its magnetization and TC at the expense of the
anisotropy; the effect of other substations (V, Mo, Ni, Cu) for Fe is considered using a lattice
inversion method and acquiring the effective interatomic potentials [2001Wan1].
Interstitial atoms are introduced into the crystals to modify the magnetic properties. An
increase in the saturation magnetization upon hydrogenation results from the volume expan-
sion. Moreover, the hydrogenation enhances the easy c-axis anisotropy. Hydrogenation
increases the magnetization and Curie temperature of τ1 [2001Ter], [2005Ter].
The insertion of nitrogen (at 500˚C) in τ1 (to 0.5 N atoms per f.u.) does not change the
tetragonal structure, slightly increases the unit cell volume [1991Yan].
Interstitial modification of τ2 by H, N, and C is reported to increase its magnetization and
Curie temperature. The nitrogenation of the phase increases the magnetic properties and
decreases the anisotropy field [2000Kim].
. Table 1
Investigations of the Fe-Ti-Y Phase Relations, Structures and Thermodynamics
[1988Moo] Arc melting of at least 99.9% purity YTixFe12–x with x = 1.2 corresponds to the
components, annealing at 850˚C for 2-3 correct stoichiometry of the ThMn12-type
weeks / XRD / magnetization structure, space group I4/mmm; for
measurements YTi1.2Fe10.8 the lattice parameters were
determined, TC = 247˚C.
[1988Moz] Arc melting, annealing at 950˚C for 72 h / YTiFe11 and YTiFe10 stoichiometries have
XRD, neutron diffraction, magnetic the ThMn12 type structure.
measurements
[1988Obb] Levitation melting 99.9% Y, 99.5 Ti and Fe, For YTiFe10, and YTiFe11 stoichiometries,
annealing at 850˚C for 2 weeks / XRD, TGA the lattice parameters were determined.
[1989Zha] R.f. (radio frequency) induction melting of τ1 (with the YTiFe11 stoichiometry) with
99.95% Y, 99.95% Ti, and 99.99% Fe, the ThMn12 type structure was prepared;
annealing, / X-ray diffraction, the lattice parameters were determined.
thermomagnetic analysis, magnetic
measurements, hydrogenation
[1993Rev] Arc melting of 99.9% purity components, YTi0.5Fe9.5 (1:12 + 2:17), YTi2Fe9 (1:11 +
annealing at 1050˚C for 3 weeks, water TiFe2), YTiFe9 (1:12 + 1:11), YTi1.5Fe8 (1:11),
quenching/XRD, neutron diffraction, YTi1.7 Fe7.5 (1:11 + TiFe2 + YFe3), YTi2Fe7
magnetic measurements, hydrogenation (TiFe2 + Y6Fe23 + YFe3); for YTi1.1Fe8.6, a
defect CeMn6Ni5 type structure, space
group P4/mbm, a = 820.9 pm,
c = 481.4 pm.

4 33 Fe–Ti–Y
[1994Li] Arc melting of ≥99.9% purity τ2 was successfully prepared from the
components, annealing at 960˚C for 3 Y9Ti5Fe86 composition (20% of τ1 impurity
days, water quenching / XRD, SEM, TGA in phase); the lattice parameters were
the presence of magnetic field, determined.
[1994Lin] High-frequency induction melting of Isothermal section at 500˚C. Only one
99.9% Fe, 99.8 Ti, and 99,9% Y, annealing ternary τ1 phase with the ThMn12-type
at 900˚C for 30 days, cooling to 500˚C and structure is observed. Isothermal section
annealing for 5 days, ice-water quenching consists of ten single-phase, eighteen
/ XRD of powders annealed at 500˚C for 5 two-phase, and nine three-phase regions.
days and quenched in liquid nitrogen, The maximum solubility of Ti in-Fe and
DTA to 1200˚C (for samples annealed at Y2Fe17 at this temperature is 3.0 and 1.5
500 and 1050˚C), SEM, EDX at.%, respectively. The lattice parameters
were determined; the phase is stable to
1200˚C.
[1996Has] Arc melting of 99.9% purity components, A nonstoichiometric compound R2(M,
annealing at 600-1150˚C for 2-100 h (for Fe)17+δ (δ = 1.0-4.0) can be formed for
different rare-earth metals) R = Y and M = Ti with a hexagonal
structure, space group P 62m that exists in
the intermediate region between 2:17
and 1:12. The nonstoichiometry of this
compound can be attributed to the
diversity in the atomic orders in the c
planes.
[1996Tel] Induction melting of Y, Ti, and Fe of 99.9% Y3Ti1.6Fe27.4 (single-crystal) powder
purity, annealing at 900˚C for 2 weeks / (20 μm) with the monoclinic R3(Ti,Fe)29
XRD, magnetic measurements type structure, space group P21/c or A2/m
was prepared. The lattice parameters
were determined. The formation of the
+
compound can be understood by τ2

Y2Fe17 + τ1 the transformation.
[1996Val] Arc melting, annealing at 1100-1200˚C for For Y3TiFe29–x stoichiometry with x = 1
3 days, quenching in water / XRD, and 2 (containing a secondary phase), the
thermomagnetic analysis, magnetic lattice parameter were determined.
measurements

Fe–Ti–Y 33 5
[1997Liu] 99.95% ingot Y, 99.9 electrolytic Fe, and YTixFe12–x Isothermal section at 600˚C
99.5 industrial grade Ti / diffusion couple (studied compositions (7.2, 22. 73 at.%)
technique (annealing at 600˚C for 500 h) Y - 79, 76.2, 61.2 at.%) Fe – (1.8, 1.8, 3.8 at.
and equilibrium alloying method (arc %) Y; coexisting phases Fe3Y + Fe23Y6 +
melting) + annealing at 600˚C for 500-700 Fe2Ti YTiFe11 + Y2Fe17 + -Fe; YFe2 + -Y +
h + quenching into liquid nitrogen / TiFe2; Section consists of 11 single-phase,
optical microscopy, EPMA, XRD 20 two-phase, and 10 three-phase
regions. τ1 with the YTi1.2Fe10.8
stoichiometry is stable at 900˚C, does not
decompose down to 600˚C. τ2 is not
observed at 600˚C.
[1997Yan] Fourfold arc melting of 99.9% purity τ2 ternary phase with the Nd3(Ti,Fe)29 type
components, annealing at 960˚C for 3 structure, A2/m space group. Lattice
days, water quenching/magnetic parameters were determined for the
measurements/XRD, magnetic Y3Ti1.4Fe27.6 stoichiometry; ρ = 7.22
measurements g·cm–3. Based on magnetic measurement
data, the decomposition of the phase is
likely to occur at 550-800˚C.
[1998And] Induction melting of 99.8% purity Y and Single-crystal τ1 phase; temperature
99.99% purity Fe and Ti, remelting in dependence of the lattice parameters was
resistance furnace / XRD dilatometer, determined.
metallography, thermomagnetic analysis
[1999Pao] Threefold arc melting, annealing at 950˚C 3 : 29 monoclinic cell is formed by
for 4 d, water quenching/magnetic alternate stacking of the tetragonal 1 : 12
measurements and hexagonal or rhombohedral 2 : 17
units, real composition of the compound
should actually correspond to the
Y3TiFe28 stoichiometry.
[1999Sha] Arc melting, annealing at 960-1075˚C, The τ2 phase with the Y3Ti1.5Fe27.9
quenching in ice water/magnetic stoichiometry was synthesized and the
measurements, Mössbauer spectroscopy lattice parameters were determined.
[2001Ell] Induction melting of > 99% purity Y2TiFe16 has a hexagonal structure of
components, annealing at 1150˚C for 20 d Th2Ni17 type with the lattice parameters
/ XRD, SEM, magnetic measurements a = 848.1 pm and c = 837.40 pm,
V = 521.62·106pm3

6 33 Fe–Ti–Y
[2000Kim] Arc melting, annealing at 950-1150˚C for τ2 (Y3(Ti0.04Fe0.96)29 stoichiometry) has the
72 h, waster quenching / XRD, magnetic Nd3(Ti,Fe)29 type structure (P2I/c space
measurements group); the sample was not single-phase.
[2004Tel] XRD, Mössbauer spectroscopy, magnetic The lattice parameters were determined
measurements / nitrogenation for the Y3Ti1.6Fe27.4N2.6 stoichiometry.
[2006Sor] Arc melting, annealing at 950-1050˚C for For the YTi0.5Fe2.5 stoichiometry, Ti
10 d/ XRD, Mössbauer spectroscopy substitutes for Fe at 6c sites.
. Table 2
Pearson
Symbol/
(ωTi) hP3 a = 462.5 at 25˚C, HP > 1 atm [Mas2]

P6/mmm c = 281.3
ωTi
(βTi) cI2 a = 330.65 [Mas2]
1670 - 882 Im3m
W
(αTi) hP2 a = 295.06 at 25˚C [Mas2]
< 882 P63/mmc c = 468.35
Mg
(αδFe) cI2
Im3m
(δFe) W a = 293.15 at 1390˚C [V-C2, Mas2]
1538 - 1394
(αFe) a = 286.65 at 25˚C [Mas2]
< 912
(γFe) cF4 a = 364.67 at 915˚C [V-C2, Mas2]
1394 - 912 Fm3m
Cu
(βY) cI2 a = 407 [Mas2]
1522 - 1478 Im3m
W
(αY) hP2 a = 364.82 at 25˚C [Mas2]
< 1478 P63/mmc c = 573.18
Mg

Fe–Ti–Y 33 7
Pearson
Symbol/
βY2Fe17 hP38 a = 846.3 [1992Zha]

1400 - ? P63/mmc c = 828.2
Th2Ni17
αY2Fe17 hR57 a = 846.0 [1992Zha]
<? R
3m c = 1241.0
Th2Zn17
Y6Fe23 cF116 a = 1208.4 [1992Zha]
< 1300 Fm3m
Th6Mn23
YFe3 hR a = 513.7 [1992Zha]
< 1400 36 c = 2461.0
R
3m
PuNi3
YFe2 cF24 has a small composition range between
< 1125 ± 25 Fd
3m a = 736.3 65.0 and 68.0 at.% Fe [1992Zha]
MgCu2
TiFe2 hP12 a = 477.7 at 64.6 at.% Fe
< 1427 P63/mmc c = 780.7 at 71.4 at.% Fe
MgZn2 a = 478.1 the homogeneity range 64.5-72.4 at.%
c = 779.5 Fe [1987Mur]
TiFe cP2 a = 297.8 ± 0.2 at 50 at.%
< 1317 Pm3m the homogeneity range 47.5-50.3 at.%
CsCl Fe at 1317˚C [1987Mur]

8 33 Fe–Ti–Y
Pearson
Symbol/
* τ1, Y(Ti,Fe)12 tI26 a = 850.9 YTi1.2Fe10.8

(YTiFe11 I4/mmm c = 475.7 [1988Moo]
stoichiometry) ThMn12
> 1200 a = 850.93 V = 347.37·106pm3
c = 479.74 [1988Moz]
a = 852.2 for YTiFe10
c = 479.6 [1988Obb]
a = 851.8 for YTiFe11
c = 479.7 [1988Obb]
a = 848.6 [1988Yan]
c = 478.4
a = 849.6 V = 345.246·106pm3
c = 478.3 [1989Zha]
a = 850.3 V = 347·106pm3
c = 480 [1991Yan]
a = 851.4 [1994Lin]
c = 479.8
a = 847.97 V = 343.08·106pm3
c = 477.13 [1997Obb]
a = 850.9 V = 346.6·106pm3
c = 478.3 [1998Nik2], [1999Nik], [2001Nik]
[2001Ter]
a = 864.9 calculated for YTiFe11
c = 480.5 [2001Wan1]
a = 849.3 to 851.8 V = 344.8-348.1·106pm3
c = 478.0 to 479.8 for YTixFe12-x with x = 0.85-1.30
[2001Wan2]
a = 853.6 calculated for YTiFe11 [2005Qia]
c = 481.4

Fe–Ti–Y 33 9
Pearson
Symbol/
τ2, Y3(Ti,Fe)29 mP* a = 1060.68 for Y3(TixFe1–x)29 [1994Li]

950 - 1050 P21/c b = 852.24
or c = 969.26
A2/m β = 97.153˚
Nd3(Fe,Ti)29
a = 1059.3 for Y3Ti1.6Fe27.4 [1996Tel]
b = 850.2
c = 966.6
β = 97.153˚
a = 1060 for Y3Ti1Fe28 [1996Val]
b = 851
c = 971
β = 97.2˚
a = 1062 for Y3Ti2Fe27 [1996Val]
b = 850
c = 973
β = 97.1˚
a = 1056 for Y3Ti1.4Fe27.6 [1997Yan]
b = 850
c = 968
β = 96.76˚
a = 1058.0 for Y3Ti1.5Fe27.5 [1999Sha]
b = 850.81
c = 967.61
β = 97.052˚
. Table 3
Investigations of the Fe-Ti-Y Materials Properties
[1988Moo] Faraday method For YTi1.2Fe10.8 stoichiometry, TC = 247˚C.

[1988Moz] Thermomagnetic analysis, singular point YTiFe11: TC = 245˚C, Ha = 37 kOe (29.45
detection kA·m–1); YTiFe10: TC = 238˚C, Ha = 21 kOe
(16.7 kA·m–1); temperature dependence
of magnetic anisotropy field is available.
[1988Obb] Faraday torque, axial extraction YTiFe10: TC = 257˚C, YTiFe11: TC = 262˚C;
magnetometer / hydrogenation Increase in the Curie temperature and Fe
moment upon hydrogenation is
observed.

10 33 Fe–Ti–Y
[1988Yan] Neutron diffraction, electron microscopy, Y(Ti,Fe)12 is ferromagnetic at room

thermomagnetic analysis temperature with TC = 252˚C; K1 =
0.908 ·107 erg·cm–3
[1989Zha] Faraday balance, vibrating-sample Increase in the Curie temperature and
magnetometer anisotropy field for τ1 by hydrogenation:
TC from 247 to 294˚C and anisotropy field
Ha from 45 (35.82 kA·m–1) to 60 kOe
(47.76 kA·m–1) at room temperature and
increase on the saturation magnetization
as well.
[1992Szy] Bridgman technique / XRD, magneto- Single-crystal YTi1.2Fe0.8, TC = 251˚C, Ms
optic polar Kerr effect, Bitter technique = 890 G (0.089 T), domain wall energy
γth = 7.5 erg·cm–2.
[1993Kou] Ac susceptibility measurements, singular τ1, temperature dependence of the
point technique, high-field anisotropy field, Ha = 4.05 T (at 4.2 K) and
magnetization 2.23 T (at room temperature).
[1993Rev] SQUID magnetometer, home-built YTi1.1Fe8.6 is non-magnetic (very low
magnetometer based on Faraday spontaneous magnetization),
method temperature dependence of magnetic
moment (in the presence of 1% of Y6Fe23
impurity is available.
[1994Li] TGA in the presence of magnetic field For τ2, TC = 113˚C; the average Fe
magnetic moment is 1.3 μB.
[1996Cou] XRD, TGA Model for prediction of the easy
magnetization direction in the R3(Fe,M)29
compounds based on the XRD data for
Y3(Ti5.2Fe94.8)29.
[1996Tel] Pulsed-field magnetometry / singular Temperature dependence of ac
point detection, spinning-sample- susceptibility, temperature dependence
magnetic-alignment method of the anisotropy field from 4.2 to
TC = 115˚C; EMD is in the monoclinic
(204) plane has an angle of 60˚ to the
c-axis.
[1996Val] Thermomagnetic analysis, magnetic For Y3TiFe28, TC = 102˚C and
measurements Ms = 51.52 μB/f.u. For Y3Ti2Fe27, TC =
125˚C, Ms = 45.90 μB/f.u.
[1997Obb] Neutron diffraction, Mössbauer Magnetization curves, Ha = 5.7 T at 4.2 K
spectroscopy / magnetization and ac and 4.8 T at room temperature. Changes
magnetic susceptibility measurements, in the magnetic anisotropy upon
hydrogenation hydrogenation are considered.

Fe–Ti–Y 33 11
[1997Yan] Thermomagnetic analysis, vibrating- For Y3Ti1.4Fe27.6, the ordering

sample magnetometer temperature is 127˚C; the saturation
magnetization at 4.2 K and room
temperature is 52.1 and 38.0 μB/f.u.,
respectively. Ha = 5.2 T (at 4.2 K).
Temperature dependence of
magnetization, isotherms of
magnetization and SPD signal were
measured; saturation magnetization was
also calculated.
[1998And] Thermomagnetic analysis For τ1, spontaneous volume
magnetostriction at 5 K is 9.4 ·10–3;
temperature dependences of linear
magnetostriction strain and volume
magnetostriction strain were
determined.
[1998Nik1] XRD / X-ray Laue method/vibrating- Temperature dependences of magnetic
sample magnetometer, torque and anisotropy constants for τ1 are
magnetization measurements considered; EMD is parallel to the
tetragonal c-axis.
[1998Nik2] XRD, Laue X-ray technique / vibrating- For single-crystal τ1, temperature
sample magnetometer, torsion dependences of the magnetic anisotropy
magnetometer, magnetization constants K1 and K2, torque curves,
measurements, hydrogenation magnetization curves, temperature
dependences of saturation
magnetization, are given;
K1 = 0.85 · 107 erg·cm–3 and
K2 = 0.032 · 107 erg·cm–3.
[1999Nik] XRD/ torque and pendulum Temperature dependences of saturation
magnetometer, hydrogenation magnetization and anisotropy constants
K1 and K2, torque curves are given; TC =
265˚C, K1 = 0.85 · 107 erg·cm–3, and σs =
120 emu·g–1.
[1999Pao] Thermomagnetic analysis, singular point For YTixFe12–x with 0.8 ≤ x ≤ 1.2, TC =
technique 245˚C. EMD of Y2TixFe17–x lies in the basal
plane. For Y3(Ti,Fe)29, the {20
1} direction
being the easy magnetization direction
lies in the a-c plane of the monoclinic
structure; temperature dependence of
the second-order anisotropy constant
was measured.

12 33 Fe–Ti–Y
[1999Sha] SQUID magnetometer For Y3Ti1.5Fe27.9, TC = 113˚C;

magnetization curves were measured
and saturation magnetization was
measured and calculated. Ms = 178 (5 K)
and 138 (at room temperature) emu·g–1.
[2000Kim] Ac susceptibility measurements, For Y3(Ti0.04Fe0.96)29, easy-cone type
vibrating-sample magnetometer anisotropy, TC = 130˚C, iron
magnetization is 1.87 μB at 4.2 K; σs =
155 Am2·kg–1, Ms = 52.1 μB/f.u., Ha = 9.0 T.
[2001Ell] Vibrating-sample magnetometer, TC = 127˚C, Ms = 105.7 emu·g–1 for
thermomagnetic analysis by Faraday Y2TiFe16.
balance. A new method of
hydrogenation
[2001Kam] Magnetization measurements under For τ1, the saturation magnetization up to
hydrostatic pressure, SQUID 9 kbar at 5-300 K was measured.
magnetometer
[2001Nik] XRD, Laue X-ray technique/pendulum Single-crystal τ1, Ms = 18.8 (at 4.2 K) and
and torque magnetometer, 16.1 (at room temperature) μB f.u.–1, Ha =
hydrogenation, nitrogenation 4 kOe (3.184 kA·m–1) (at 4.2 K) and 20 kOe
(15.92 kA·m–1) (at room temp.).
[2001Ter] XRD/ Mössbauer spectroscopy, Single-crystal τ1, Ms = 19.3 μB f.u.–1 (at 4.2
magnetization measurements, K); temperature dependence of second-
hydrogenation order magnetic anisotropy constant, field
dependence of magnetization,
temperature dependence of
spontaneous magnetization were
measured.
[2001Wan2] XRD / vibrating-sample magnetometer, For YTixFe12–x with x = 0.85, 1.0, 1.1. 1.2,
extracting-sample magnetometer, 1.3, EMD is along the c-axis; TC is almost
thermomagnetic analysis independent on the Ti content, Ms and
anisotropy field decrease and the
lattice parameter increases with
increasing Ti content.
[2002Wan] XRD / thermomagnetic analysis, τ1 exhibits pronounced positive
vibrating-sample magnetometer, SQUID spontaneous volume magnetostriction
magnetometer/thermal expansion below Curie temperature.
measurements by ‘push-rod’ linear Temperature dependences of the linear
differential transformer method thermal expansion and LTE coefficient
were measured.

Fe–Ti–Y 33 13
[2004Tel] Singular point detection / SQUID Temperature dependences of the

magnetometer, nitrogenation saturation magnetization and magnetic
anisotropy constant were determined for
the Y3Ti1.6Fe27.4 stoichiometry and
Y3Ti1.6Fe27.4N2.6.
[2005Sko] Optical microscopy, thermomagnetic Alloys Y3TiFe28, Y3Ti2Fe27, and Y3Ti3Fe26
analysis, magnetic susceptibility are two-phase; single crystals Y3Ti3Fe33–x
measurements have the tetragonal structure of the
ThMn12 type. Temperature dependences
of the magnetic susceptibility and Curie
temperatures for Y3TixFe29–x and Y3Ti3Fex
were measured.
[2005Ter] X-ray Laue method / torque and For YTiFe11–xCox (0 ≤ x ≤ 3) single crystals,
capacitance magnetometry, magnetization and torque curves,
hydrogenation temperature and compositional
dependences of magnetic anisotropy
constant are given.

14 33 Fe–Ti–Y
. Fig. 1
Fe-Ti-Y. Isothermal section at 600˚C

Fe–Ti–Y 33 15
References
[1987Mur] Murray, J.L., “The Fe-Ti (Iron-Titanium) System” in “Phase Diagram of Binary Titanium Alloys”, ASM
Inter., Metal Park, Ohio, Murray, J.L., (Ed.), 99–111 (1987) (Experimental, Phase Diagram, Phase
Relations, Thermodyn., #, 112)
[1988Moo] De Mooij, D.B., Buschow, H.J., “Some Novel Ternary ThMn12-Type Compounds”, J. Less-Common
Met., 136, 207–215 (1988) (Crys. Structure, Experimental, *, 5)
[1988Moz] Moze, O., Pareti, L., Solzi, M., David, W.I.F., “Neutron Diffraction and Magnetic Anisotropy Study of
Y-Fe-Ti Intermetallic Compounds”, Solid State Commun., 66(5), 465–469 (1988) (Experimental, Crys.
[1988Obb] Obbade, S., Miraglia, S., Fruchart, D., Pre, M., L´Heritier, P., Barlet, A., “Structural and Magnetic
Properties of the ThMn12 Type Iron Alloys: Effects of Hydridation”, Compt. Rend. Acad. Sci. Paris, Ser. 2,
307, 889–895 (1988) (Crys. Structure, Magn. Prop., Experimental, 11)
[1988Yan] Yang, Y., Sun, H., Kong, L., Yang, J., Ding, Y., Zhang, B., Ye, C., Jin, L., Zhou, H., “Neutron Diffraction
Study of Y(Ti,Fe)12”, J. Appl. Phys., 64(10), 5968–5970 (1988) (Experimental, Magn. Prop., 10)
[1989Zha] Zhang, L.Y., Wallace, W.E., “Structural and Magnetic Properties of RTiFe11 and their Hydrides (R = Y,
Sm)”, J. Less Common Met., 149, 371–376 (1989) (Experimental, Crys. Structure, Magn. Prop., 16)
[1991Yan] Yan, Y.-C., Zhang, X.-D., Kong, L.-S., Ran, Q., “Magnetocrystalline Anisotropies of RTiFe11Nx
Compounds”, Appl. Phys. Lett., 58(18), 2042–2044 (1991) (Crys. Structure, Experimental, 4)
[1992Szy] Szymczak, R., Zawadzki, J., Manh, D.H., Slepowronski, M., “Domain-Structure in Y(Fe,T)12 (T = Ti,
Cr, Si) Compounds”, J. Magn. Magn. Mater., 104(1), 321–323 (1992) (Experimental, Magn. Prop., 10)
[1992Zha] Zhang, W., Liu, G., Han, K., “The Fe-Y (Iron-Yttrium) System”, J. Phase Equilib., 13(3), 304–308
(1992) (Phase Diagram, Phase Relations, #, Review, 29)
[1993Kou] Kou, X.C., Zhao, T.S., Groessinger, R., Kirchmayr, H.R., Li, X., de Boer, F.R., “Magnetic Phase-
Transitions, Magnetocrystalline Anisotropy, and Crystal-Field Interactions in the RFe11Ti Series
(where R = Y, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, or Tm)”, Phys. Rev. B, 47(6), 3231–3242 (1993)
(Calculation, Experimental, Magn. Prop., 52)
[1993Rev] Revel, R. Tomey, E. Soubeyroux, J.L. Fruchart, D. Jacobs, T.H. Buschow, K.H.J., “Crystal Structure and
Magnetic Properties of the Ternary Compound YFe8.6Ti1.1 and its Hydride”, J. Alloys Compd., 202(1-2),
[1994Li] Li, H.-S., Courtois, D., Cadogan, J.M., Xu, J.-M., Dou, S.X., “Structural and Magnetic Properties of the
Novel Ternary Compound Y3(Fe,Ti)29”, J. Phys.: Condens. Matter, 6(49), L771–L775 (1994) (Crys.
Structure, Experimental, Magn. Prop., *, 16)
[1994Lin] Lingmin, Z., Junqin, J., Xianji, S., Yinghong, Z., “Phase Equilibria in the Y-Ti-Fe System at 500˚C”, Z.
Metallkd., 85(9), 625–627 (1994) (Experimental, Phase Diagram, *, #, 15)
[1996Cou] Courtois, D., Li, H.-S., Cadogan, J.M., “Determination of the Easy Magnetisation Direction by X-ray
Diffraction Analysis at Room Temperature in the R3(Fe,M)29 Compounds: R=Pr, Nd, Sm, Gd, Tb, Dy
and Y; M=Ti and V”, Solid State Commun., 98(6), 565–570 (1996) (Crys. Structure, Experimental, 12)
[1996Has] Hasebe, A., Otsuki, E., “Crystal Structure and Magnetic Properties of R2(Fe,M)17+δ”, Mater. Trans.,
JIM, 37(4), 870–877 (1996) (Crys. Structure, Experimental, 12)
[1996Tel] Tellez-Blanco, J.C., Kou, X.C., Groessiger, R., “Magnetocrystalline Anisotropy of Y3Fe27.4Ti1.6”, J. Magn.
Magn. Mater., 164(1-2), L1–L6 (1996) (Experimental, Magn. Prop., Phase Relations, 23)
[1996Val] Valeanu, M., Plugaru, N., Galateanu, A., Burzo, E., Laforest, J., “Magnetic Study of R3Fe29–xMx, with
R=Y,Gd and M=V,Ti”, J. Magn. Magn. Mater., 157–158, 383–384 (1996) (Crys. Structure, Experimental,
Magn. Prop., 8)
[1997Liu] Liu, Z., Jin, Z., Xia, C., “873 K Isothermal Section of Phase Diagram for Y-Fe-Ti Ternary System”, Scr.
Mater., 37(8), 1129–1134 (1997) (Experimental, Phase Relations, *, #, 7)
[1997Obb] Obbade, S., Fruchart, D., Bououdina, M., Miraglia, S., Souberyroux, J.L., Isnard, O., “About Hydrogen
Insertion in ThMn12 Type Alloys”, J. Alloys Compd., 253–254, 298–301 (1997) (Crys. Structure, Magn.
[1997Yan] Yang, F.M., Xiu-Feng, Han, de Boer, F.R., Li, H.S., “Analyses of the Magnetic Properties of Y3Fe 29–xTix
and Other Associated Compounds”, J. Phys. Condens. Matter, 9, 1339–1346 (1997) (Crys. Structure,
Experimental, Magn. Prop., Calculation, 24)

16 33 Fe–Ti–Y
[1998And] Andreev, A.V., Zadvorkin, S.M., “Thermal Expansion Anomalies and Spontaneous Magnetostriction
in RFe11Ti Single Crystals”, Philos. Mag. B, 77(1), 147–161 (1998) (Crys. Structure, Magn. Prop.,
Experimental, 28)
[1998Nik1] Nikitin, S.A. Ivanova, T.I., Tereshina, I.S., “Effect of Rare-Earth Sublattice on the Magnetic Anisotropy
of RFe11Ti (R = Y, Sm, Tb) Single Crystals”, Inorg. Mater. (Engl. Trans.), 34(5), 458–461 (1998) (Crys.
Structure, Magn. Prop., Experimental, 12)
[1998Nik2] Nikitin, S.A., Tereshina I.S., Verbetskii, V.N., Salamova, A.A., “Magnetic Anisotropy of YFe11Ti and its
Hydride”, Phys. Solid State, 40(2), 258–262 (1998) (Crys. Structure, Experimental, 20)
[1999Nik] Nikitin, S.A., Tereshina, I.S., Verbetsky, V.N., Salamova, A.A., “Magnetic Anistropy of YFe11Ti Single
Crystal and its Hydride”, Int. J. Hydrogen Energy, 24, 217–219 (1999) (Crys. Structure, Experimental,
Magn. Prop., 10)
[1999Pao] Paoluzi, A., Pareti, L., “Magnetocrystalline Anisotropy in Iron-Rich Rare-Earth Intermetallics.
A Phenomenological Approach for the Comparison of the Overall and Fe Sublattice Anisotropies in
RE(FeTi)(12), RE2(FeTi)(17) and RE3(FeTi)(29) Related Compounds (RE = Y,Sm)”, J. Phys.: Condens.
Matter, 11(29), 5613–5621 (1999) (Calculation, Crys. Structure, Experimental, Magn. Prop., 32)
[1999Sha] Shan, V.R., Markandeyulu, G., Rama Rao, K.V.S., Huang, M.Q., McHenry, M.E., “Study of Structural
and Magnetic Properties and Exchange Interactions in (Y1–xGdx)3Fe27.5Ti1.5 {x = 0,0.2, 0.5, 0.8, 1.0}”,
Solid State Commun., 112, 161–166 (1999) (Crys. Structure, Experimental, Magn. Prop., Calcula-
tion, 17)
[2000Kim] Kim, H.-T., Kim, T.-K., Kim, M.-J., Song, M.-S., Yang, J.-H., Kim, C.-S., Kim, Y.-B., Xiao, Q.-F., Lui,
W., Zhang, Z.-D., “Structural and Intrinsic Magnetic Properties of Y3(Fe0.96Ti0.04)29 and Its Nitride”,
IEEE Trans. Magn., 36, 3339–3341 (2000) (Crys. Structure, Experimental, Magn. Prop., 14)
[2000Gir] Girt, E., Altounian, Z., “Model for Predicting Atomic Substitutions in Intermetallic Compounds”,
J. Appl. Phys., 87(9), 4747–4749 (2000) (Calculation, Crys. Structure, 19)
[2000Rag] Raghavan, V., “Fe-Ti-Y (Iron-Titanium-Yttrium)”, J. Phase Equilib., 21(5), 467 (2000) (Phase Relations,
Review, #, 3)
[2001Ell] Ellouze, M., l’Heritier, Ph., Cheikh-Rouhou, A., Joubert, J.C., “New Method of Insertion of Hydrogen
of Hydrogen in R2Fe16Ti Alloys with R = Y and Nd”, J. Alloys Compd., 322, 211–213 (2001) (Crys.
Structure, Experimental, Magn. Prop., 11)
[2001Kam] Kamarad, J., Garcia-Landa, B., Mikulina, O., Arnold, Z., Ibarra, M.R., Algarabel, P.A., “Pressure Effects
on Magnetic Properties of R(Fe,M)12 Single Crystals (R = Rare Earth, M = Ti, Mo)”, J. Magn. Magn.
Mater., 226(2), 1446–1448 (2001) (Experimental, Magn. Prop., 10)
[2001Nik] Nikitin, S.A. Tereshina, I.S. Verbetsky, V.N. Salamova, A.A., “Transformations of Magnetic Phase
Diagram as a Result of Insertion of Hydrogen and Nitrogen Atoms in Crystalline Lattice of RFe11Ti
Compounds”, J. Alloys Compd., 316, 46–50 (2001) (Crys. Structure, Experimental, Magn. Prop., 14)
[2001Rag] Raghavan, V., “Fe-Ti-Y (Iron-Titanium-Yttrium)”, J. Phase Equilib., 22(5), 577 (2001) (Phase Relations,
Review, *, 3)
[2001Ter] Tereshina, I.S., Gaczynski, P., Rusakov, V.S., Drulis, H., Nikitin, S.A., Suski, W., Tristan, N.V., Palewski,
T., “Magnetic Anisotropy and Moessbauer Effect Studies of YFe11Ti and YFe11TiH”, J. Phys.: Condens.
Matter, 13(35), 8161–8170 (2001) (Crys. Structure, Experimental, Magn. Prop., 20)
[2001Wan1] Wang, Y., Shen, J., Chen, N.X., Wang, J.L., “Theoretical Investigation on Site Preference of
Foreign Atoms in Rare-Earth Intermetallics”, J. Alloys Compd., 319, 62–73 (2001) (Calculation, Crys.
Structure, 33)
[2001Wan2] Wang, W.Q., Wang, J.L., Tang, N., Fuquan, B., Wu, G.H., Yang, F.M., Jim, H.M., “Structural and
Magnetic Properties of RCo12–xTix (R = Yand Sm) amd YFe12–xTix Compounds”, J. Phys. D: Appl. Phys.,
34, 307–312 (2001) (Crys. Structure, Experimental, Magn. Prop., 9)
[2002Wan] Wang, J.L., Marquina, C., Garcia-Landa, B., Ibarra, I., Yang, F.M., Wu, G.H., “Magnetovolume Effect
in ThMn12-Type Fe-Rich R(Fe, Nb)12-Based Compounds”, Physica B, 319(1-4), 73–77 (2002) (Experi-
mental, Magn. Prop., Phys. Prop., 14)
[2004Tel] Tellez-Blanco, J.S., Groessinger, R., Wiesinger, G., Levitschnig, H., Hilscher, G., “Untrinsic Properties
of Y3Fe27.4Ti1.6 and its Interstitial Nitride”, J. Magn. Magn. Mater., 272–276(2), 802–803 (2004)
(Experimental, Magn. Prop., 6)
[2005Qia] Qian, P., Chen, N.-X., Shen, J., “Atomistic Simulation for the Phase Stability, Site Preference and
Thermal Expansion of YFe12–xTx (T = Ti, V, Cr, Mn, Zr, Nb, Mo,W)”, Solid State Commun., 134(11),
771–776 (2005) (Calculation, Crys. Structure, Electronic Structure, Magn. Prop., 42)

Fe–Ti–Y 33 17
[2005Sko] Skokov, K., Grushishev, A., Khokholkov, A., Pastushenkov, Yu., Pankratov, N., Ivanova, T., Nikitin, S.,
“Structural and Magnetic Properties of R3Fe(29–x)Ti(x) Alloys and R3Fe(33–x)Ti3 Single Crystals, R=Y,
Gd, Tb, Dy, Ho, Er”, J. Magn. Magn. Mater., 290–291(1), 647–650 (2005) (Crys. Structure, Experimen-
tal, Magn. Prop., 6)
[2005Ter] Tereshina, E., Telegina, I., Palewski, T., Skokov, K., Tereshina, I., Folcik, L., Drulis, H., “The
Magnetocrystalline Anisotropy in Y(Fe,Co)11TiH Single Crystals”, J. Alloys Compd., 404–406, 208–211
(2005) (Crys. Structure, Experimental, Magn. Prop., 16)
[2006Sor] Sorescu, M., Diamandescu, L., Valeanu, M., “Substitutional Effects in RFe3 Intermetallics (R=Dy, Sm,
Y)”, Intermetallics, 14(3), 332–335 (2006) (Crys. Structure, Experimental, 9)
(1990)

Fe–Ti–Zr 34 1
Iron – Titanium – Zirconium

Tamara Velikanova, Kostyantyn Korniyenko
Introduction
Phase relationships in the Fe-Ti-Zr ternary system are of great interest, in the first instance,
because this system contains two Laves phases with a component of the iron triad (iron,
cobalt, nickel). Metallides of this type are used as components of heat-resistant alloys and
austenitic steels owing to their influence on mechanical properties (hardness, tensile strength,
improved plasticity at high temperatures etc). Studies of (Zr1–xTix)Fe2 ternary alloys are of
great technological importance because their magnetic and structural properties can be
tailored by changing the zirconium and titanium concentration.
Another important aspect is related to applications of alloys based on the intermetallic
compound TiFe with a partial substitution of iron by zirconium with a view to increasing its
potential for use in hydrogen storage and purification applications [1988Nag, 1999Sin,
2000Nis]. The Fe-Ti-Zr system is also interesting as it contains titanium and a 3d transition
metal forming quasicrystals.
However, information about the constitution of the Fe-Ti-Zr system is incomplete.
Experimental studies of the alloy system have dealt with the temperature-composition section
ZrFe2-TiFe2 [1963Pie, 1971Pet, 1973Sve, 1987Bla, 2001Bud, 2003Sur] and an isothermal
section at 900˚C [2007Zho]. It should be noted that the reported data for as-cast alloys
[1963Pie, 1987Bla, 2001Bud, 2003Sur] and phase equilibria at 900˚C [2007Zho] on the one
hand and in the ZrFe2-TiFe2 section after [1971Pet, 1973Sve] on the other, seem to be in
conflict. The effect of titanium on the stabilization of the body-centered cubic (βZr) phase was
considered in [1982Sil].
Publications devoted to the experimental study of phase relations, crystal structures and
thermodynamics are listed in Table 1 together with the techniques used. Alloys based on Zr3Fe
were studied by [1991Ard]. Rapidly quenched alloys containing icosahedral and related phases
were studied by [1995Kim, 1998Kim1, 1998Kim2]. The crystal structures of the phases in Fe-
Zr alloys with titanium additions as well as the Zr0.2Ti1.3Fe0.8 alloy are reported in [1982Sil]
and [1999Sin], respectively. Results of calculations of site occupancy of the added zirconium in
the TiFe-based alloys are reported by [2002Boz]. Experimental studies of thermodynamic
properties are focused on the determination of the mixing enthalpies of liquid Fe-Ti-Zr alloys
[1999Thi]. A review of the literature concerns information on phase equilibria in the Fe-Ti-Zr
system and the crystal structures of the phases [1992Rag].
Binary Systems
The Fe-Zr boundary binary system is accepted from [2002Ste]. The Ti-Zr system is accepted
from [1994Kum] (Fig. 1), which is essentially the same as in [Mas2]. The Fe-Ti boundary
system is accepted from [1987Mur, Mas2].

2 34 Fe–Ti–Zr
Solid Phases
No stable ternary phases have been found in this system. Crystallographic data on the solid
phases of the Fe-Ti-Zr system are listed in Table 2.
High mutual solubilities exist between the TiFe2 (λ1) and ZrFe2 (λ2) Laves phases.
[1963Pie] found that as-cast alloys of compositions along with the ZrFe2-TiFe2 section lay
in the two-phase ZrFe2 + TiFe region in the range of compositions from 60 to 80 mol% of
ZrFe2 (6.7 to 13.3 at.% Ti). The wide TiFe2 and ZrFe2 solubility ranges at high temperatures
are supported by studies of as-cast alloys [1987Bla, 2001Bud, 2003Sur]. A TiFe2 solubility in
ZrFe2 of about 23 mol% (7.7 at.% Ti), close to that found for as-cast alloys, was reported by
[1971Pet] for 900˚C, based on XRD data from alloys annealed for 200 h. These findings have
not been confirmed. A solubility of about 8.1 at.% Zr (corresponding to 25.2 at.% Ti) was
reported by [2007Zho]. They determined an isothermal section for the whole system at 900˚C
using the diffusion-triple technique, employing an annealing time of 1440 h (compared with
200 h as used by [1971Pet]) that was sufficient to allow complete equilibrium being achieved.
Therefore, the data of [2007Zho] for 900˚C are preferable. The solubility of titanium in the
λ2 phase at 900˚C is approximately 11.3 at.%, according to the data of [2007Zho].
Figure 2 presents the concentration dependences of the lattice parameters of the λ1 and λ2
Laves phases in the ZrFe2-TiFe2 quasibinary system derived by [1963Pie] from studies of as-
cast specimens. The a and c parameters for the λ1 phase increase continuously with decreasing
titanium content to 8.3 at.% Ti. The same tendency was reported by [1987Bla]. [2001Bud,
2003Sur] reported the a and c lattice parameters for the λ1 phase present in alloys of
composition (Zr1–xTix)Fe2 with x from 0.2 to 1. The reported values agree well with the
data of [1963Pie, 1987Bla], but both Laves phases (λ1 and λ2) were observed simultaneously in
alloys over a wider composition range as compared with the work of [1963Pie] - from 40 to 80
mol% ZrFe2 (correspond to the range 6.7 to 20 at.% Ti). This could be due to the partial
decomposition of the λ1 phase during cooling of the as cast specimens after arc melting.
The solubilities of titanium in Zr2Fe and of zirconium in the TiFe phase at 900˚C were
reported by [2007Zho] as about 26.9 and 7.2 at.%, respectively.
A phase with the Ti2Ni type crystal structure was found in rapidly quenched Zr15Ti60Fe25
and Zr10Ti65Fe25 alloys by [1995Kim, 1998Kim1, 1998Kim2]. A phase with the same structure
was obtained in a Zr0.2Ti1.3Fe0.8 alloy that had been prepared by induction melting and
subjected to a hydrogenation treatment [1999Sin]. This phase is denoted in Table 2 as the
τ phase. It should be thermodynamically unstable.
The icosahedral, I (ZrTiFe) and 1/1 bcc (labeled as M (ZrTiFe)) approximant phases are
reported by [1995Kim, 1998Kim2]. The icosahedral quasicrystal phase was observed in rapidly
quenched Fe-Ti-Zr ternary alloys with a titanium content between 45 to 70 at.%, zirconium
from 5 to 25 at.% and iron from 20 to 30 at.% [1995Kim, 1998Kim1]. TEM studies indicate
the crystal structure of the I phase to be strongly disordered. The quasilattice constant is given
in Table 2.
Studies of melt spun arc melted Zr15Ti60Fe25 and Zr10Ti65Fe25 alloys revealed three
metastable ternary phases [1998Kim1]. The Zr15Ti60Fe25 alloy contained the τ phase (Ti2Ni
type, fcc with a ≈ 1150 pm) and an ordered bcc TiFe-based solid solution (CsCl type)
as dominant phases along with small amounts of the I phase. At the same time, in the
Zr10Ti65Fe25 alloy, the I phase was dominant while the τ phase was the secondary
phase. Additionally, the M (ZrTiFe) 1/1 approximant (bcc, a = 1330 pm), the face-centred

Fe–Ti–Zr 34 3
orthorhombic (a = 3200 pm, b = 2660, c = 1040 pm) and the λ1 Laves phase (hcp; a = 515,
c = 837 pm) were found in both of these alloys.
The addition of Ti was found to stabilize a (βZr) solid solution containing 4 at.% Fe
[1982Sil]. This effect was observed during investigations of ternary alloys of composition
Zr1–xTixFe0.04 that had been prepared by arc melting followed by homogenizing for 6 days at
1000˚C before quenching into cold water; even with only a 1 at.% titanium addition. Two
phases, namely the β and α2 phases have been identified in all samples containing up to 7 at.%
Ti, while only the β phase was seen in the sample with the Zr0.89Ti0.08Fe0.04 composition and
for those of higher titanium contents. It was postulated that short-range ordering produced by
the formation of Ti-Fe pairs in the lattice inhibits the β → α2 transformation on quenching to
room temperature.
The substitutional site preference of ternary alloying additions to B2 compounds (stable at
room temperature and with stoichiometry 1:1) was determined by [2002Boz] using the
Bozzolo-Ferrante-Smith (BFS) method. This quantum approximate method was applied, in
particular, to the study of zirconium additions to the TiFe based phase. The energy of
formation per atom in the perfectly ordered B2 TiFe 72-atom cell is –0.7149 eV·atom–1. The
energy of formation per atom of a 72-atom cell with one Zr (Ti) substitution is –0.6808
eV·atom–1; slightly higher than that of the ground state. In the case of Fe rich TiFe alloys,
Zr prefers to occupy Fe sites, with the energy of formation of a 72-atom cell being in this
case –0.5341 eV·atom–1.
Quasibinary Systems
The quasibinary temperature-composition section ZrFe2-TiFe2 has been established in the
ternary system [1971Pet]. The section is given in Fig. 3, based on the data of [1963Pie, 1971Pet,
1987Bla, 2007Zho]. The system is of peritectic type with considerable mutual solubility of the
components. Direct experimental evidence of the λ2 phase boundary at the peritectic temper-
ature is absent in the work of [1971Pet] but is presumed to be present and is indicated in the
diagram. Obviously, the value of Zr solubility in TiFe2 reported by [1971Pet], namely 16-17
at.% Zr at 900-1470˚C, cannot be considered as reliable because of uncertainty in the
concentration dependence of the lattice periods of the λ1 phase; only one specimen was
prepared in the single-phase region. Moreover, the alloys were not fully equilibrated owing
to the short annealing time employed; as is now clear taking into account the results of
[2007Zho]. The solubility range of the λ1 phase at 900˚C as given by [1971Pet] is too high in
comparison with the data of [1963Pie] determined for as-cast alloys and with the data of
[1987Bla] obtained from annealed (at 800-1500˚C) and quenched specimens. In Fig. 3, the
phase boundaries λ2/λ2+λ1 and λ2+λ1/λ1 are drawn by taking into account the wide extension
of λ1 and λ2 homogeneity ranges at high temperatures deduced by [1963Pie, 1987Bla] (see the
“Solid Phases” section) and the reduction in their extensions at 900˚C after [2007Zho]. It can
be seen that the solubilities of the λ1 and λ2 phases given by [1971Pet] correspond to
temperatures of about 1300˚C and the solidus temperature, respectively. Thus, the constitu-
tion of the investigated alloys corresponded to the high-temperature state because the anneal-
ing time was not sufficient. Therefore, the low-temperature solubility data of [1971Pet] cannot
be accepted.

4 34 Fe–Ti–Zr
The existence of the three-phase invariant equilibrium L + λ2 Ð λ1 of incongruent type follows

from quasibinarity of the ZrFe2-TiFe2 section [1971Pet]. Temperature of the above equilibri-
um was determined as 1470±10˚C on the basis of differential thermal analysis data. Composi-
tions of the phases taking part in this reaction are shown in Table 2.
Isothermal Sections
A complete isothermal section for 900˚C was constructed by [2007Zho] who used a diffusion-
triple method with EMPA to study the equilibria. The section is presented in Fig. 4. The tie-
lines across two-phase fields are drawn with solid lines while the positions of three-phase fields
are marked by dashed lines based on the tendencies of directional changes of the boundary
binary tie-lines.
Thermodynamics
The mixing enthalpies of liquid Fe-Ti-Zr alloys were calculated by [1996Wan] from enthalpy
data for the three boundary binary systems. The enthalpies of mixing of liquid ternary
Fe-Ti-Zr alloys at 1600˚C were obtained using the Hillert-2 interpolation algorithm
[1980Hil] using suitable interpolation geometry.
Enthalpies of mixing of ternary liquid alloys have been presented by [1999Thi]. Measure-
ments were performed along the ZrFe2-Ti, TiFe2-Zr and Zr37Ti63-Fe sections using a levitation
alloying calorimeter (LAC), as described by [1994Qin]. The experimental data obtained were
in a good agreement with calculations carried out using a regular associate model. Figure 5
shows the mixing enthalpy of liquid Fe-Ti-Zr alloys for 1879˚C in the form of isoenthalpy
curves. The extreme value of the mixing enthalpy, of about –23 kJ·mol–1, is located in the
Fe-Zr binary system at 45 at.% Zr. The excess heat capacities of liquid Fe-Ti-Zr alloys at 1879˚
C presented in [1999Thi], calculated using the regular associate model, are shown in Fig. 6.
The Fe-Ti-Zr and related alloys are of great interest for practical applications in modern
technology owing to their valuable electrical, magnetic, optical and structural properties.
Moreover, TiFe-based alloys with a partial substitution by iron are promising materials for
the storage and purification of hydrogen [1988Nag, 1999Sin, 2000Nis].
The properties of the Fe-Ti-Zr alloys investigated and experimental techniques used are
listed in Table 3.
Magnetic property investigations of alloys in the ZrFe2-TiFe2 section carried out by
[1963Pie] demonstrated that the TiFe2-based phase behaves as a strongly paramagnetic
material with a susceptibility that is practically temperature independent, whereas the
ZrFe2-based phase is ferromagnetic with a Curie temperature of 355˚C. The effective moment
per iron atom, obtained from the observed saturation magnetization at 4 K, is 1.62 μB. The
reduced moment of the iron atoms in both the TiFe2 and ZrFe2 phases as compared to that of
Fe–Ti–Zr 34 5
elemental iron was attributed by the authors to a transfer of charge from Ti or Zr to iron. Later,
the magnetic behavior of ZrFe2-TiFe2 alloys was studied in more detail by [2001Bud] and
[2003Sur]. Both the Zr2Fe and Zr3Fe compounds demonstrated paramagnetic properties at
room temperature [1991Ard].
The hydrogen behavior characteristics of zirconium-substituted TiFe and Zr0.2Ti1.3Fe0.8
alloys were studied by [1988Nag, 2000Nis] and [1999Sin], respectively. In particular, the
structural and microstructural characteristics of the hydrogen storage material Zr0.2Ti1.3Fe0.8
revealed that this alloy is multiphase [1999Sin]. The storage capacity for this material was
found to be about 1.2 mass% at 200˚C and the desorption kinetics were found to be two times
higher than the native material, Ti1.3Fe. The improved activation process and faster kinetics
were thought to arise from the presence of a higher density of interfaces and volume expansion
induced cracking of (βTi) facilitating hydrogen absorption and desorption in the lattice.
It was shown by [1987Bla] that Vickers microhardness values of the λ1 phase in the ZrFe2-
TiFe2 quasibinary system decrease linearly with increasing titanium content, from 13.3 up to
33.3 at.% (Fig. 7).
. Table 1
Investigations of the Fe-Ti-Zr Phase Relations, Structures and Thermodynamics
[1963Pie] Levitation melting, X-ray diffraction (GE XRD-3 Zr1–xTixFe2, 0 < x < 1
diffractometer)
[1971Pet] Arc melting, annealing in evacuated ampoules 900˚C (annealing for 200 h); the
with quenching in cold water, differential ZrFe2-TiFe2 section
thermal analysis, X-ray diffraction, chemical
etching, optical microscopy
[1973Sve] Arc melting, differential thermal analysis, X-ray 900˚C (annealing for 200 h); the
diffraction, optical microscopy, microprobe ZrFe2-TiFe2 section
analysis
[1982Sil] Arc melting, annealing in evacuated ampoules 1000˚C (annealing temperature);
with quenching in cold water, Mössbauer 4 at.% Fe
spectroscopy, X-ray diffraction
[1987Bla] Arc melting, annealing in vacuum, quenching, 1500-800˚C (annealing
slow cooling, X-ray diffraction (Philips temperature); 66.7 at.% Fe, 6.7 to
PW1050diffractometer), optical microscopy 33.3 at.% Fe
[1991Ard] X-ray diffraction 25 and 33 at.% Fe
[1995Kim] Arc melting, high speed crystallization, Rapidly quenched alloys;
transmission electron microscopy (TEM) 20 to 30 at.% Fe, 45 to 70 at.% Ti,
5 to 25 at.% Zr

6 34 Fe–Ti–Zr
[1998Kim1] Arc melting, high speed crystallization, TEM Zr15Ti60Fe25 (at.%)

[1998Kim2] (JEOL 2000FX transmission electron
microscope), energy-dispersive X-ray
spectrometry, X-ray diffraction, Archimedes
weighing technique, neutron powder
diffraction
[1999Sin] Induction melting, X-ray diffraction (PW-1710 Zr0.2Ti1.3Fe0.8
diffractometer), scanning electron microscopy
(SEM)
[1999Thi] Levitation alloying calorimetry The ZrFe2-Ti, TiFe2-Zr and
Zr37Ti63-Fe sections
57
[2001Bud] Fe Mössbauer spectroscopy, X-ray diffraction The ZrFe2-TiFe2 section
[2003Sur] Arc melting, X-ray diffraction, 57Fe Mössbauer The ZrFe2-TiFe2 section (0 to 6.7
spectroscopy, neutron diffraction and 23.3 to 33.3 at.% Ti)
[2007Zho] Diffusional welding, annealing, quenching, 900˚C (annealing for 1440 h); the
EPMA (JX-8800R apparatus) whole range of compositions
. Table 2
Crystallographic Data of Solid Phase
Pearson
Symbol/
β, Zr1–x–yTixFey cI2 y = 0, 0 < x < 1 [1994Kum]

Im3m
W
(βZr) a = 360.90 x = 0, y = 0, T > 863˚C [Mas2, V-C2]
1855 - 863 dissolves 4.2 at.% Fe
at 928˚C [2002Ste]
(βTi) a = 330.65 x = 1, y = 0, T > 882˚C [Mas2, V-C2]
1670 - 882 dissolves 22 at.% Fe at 1085˚C
[1987Mur, Mas2]
α1, ZrxTiyFe1–x–y x = 0, 0 < y < 0.1,
T = 1289˚C [1987Mur, Mas2]
(δFe) y = 0, 0 < x < 0.02, T = 1374˚C [2002Ste]
1538 - 1394
a = 293.15 x = 0, y = 0, T = 1360˚C [V-C2]
(αFe) (ferrite) y = 0, 0 < x ≤ 0.001, T = 800˚C [2002Ste]
< 912 a = 286.64 x = 0, y = 0, T = 20˚C [V-C2]

Fe–Ti–Zr 34 7
Pearson
Symbol/
(γFe), cF4 a = 364.68 x = 0, y = 0, T = 912˚C [V-C2]

ZrxTiyFe1–x–y Fm3m x = 0, 0 < y < 0.006, T ≈ 1100˚C
1394 - 912 Cu [1987Mur, Mas2]
y = 0, 0 < x < 0.007, T = 1305˚C [2002Ste]
α2, Zr1–x–yTixFey hP2 y = 0, 0 < x < 1
< 882 P63/mmc [1994Kum]
Mg
(αZr) a = 323.16 x = 0, y = 0, T = 25˚C [Mas2, V-C2]
< 863 c = 514.75 x = 0, 0 < y < 0.0003,T = 775˚C [Mas2]
(αTi) a = 295.06 x = 1, y = 0, T = 25˚C [Mas2, V-C2]
< 882 c = 468.35 dissolves 0.04 at.% Fe at 595˚C [1987Mur, Mas2]
(ωTi) HP hP3 a = 462.5 pure Ti, HP → 1 atm,
P6/mmm c = 281.3 T = 25˚C [Mas2]
ωTi
TiFe cP2 47.5 to 50.3 at.% Fe [1987Mur, Mas2]
< 1317 Pm3m
CsCl a = 298.6 to 297.6 47 to 50 at.% Fe [V-C2]
dissolves 7.2 at.% Zr at T = 900˚C [2007Zho]
λ1, (Zr1–xTix)Fe2 hP12 0.757 ≲ x < 1, T = 900˚C [2007Zho]
P63/mmc a = 493.5 to 479 0.35 ≤ x ≤ 1, as-cast alloys [1963Pie]
MgZn2 c = 790 to 777
a = 495.7 0.2 ≤ x ≤ 0.3, as-cast [1963Pie]
c = 789
a = 493 x = 0.37 and x = 0.294, in the alloys annealed at
c = 805 900˚C and quenched in cold water [1971Pet]
a = 496.9 to 481.3 0.2 ≤ x ≤ 0.8 [1987Bla]
c = 804.2 to 785.6
a = 492 to 480 0.2 ≤ x ≤ 1, in the as-cast samples [2001Bud]
c = 804 to 784
TiFe2 64.8 to 72.4 at.% Fe in Fe-Ti [1987Mur, Mas2]
< 1427
a = 478.7 at 66.7 at.% Fe [1987Bla]
c = 781.4
a = 479.0 at 66.7 at.% Fe [V-C2]
c = 781.0
a = 479.9 at 60.5 at.% Fe, in the alloy annealed at 900˚C
c = 783.0 and quenched in cold water [1971Pet]
a = 478.4 at 72.7 at.% Fe, in the alloy annealed at 900˚C
c = 780.7 and quenched in cold water
[1971Pet]

8 34 Fe–Ti–Zr
Pearson
Symbol/
λ2, (Zr1–xTix)Fe2 cF4 0 < x ≲ 0.339, T = 900˚C [2007Zho]

Fd3m C15 structure
MgCu2 a = 706 to 699.5 0 ≤ x ≤ 0.2, in the as-cast alloys [1963Pie]
a = 705.4 0.25 ≤ x ≤ 0.37, in the alloys annealed at 900˚C
and quenched in cold water [1971Pet]
a = 702.7 x = 0.2, together with the λ1 phase [1987Bla]
a = 699.2 x = 0.6, together with the λ1 phase [1987Bla]
a = 708 to 704 0 ≤ x ≤ 0.4, in the as-cast samples [2001Bud]
x = 0.1, as-cast sample:
a = 709.9 T = 397˚C
a = 707.7 T = 97˚C
a = 705.4 T = 17˚C [2003Sur]
a = 708.2 T = 397˚C
a = 704.5 T = 127˚C
a = 705.0 T = 17˚C [2003Sur]
a = 704.5 T = 377˚C
a = 704.4 T = 127˚C and 17˚C [2003Sur]
βZrFe2 a = 702 to 709 27.5 to 34.4 at.% Zr in the binary Zr-Fe system
< 1673 [2002Ste]
a = 706.5 at 66.7 at.% Fe [V-C2]
λ3, αZrFe2 hP24 26.5 to 27 at.% Zr [2002Ste]
1345 - 1240 P63/mmc C36 structure
MgNi2 a = 495.34 in the alloy Zr25Fe75 (at.%) annealed at 1290˚C
c = 1614.3 for 7.5 h, together with (αFe) and Zr6Fe23 phase
[2002Ste]
a = 498.8 at 1100˚C [V-C2]
c = 1632
Zr2Fe tI12 66.7 to 67.2 at.% Zr [2002Ste]
951 - 780 I4/mcm C16 structure
CuAl2 a = 641 in the alloy Zr69Fe31 [1991Ard]
c = 556
without visible solubility of titanium [1991Ard]
a = 637.9 in the alloy Zr40Fe60 (at.%) annealed at 800˚C for
c = 559.4 500 h, together with the βZrFe2 and Zr3Fe phases
[2002Ste]
dissolves 26.9 at.% Ti at T = 900˚C [2007Zho]

Fe–Ti–Zr 34 9
Pearson
Symbol/
Zr3Fe oC16 74.8 to 75.4 at.% Zr [2002Ste]

< 851 Cmcm without visible solubility of titanium [1991Ard]
Re3B
a = 332.16 in the alloy Zr60Fe40 (at.%) annealed at 700˚C for
b = 1096.4 1000 h, together with the βZrFe2 phase and
c = 882.3 traces of the Zr2Fe phase [2002Ste]
a = 333 at 75 at.% Zr [1991Ard]
b = 1095
c = 882
Zr6Fe23 cF116 20.6 to 21.6 at.% Zr; metastable; an oxygen-
Fm3m stabilized phase [2002Ste]
Th6Mn23 a = 1172 in the alloy Zr30Fe70 (at.%) annealed at 1000˚C
for 200 h, together with the βZrFe2 phase
[2002Ste]
a = 1169 [V-C2]
τ, (ZrxTi1–x)2Fe cF96 a ≈ 1150 metastable, in the Zr15Ti60Fe25 and Zr10Ti65Fe25
Fd3m alloys produced by high speed crystallization
Ti2Ni [1998Kim1]
M (ZrTiFe) cI146 a = 1330.7 1/1 bcc, approximant, metastable
Im3 Zr11Ti64Fe25 [1995Kim, 1998Kim2]
I (ZrTiFe) c** a = 485 quasicrystal, metastable, composition is closed
to M (ZrTiFe) [1995Kim, 1998Kim2]
. Table 3
Investigations of the Fe-Ti-Zr Materials Properties
[1963Pie] Faraday method: dynamic measurements Magnetization, magnetic susceptibility,

(thermomagnetic analyses, TMA) and saturation magnetization at 4 to 650 K,
static measurements Curie temperature
[1987Bla] PMT-3 mechanical tests Microhardness
[1988Nag] Energy dispersive X-ray analysis (EDX), Hydriding rate, pressure-composition
volumetric method (Sievert’s apparatus isotherms
measurements), SEM
[1991Ard] Magnetic properties tests Quadrupole splitting, isomer shift
[1999Sin] Volumetric method (Sievert’s apparatus Hydriding rate, pressure-composition
measurements) isotherms

10 34 Fe–Ti–Zr
[2000Nis] Hydriding using a conventional pressure- Desorption and adsorption isotherms,

proof vessel pressure-composition isotherms
57
[2001Bud] Fe Mössbauer spectroscopy Hyperfine interaction, quadrupole
splitting, isomer shift dependences on
concentration
57
[2003Sur] Fe Mössbauer spectroscopy Magnetic structure, hyperfine interaction,
quadrupole splitting, isomer shift
dependences on concentration

Fe–Ti–Zr 34 11
. Fig. 1
Fe-Ti-Zr. The Ti-Zr phase diagram

12 34 Fe–Ti–Zr
. Fig. 2
Fe-Ti-Zr. Lattice parameters of the Laves phases in the quasibinary system ZrFe2-TiFe2

Fe–Ti–Zr 34 13
. Fig. 3
Fe-Ti-Zr. Quasibinary system ZrFe2-TiFe2

14 34 Fe–Ti–Zr
. Fig. 4
Fe-Ti-Zr. Isothermal section at 900˚C

Fe–Ti–Zr 34 15
. Fig. 5
Fe-Ti-Zr. Mixing enthalpy of liquid Fe-Ti-Zr alloys at 1879˚C. Values denote the mixing enthalpies
in kJ·mol–1

16 34 Fe–Ti–Zr
. Fig. 6
Fe-Ti-Zr. Excess heat capacity of liquid Fe-Ti-Zr alloys at 1879˚C. Values denote the excess heat
capacities in J·mol–1·K–1

Fe–Ti–Zr 34 17
. Fig. 7
Fe-Ti-Zr. Vickers microhardness values of the λ1 phase in the ZrFe2-TiFe2 quasibinary system

18 34 Fe–Ti–Zr
References
[1963Pie] Piegger, E., Craig, R.S., “Structural and Magnetic Characteristics of TiFe2-ZrFe2 and ZrCo2-ZrFe2
Alloys”, J. Chem. Phys., 39(1), 137–145 (1963) (Crys. Structure, Experimental, Magn. Prop., 15)
[1971Pet] Pet’kov, V.V., Kocherzhinskiy, Yu.A., Markiv, V.Ya., “Investigation of the Polythermal Sections ZrFe2-
TiFe2 and ZrCo2-TiCo2” (in Ukrainian), Dop. Akad. Nauk Ukr. RSR, Ser. A, (10), 942–944 (1971) (Crys.
Structure, Phase Diagram, Phase Relations, Experimental, #, 6)
[1973Sve] Svechnikov, V.N., Kocherzhinsky, Yu.A., Markiv, V.Ya., Pet’kov, V.V., “Laves Phases in Transition Metal
Systems of the IV-VIII Groups of Periodic System” (in Russian), Akad. Nauk Ukr. SSR, Metallofizika,
46, 35–45 (1973) (Phase Diagram, Phase Relations, Experimental, Review, #, 74)
[1980Hil] Hillert, M., “Empirical Methods of Predicting and Representing Thermodynamic Properties of Ternary
Solution Phases”, Calphad, 4, 1–12 (1980) (Thermodyn., Calculation) as quoted by [1996Wan]
[1982Sil] da Silva, E.G., Coelho, J.S., Mansur, R.A., “The Effect of Titanium on the Stabilization of the β-Zr (Fe)
Phase”, Acta Metall., 30, 1829–1833 (1982) (Crys. Structure, Morphology, Phase Relations, Experimen-
tal, *, 8)
[1987Bla] Blazina, Z., Trojko, R., “On Friauf-Laves Phases in the Zr1–xAlxT2, Zr1–xSixT2 and Zr1–xTixT2 (T = Mn,
Fe, Co) Systems”, J. Less-Common Met., 133(2), 277–286 (1987) (Crys. Structure, Morphology, Experi-
mental, Electronic Structure, Mechan. Prop., 10)
[1987Mur] Murray, J.L., “Fe-Ti” in “Phase Diagrams of Binary Titanium Alloys”, Springer Verlag, Berlin (1987)
(Crys. Structure, Phase Diagram, Review, 117)
[1988Nag] Nagai, H., Kitagaki, K., Shoji, K.-I., “Hydrogen Storage Characteristics of FeTi Containing Zirconium”,
Trans. JIM, 29(6), 494–501 (1988) (Morphology, Phase Diagram, Phase Relations, Experimental, Phys.
Prop., 8)
Alloy Systems (Zr1–xTix)2Fe and (Zr1–xTix)3Fe in the Range 0 ≤ x ≤ 0.2”, Scr. Met. Mater., 25(6),
abstract
[1992Rag] Raghavan, V., “The Fe-Ti-Zr (Iron-Titanium-Zirconium) System” in “Phase Diagrams of Ternary Iron
Alloys”, Indian Institute of Metals, Calcutta, 6B, 1223–1224 (1992) (Crys. Structure, Phase Diagram,
Phase Relations, Review, #, 4)
[1994Kum] Kumar, H., Wollants, P., Delaey, L., “Thermodynamic Assessment of the Ti-Zr System and Calculation
of the Nb-Ti-Zr Phase Diagram”, J. Alloys Compd., 206(1), 121–127 (1994) (Phase Diagram, Thermo-
dyn., Assessment, Calculation, 32)
[1994Qin] Qin, J., Roesner-Kuhn, M, Schaefers, K., Frohberg, M.G., “Consideration of the Excess Heat Capacity
for the Evaluation of Mixing Enthalpies Measured by Levitation Alloying Calorimetry”, Z. Metallkd.,
85(10), 692–695 (1994) (Thermodyn., Calculation, Experimental, 12)
[1995Kim] Kim, W.J., Kelton, K.F., “Icosahedral and Related Phase Formation in Rapidly Quenched Ti-Zr-Fe
Alloys”, Philos. Mag. A, 72(5), 1397–1408 (1995) (Crys. Structure, Morphology, Experimental, 17)
[1996Wan] Wang, H., Lueck, R., “Mixing Enthalpy of Liquid T-Ti-Zr (T = Fe, Co, Ni) Alloys”, J. Non-Cryst. Solids,
205–207, 417–420 (1996) (Thermodyn., Calculation, Experimental, 23)
[1998Kim1] Kim, W.J., Gibbons, P.C., Kelton, K.F., “Icosahedral Quasicrystal Formation in Ti-Zr-Based Alloys and
a New Classification Technique”, Philos. Mag. A, 78(5), 1111–1124 (1998) (Crys. Structure, Experi-
mental, Review, 37)
[1998Kim2] Kim, W.J., Gibbons, P.C., Kelton, K.F., Yelon, W.B., “Structural Refinement of 1/1 bcc Approximants to
Quasicrystals: Bergman-Type W (TiZrNi) and Mackay - Type M (TiZrFe)”, Phys. Rev. B, 58(5),
[1999Sin] Singh, B.K., Singh, A.K., Pandey, C.S., Srivastava, O.N., “Investigation on Synthesis, Characterization
and Hydrogenation Behaviour of Hydrogen Storage Material: Fe1–xZrxTi1.3 (x = 0.2)”, Int. J. Hydrogen
Energy, 24(11), 1077–1082 (1999) (Crys. Structure, Morphology, Phase Relations, Experimental, Phys.
Prop., 10)
[1999Thi] Thiedemann, U., Roesner-Kuhn, M., Drewes, K., Kuppermann, G., Frohberg, M.G., “Mixing Enthalpy
Measurements of Liquid Ti-Zr, Fe-Ti-Zr and Fe-Ni-Zr Alloys”, Steel Res., 70(1), 3–8 (1999) (Thermo-
dyn., Calculation, Experimental, 20)

Fe–Ti–Zr 34 19
[2000Nis] Nishimiya, N., Wada, T., Matsumoto, A., Tsutsumi, K., “Hydriding Characteristics of Zirconium-
Substituted FeTi”, J. Alloys Compd., 313, 53–58 (2000) (Phase Relations, Thermodyn., Experimental,
Phys. Prop., 13)
[2001Bud] Budzyn’ski, M., Sarzyn’ski, J., Surowiec, Z., Wiertel, M., “Moessbauer and X-Ray Diffraction Studies of
Zr1–xTixFe2 Laves Phase Compounds”, Acta Phys. Pol. A, 100(5), 717–722 (2001) (Crys. Structure,
Experimental, Magn. Prop., 8)
Intermetallics, 10, 149–159 (2002) (Crys. Structure, Calculation, Electronic Structure, 27)
(2002) (Crys. Structure, Morphology, Phase Diagram, Phase Relations, Assessment, Experimental,
Review, 88)
[2003Sur] Surowiec, Z., Wiertel, M., Beskrovnyi, A.I., Sarzyn’ski, J., Milczarek, J.J., “Investigations of Microscopic
Magnetic Properties of the Pseudo-Binary System (Zr1–xTix)Fe2”, J. Phys.: Condens. Matter, 15(37),
[2007Zho] Zhou, G., Jin, S., Liu, L., Liu, H., Jin, Z., “Determination of Isothermal Section of Fe-Ti-Zr Ternary
System at 1173 K”, Trans. Nonferrous Met. Soc. China, 17, 963–966 (2007) (Experimental, Morphology,
(1990)


(Landolt-Börnstein - Group IV Physical Chemistry 11D5 _ Physical Chemistry) Günter Effenberg, Svitlana Ilyenko (Eds.)-Ternary Alloy Systems_ Phase Diagrams, Crystallographic and Thermodynamic Data Cri

Загружено:

Сведения о документе

Авторское право

Доступные форматы

Поделиться этим документом

Поделиться или встроить документ

Параметры публикации

Этот документ был вам полезен?

Это неприемлемый материал?

Авторское право:

Доступные форматы

(Landolt-Börnstein - Group IV Physical Chemistry 11D5 _ Physical Chemistry) Günter Effenberg, Svitlana Ilyenko (Eds.)-Ternary Alloy Systems_ Phase Diagrams, Crystallographic and Thermodynamic Data Cri

Загружено:

Авторское право:

Доступные форматы

Landolt-Börnstein

Numerical Data and Functional Relationships in Science and Technology

Group IV: Physical Chemistry

Ternary Alloy Systems

ISBN 978-3-540-70885-8 Springer Berlin Heidelberg New York

Library of Congress Cataloging in Publication Data

Springer is a part of Springer Science+Business Media

Cover layout: Erich Kirchner, Heidelberg

SPIN: 1221 0152 63/3020 - 5 4 3 2 1 0 – Printed on acid-free paper

MSI, Materials Science International Services GmbH

Authors: Materials Science International Team, MSIT®

Bulanova, Kyiv, Ukraine Gabriele Pankaj Nerikar, Gainesville, USA Pierre

Fabrichnaya, Freiberg, Germany Yulia Changsha, China Jean-Claude Tedenac,

Fartushna, Kyiv, Ukraine Baiyun Huang, Montpellier, France Vasyl Tomashik,

Changsha, China Volodymyr Ivanchenko, Kyiv, Ukraine Lyudmilla Tretyachenko,

Russia Kostyantyn Korniyenko, Kyiv, Xiong, Changsha, China Honghui Xu,

Ukraine Artem Kozlov, Clausthal-Zellerfeld, Changsha, China Chao Zhang, Changsha,

Shuhong Liu, Changsha, China Weiwei Zhang, Changsha, China

The Baikov Institute of Metallurgy, Academy of School of Chemical and Metallurgical

Moscow State University, Department of General University of Florida, Department of Materials

Northwestern University, Department of University of Leeds, Department of Materials,

An English poem from the 19th century tells us

Gold is for the mistress

It is still actual and true.

Prof. Dr. ir. Patrick Wollants

IV/11D5 Ternary Alloy Systems

Subvolume D Iron Systems

Part 5 Selected Systems from Fe-N-V to Fe-Ti-Zr

Fe–N–V (Iron – Nitrogen – Vanadium)..................................................................................................1

Structure of a System Report

Landolt‐Börnstein DOI: 10.1007/978-3-540-70890-2_1

Liquidus, Solidus, Solvus Surfaces

Landolt‐Börnstein DOI: 10.1007/978-3-540-70890-2_1

DOI: 10.1007/978-3-540-70890-2_1 Landolt‐Börnstein

In the polythermal projection of the liquidus surface, monovariant liquidus grooves

Temperature – Composition Sections

Landolt‐Börnstein DOI: 10.1007/978-3-540-70890-2_1

Notes on Materials Properties and Applications

DOI: 10.1007/978-3-540-70890-2_1 Landolt‐Börnstein

Landolt‐Börnstein DOI: 10.1007/978-3-540-70890-2_1

DOI: 10.1007/978-3-540-70890-2_1 Landolt‐Börnstein

Index of Alloy Systems

Index of Ternary Iron Alloy Systems Fe-N-V to Fe-Ti-Zr

Fe–N–V (Iron – Nitrogen – Vanadium)

Landolt‐Börnstein DOI: 10.1007/978-3-540-70890-2_2

Iron – Nitrogen – Vanadium

Landolt‐Börnstein DOI: 10.1007/978-3-540-70890-2_3

DOI: 10.1007/978-3-540-70890-2_3 Landolt‐Börnstein

Temperature – Composition Sections

Notes on Materials Properties and Applications

DN / cm2·s–1 = 0.0066 exp(–13 300 / T), which corresponds to an activation energy of

Landolt‐Börnstein DOI: 10.1007/978-3-540-70890-2_3

DOI: 10.1007/978-3-540-70890-2_3 Landolt‐Börnstein

Phase/ Pearson Symbol/

Landolt‐Börnstein DOI: 10.1007/978-3-540-70890-2_3

Phase/ Pearson Symbol/

Temperature Quantity, per mol of

½ N2 Ð {N} (in Liquid Fe) 2000 ΔrH˚ = + 5600 [1975Pom]

DOI: 10.1007/978-3-540-70890-2_3 Landolt‐Börnstein

Reference Method / Experimental Technique Type of Property

Landolt‐Börnstein DOI: 10.1007/978-3-540-70890-2_3

DOI: 10.1007/978-3-540-70890-2_3 Landolt‐Börnstein

Landolt‐Börnstein DOI: 10.1007/978-3-540-70890-2_3

DOI: 10.1007/978-3-540-70890-2_3 Landolt‐Börnstein