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2008
137th Annual Meeting & Exhibition
Supplemental Proceedings
Volume 3:
General Paper Selections
AM08 Coll.Proc. Book Vol III_ins1 1 1/28/2008 1:49:21 PM

2008
Other TMS 2008 Annual Meeting Publications:

• TMS 2008 Annual Meeting Supplemental Proceedings,
Volume 1: Materials Processing and Properties
• TMS 2008 Annual Meeting Supplemental Proceedings,
Volume 2: Materials Characterization, Computation and Modeling
• Light Metals 2008
• Magnesium Technology 2008
• EPD Congress 2008
• Carbon Dioxide Reduction Technology
• Aluminum Alloys: Fabrication, Characterization and Applications
• Plasticity, Failure and Fatigue in Structural Materials-from Macro to Nano:
Proceedings of the Hael Mughrabi Honorary Symposium
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2008
Supplemental Proceedings
Volume 3: General Paper Selections
About This Volume

The TMS 2008 Annual Meeting Supplemental Proceedings, Volume 3: General
Paper Selections, is a collection of papers from the TMS 2008 Annual Meeting &
Exhibition, held March 9-13, in New Orleans, Louisiana, USA.
The papers in this volume were selected based on technical topic compatibility
and represent five symposia from the meeting. This volume, along with the other
proceedings volumes published for the meeting (listed on the next page), and
archival journals, such as Metallurgical and Materials Transactions and the
Journal of Electronic Materials, represents the available written record of the 56
symposia held at the TMS 2008 Annual Meeting.
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are presented “as is.” The opinions and statements expressed within the papers
are those of the individual authors only and are not necessarily those of anyone
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TABLE OF CONTENTS
Supplemental Proceedings: Volume 3: General
Paper Selections
General Abstracts: Materials Processing and

Manufacturing Division
Austenite Grain Refining of As-Cast Bloom Surface by
Reduction of Oscillation Mark Depth...................................................................3
Y. Ohba, S. Kitade, and I. Takasu
Quality Assessment of Casting Filling Method ....................................................9

M. Jolly, and C. Reilly
Phase Field Simulation of Irregular Eutectic Solidification................................15

R. Zhang, M. Li, and J. Allison
A Numerical Scheme for Solving Microsegregation for

Solidifying Metallic Alloys ................................................................................21
S. Uddin, and M. Hasan
Advances in NDT Techniques for Friction Stir Welding Joints

of AA2024 ..........................................................................................................27
T. Santos, P. Vilaça, L. Reis, L. Quintino, and M. de Freitas
A Thermal Model of Friction Stir Welding Applied to

Aluminum 7136-T76511 Extrusions ..................................................................33
C. Hamilton, S. Dymek, M. Blicharski, and I. Kalemba
Effect of Ultrasonic Vibration on Solidification Structure of

TCS Stainless Steel.............................................................................................41
J. Liang, L. Wang, C. Song, L. Liu, and Q. Zhai
Effect of Tin Content on the Magnetic Properties and

Recrystallization Behaviors of Grain-Oriented Electrical
Steels...................................................................................................................49
C. Liao, and C. Hou
v
Mechanical Properties and Microstructure of Friction Stir
Welded High-Strength Automotive Steel ...........................................................55
M. Miles, E. Olsen, T. Nelson, and M. Gallagher
Integrated Fabrication of Functionally Graded Ti3SiC2-TiC

Binary Phase Rod by Traveling Zone Sintering Method ....................................61
S. Tada, and K. Kobayashi
Study on Deformation of Large-Scale Hydraulic Turbine

Blade during the Casting Process .......................................................................67
J. Zhang, J. Kang, Y. Wu, J. Zhang, Z. Rong, C. Zhang, and B. Liu
Multi-Temperature Uniaxial Compression Testing of Sintered

ZrN and (Zr,Ti)N Pellets as Surrogates for PuN and (Pu,Zr)N
Fuels ...................................................................................................................73
K. Wheeler, P. Peralta, and K. McClellan
A Nano-Indentation Study of Surface Plasticity in Zirconium

Nitride.................................................................................................................79
K. Wheeler, P. Peralta, G. Egeland, and K. McClellan
Influence of High-Intensity Ultrasonic Treatment on the Phase

Morphology of Mg-9.0wt.%Al Binary Alloy .....................................................85
Z. Zhang, Q. Le, S. Guo, and J. Cu
Effect of Electric Current Pulse on Solidification Structure of

Bearing Steel with Low Voltage and High Discharging
Frequency ...........................................................................................................91
J. Li, Y. Gao, J. Ma, and Q. Zhai
A Calculation Model for Thermal Performance during Particle

Cooling in the Substate-Coatings System Based on Plasma
Spraying Processes .............................................................................................97
L. Niu, T. Zhang, J. He, and Z. Dou
Optimization of Gas Carburizing Process in Batch Furnaces

with Endothermic Carburizing Atmosphere .....................................................107
O. Karabelchtchikova, and R. Sission Jr.
Experimental and Numerical Study of Flame Load Heat

Transfer in an Experimental Furnace................................................................115
A. Kumar, R. Venuturmilli, L. Kiss, and G. Walter
vi
Influence of the Process Parameters on the Multi-Directional
Forging Operation of a Two Cylinder Crankshaft ............................................121
S. Mueller, P. Lau, and R. Nickel
Controlled Sheet Metal Straightening...............................................................129

B. Behrens, and R. Krimm
Drilling and Milling of Intermetallic γ-TiAl.....................................................137

D. Biermann, and S. Bergmann
Preparation of High-Purity Strontium Carbonate from

Celestite Concentrate by Double Decomposition-Roasting
Process ..............................................................................................................149
M. Liu, T. Jiang, and G. Li
Author Index.....................................................................................................439
Subject Index ....................................................................................................443
vii
TABLE OF CONTENTS
Paper Selections
General Abstracts: Structural Materials Division

Blocking and Self-Locking of Superdislocations in
Intermetallics ....................................................................................................165
B. Greenberg, M. Ivanov, and A. Patselov
Effect of the γ/γ' Lattice Mismatch on the Creep Behaviour at

760°C of New Generation Single Crystal Superalloys .....................................171
P. Caron, and F. Diologent
Oxidation Behavior of Mo-Si-B Alloys Produced by Reaction

Synthesis...........................................................................................................177
M. Middlemas, and J. Cochran
Pile-up/Sink-in in Nanoindentation Rate Sensitive Creeping

Solids ................................................................................................................185
A. Elmustafa
Researches Concerning the Structural Characterization of

Hybrid Composite Materials.............................................................................193
P. Moldovan, G. Popescu, C. Popescu, and B. Ghiban
Quantitative Evaluation of Creep Curve of Alloy-Type and

Metal-Type Creep in Magnesium-Aluminum Binary Alloys at
Around 0.6Tm ..................................................................................................199
H. Sato
Properties of Titanium Oxide Films Deposited by the Sol-Gel ........................205

P. Favilla, M. Alterach, M. Rosenberger, A. Ares, C. Schvezov,
and O. Amerio
Microstructural and Mechanical Properties of Alumina

Coatings Produced by Microarc Oxidation Technique on 7039
Aluminum Alloy Substrate ...............................................................................211
A. Polat, J. Baxi, Y. Kar, M. Usta, M. Makaraci, H. Liang,
and A. Ucisik
viii
Effects of Lattice Defects Induced by Hydrogen and Stress on
Environmental Degradation of Metals..............................................................217
K. Takai, and H. Shoda
Brittle Crack Susceptibility of Low Temperature Separator

Vessel Material .................................................................................................223
A. Nawaz
Direct Production of Super-Grade Materials in Nano-Particle

Based Fuels.......................................................................................................231
L. Popa-Simil, and C. Muntele
Synthesis and Microstructure of Si3N4-TiN nanocomposites..........................237

M. Yang, M. Lv, and H. Zhu
Austenite Grain Stability of Low-Manganese, High-

Chromium Carburizing Steel ............................................................................243
T. Fujimatsu, K. Hashimoto, S. Fukumoto, and A. Yamamoto
Development of High Strength Non-Oriented Electrical Steels .......................247

H. Park, S. Chang, and B. De Cooman
Characteristics of Hybrid Solid Solution Layer Formed on the

Surface of 316 L Austenitic Stainless Steels ....................................................251
O. Celik, H. Cimenoglu, and E. Kayali
Microstructure Evolution in Nano/Sub-Micron AISI 301

Stainless Steel ...................................................................................................257
S. Rajasekhara, P. Ferreira, L. Karjalainen, and A. Kyröläinen
Effects of Mo and Ni on Textures and Magnetic Properties in

3%Si Non-Oriented Electrical Steels................................................................267
S. Chang
Author Index.....................................................................................................439
Subject Index ....................................................................................................443
ix
TABLE OF CONTENTS
Paper Selections
General Abstracts: Light Metals Division

An Optimization Study for an Efficient Hydrogen Removal
during Twin Roll Casting .................................................................................275
A. Dursun, B. Çorlu, M. Dündar, and R. Erdogan
Methods of Manganese Alloying to Aluminum and Their

Impact on Melt Quality.....................................................................................283
V. Ohm, and R. Bauer
Manufacture and Characterization of Al-3Mg-Nb............................................289

N. Lopez, X. Rodríguez, S. Dominguez, L. Vazquez, V. Cortés,
M. Domínguez, G. Lara, M. Vite, J. Aguilar, and S. Buenavista
An Investigation of Hexavalent-Free Chromate Conversion

Coatings for Test and Measurement Instrumentation .......................................295
M. Powers
Fabrication of AA2024-SiC Nanocrystalline Metal Matrix

Composite.........................................................................................................301
T.Z. Lin, C. Tan, B. Liu, Q. Yang, and A. McDonald
Comparative Analysis of the Influence of Inhibitor

Concentrations on the Corrosion Susceptibility of Al - 1.0%Zn
Alloy in Acidified Vernonia Amegdalina, Pipernigrum and
Telferia Occidentalis.........................................................................................307
N. Idenyi, C. Ekuma, and S. Neife
The Impact of Corrosion on the Deformation Behaviour of Al-

Zn Alloys in 0.1M HCl and Seawater...............................................................313
N. Idenyi, I. Owate, C. Okeke, and S. Neife
Effects of Different Annealing Processes on Microstructural

Features of Twin Roll Cast 3003 and 8006 Aluminum Alloys.........................319
B. Çorlu, A. Dursun, M. Dündar, and C. Inel
x
Prefabricated Materials Preforms in Titanium Alloys using
Stationary Shoulder Friction Stir Welding........................................................333
P. Threadgill, B. Wynne, M. Russell, and P. Davies
Bonding of Steel Inserts during Aluminum Casting .........................................339

Q. Han, S. Viswanathan, K. More, M. Myers, M. Warwick,
and Y. Chen
Low Temperature Electrochemical Synthesis of Ti-Al Alloys

Using Ionic Liquid Electrolytes ........................................................................345
D. Pradhan, and R.G. Reddy
Residual Life Extension of Aged Transformers in Aluminium

Smelters ............................................................................................................353
S.K. Rajamoorthy, and S. Krishnamoorthy
Revamping of Rodding Shop Worldwide.........................................................359

J. Grunspan
Electrical Conductivity of Molten Electrolytes for Light Metal

Production.........................................................................................................365
A.A. Redkin, O.Y. Tkacheva, and A. P. Shuryghin
Author Index.....................................................................................................439
Subject Index ....................................................................................................443
xi
TABLE OF CONTENTS
Paper Selections
General Abstracts: Electronic, Magnetic, and

Photonic Materials Division
Studies on ZnO Based Diluted Magnetic Semiconductors ...............................373
S. Deka, and P.A. Joy
Tantalum Electrlytic Capacitors .......................................................................379

R.A.R. Rashid, S. Jyoth, Rajkiran, and P. Goud
Experimental Study of Co-Deposition of SiO2 and GeO2 in a

Modified Chemical Vapor Deposition (MCVD) Reactor .................................385
S. Zhan, M. Hasan, T. Wang, and Z. Chen
Lightning Causes and Effects - A Systematic Protection

Approach for the Aluminum Industry...............................................................391
F. D'Alessandro
Magneto-Optical Study of Cobalt Ferrite Nanoparticles ..................................399

B.L. Scott, C. Radu, D.A. Smith, and K.L. Stokes
Author Index.....................................................................................................439
Subject Index ....................................................................................................443
xii
TABLE OF CONTENTS
Paper Selections
General Poster Session

Application of Amide–Impregnated Fiber to Separation of
Precious Metals.................................................................................................407
H. Narita, M. Tanaka, K. Morisaku, K. Tamura, D. Sakamoto,
M. Suzuki, and T. Nadano
Effect of Cr on the Oxidation Behavior of Ti-46Al-2V Alloy..........................413

D. Pilone, and F. Felli
Elastic-Plastic Stress and Deformation Analysis of Annular

Plates under Prescribed Radial Loading ...........................................................419
A.H. Elkholy, and A.H. Falah
Inoculation of Aluminum Alloys with Nanosized Borides and

Microstructure Analysis....................................................................................425
H.E. Calderón, C. Smith, O. Menéndez, and O.M. Suárez
Microstructural Characterization in Cast AlMg Alloy-SiCp

Composites .......................................................................................................431
A. García, and S. Valdez
Author Index.....................................................................................................439
Subject Index ....................................................................................................443
xiii
Supplemental Proceedings: Volume 3: General Paper Selections
TMS (The Minerals, Metals & Materials Society), 2008
Austenite grain refining of as-cast bloom surface by reduction of oscillation

mark depth
Yasuhide Ohba, Shin-ichi Kitade and Ichiro Takasu
Sanyo Special Steel Co., Ltd.; 3007 Nakashima Shikama-Ku; Himeji, Hyogo, 672-8677, Japan
Keywords: Austenite Grain; Grain Size; Refining; Grain Growing; Continuous Casting;
Oscillation Mark; Cooling Rate; AS-Cast
Abstract
Austenite grain refining in the surface layer of as-cast bloom is effective for the reduction of
surface cracks in steel production. This study was carried out to clarify the influence of cooling
rate on the as-cast austenite grain size and its growth mechanism. The austenite grains at the
bloom surface were refined under the oscillation conditions of higher frequency and shorter
stroke. The average cooling rates were estimated to be 6-16K/s in austenite phase temperature. It
was found that the austenite grain growth direction did not vary even when characteristics of
oscillation mark changed. The austenite grain size below the surface layer was also determined
by that of bloom surface.
Introduction
Surface cracks on continuously cast blooms are sometimes generated by tensile stress and strain.
Since surface cracks are generated and propagated along the γ grain boundary at the γ phase
temperature region, it is important to refine austenite (γ) grain on as-cast bloom surface for
prevention of surface cracks 1). During continuous casting, oscillation marks (OSM) are formed
on the bloom surface. The γ grain at the bottom of OSM where the cooling rate is lower than the
top of OSM tends to be coarse 1), 2). Surface cracks on the bloom surface tend to occur at the
bottom of OSM. This tendency is considered to be due to not only the notch effect of OSM 3), 4)
but also coarse γ grain. Higher cooling rate 5) and the use of non-metallic inclusions 6) are
refining methods for γ grain. Since non-metallic inclusions can deteriorate the characteristics of
products, higher cooling rate by reducing the OSM depth was employed for the reduction of γ
grain size. In this paper, casting tests under the oscillation conditions of shorter stroke and higher
frequency were conducted to reduce the OSM depth 7). Influence of the cooling rate on the as-
cast γ grain size and the growth mechanism of the γ grain were examined.
Experimental Procedure
The chemical compositions of the bloom specimens, which are case-hardening steel of 0.20
mass% carbon, are shown in Table 1. The casting conditions are shown in Table 2. Sinusoidal
curve was adopted for mold oscillation mode. Five oscillation conditions with different strokes
and different negative strip ratios were examined by using the commercial production process.
Oscillation conditions became shorter stroke and higher frequency in order of condition 1 to 5.
The strokes in conditions 1 and 2, 4 and 5 were the same, while the negative strip ratio in
conditions 1, 3 and 5 were the same.
The steel specimens were prepared through the following procedure, cut from as-cast blooms
parallel to the casting direction, polished and etched by picric acid for dendrite structures and 5
% HNO3 for γ grain boundary. The surface layer structure of the bloom was examined by optical
3
microscope. The specimen is approximately 25 mm long, and contains 5~10 pieces of OSM on
it. Four specimens were cut out per 1 bloom, and metallographically observed. The OSM depths
were decided by referring to their microstructure, and were defined as the distance between the
bottom of the OSM and the tangential line of the 2 neighbor tops of the OSM. Grains in surface
layer were columnar shape. The minor axis of γ grain was taken as an as-cast γ grain size. The
as-cast γ grain size at each distance from bloom surface was taken from the number of grain
boundary crossed the 100 mm as Esaka et.al did 8). The cooling rate during the solidification was
estimated by using the equation 1 9), referring to secondary dendrite arm spacing.
S = 710RLS-0.39 --- (1)
Where, S is dendrite arm spacing, and RLS is the average solidification-cooling rate.
Table 1. Chemical compositions of the specimen (mass%)

C Si Mn P S Cr
0.20 0.30 0.83 0.017 0.017 1.18
Table 2. Casting conditions

Condition 1 2 3 4 5
Bloom dimension [mm×mm] 380×490
Casting velocity [m/min] 0.5
Superheat [K] 25
Oscillation stroke [mm] 4 4 2.6 2 2
Oscillation frequency [cpm] 104 129 160 135 208
Negative strip ratio [%] 75 80 75 60 75
Negative strip time [s] 0.22 0.19 0.14 0.13 0.11
Mold powder CaO/SiO2 [-] 0.6
Mold powder viscosity at 1573K [Pa·s] 2.4
Results
Fig. 1 shows appearances of bloom surfaces in the conditions 1, 3 and 5. Bloom surface in the
condition 1, 3, 5 were called as bloom 1, 3, 5 respectively. Both the intervals and the depths of
OSM have reduced in the order of condition 1 to 5. The OSM in the condition 5 was hardly
observed. The OSMs of blooms 1 and 3 were formed straightly with equal interval. These results
suggested that blooms were cast in a good condition without any troubles, such as inconsistent
infiltration of slag at meniscus, the misfit of the mold oscillation and the movement of initially
solidified shell 10).
Condition 1 Condition 3 Condition 5
Casting direction
Fig. 1 Appearance of bloom surface.

Fig. 2 shows relationship between the negative strip time 11) and the OSM depth. Average OSM
depth was reduced with oscillation conditions of shorter stroke and higher frequency 3), 11-13).
There is small difference in mold powder consumption among condition although the OSM
characteristics were different. In general, sticking of the solidified shell and the mold could occur
due to lack of powder slag infiltration 14). There was no sign of the sticking and surface cracks.
These results suggested that the slag infiltration was stable and uniform in these tests.
4
Fig. 3 shows micrographs of austenite grains at the cross section of oscillation marks. The shape
of the γ grains of as-cast bloom was columnar with their growth direction toward inside. The
results showed that the temperature gradient at the growth edge of γ grains was large 15). The γ
grains were refined, both at the bottom of OSM and at the top of OSM in shorter stroke and
higher frequency. This tendency would be due to the uniformity of cooling rate between the
bottom and the top of the OSM. This uniformity was related to not only the OSM depths but also
the OSM intervals.
Fig. 4 shows relationship between the depth from bloom surface and the average γ grain size for
different oscillation conditions. γ grains were refined in the oscillation conditions of shorter
stroke and higher frequency. γ grain was the smallest at the surface, and had been growing
inside. The depth from the bloom surface and the average γ grain size had a linear relationship.
400 1600
300 1200
γ ｇrain size, d /μm

OSM depth/μｍ
200 800
Condition 1 Condition 1
100 Condition 3 400 Condition 3
0 0
0 0.1 0.2 0.3 0 3 6 9 12
Negative strip time/s Depth from bloom surface, L /mm
Fig. 2 Relationship between negative strip time Fig. 4 Relationship between depth from bloom
and OSM depth. surface and austenite grain size for different
oscillation conditions.
Casting direction
Condition 1
Condition 3
Condition 5
2mm
Fig. 3 Micrographs of austenite grains at the cross section of oscillation marks.
Discussion
Cooling rate, grain selection behavior, inclusion, and steel composition can be factors that
influence the γ grain size. In this experiment, there was no significant difference in the steel
compositions and the inclusion levels. Therefore, the γ grain size was examined from the
viewpoint of the grain selection behavior and the cooling rate. Esaka et al. 16), 17) have reported
the relation between the normalized number of grains (n/n0), where n is the number of grains, n0
is the initial number of grains, and the normalized growth length (L/d0), where L is the growth
length, d0 is the initial grain size, by using the grain selection model. It was said that n/n0
5
decreased with L/d0, and the grain selection behavior changed from heat flow direction (π'=0) to
prioritized growth direction (π'=1) by introducing the growth direction parameter π' 16), which
showed the direction of the γ grain growth. Fig. 5 16) shows the relation among <100>, growth
direction and heat flow direction. The growth of the crystal whose priority growth direction
shifts only θ from heat flow direction follows α shifted from the heat flow direction, that is, the
direction of π’·θ. π' takes the value between 0-1 under such assumption. Fig. 6 shows the relation
between the normalized grain sizes (d/d0) and L/d0, where d is the γ grain size and L is the depth
from the bloom surface shown in Fig. 4. Each average γ grain size at the top surface of the
blooms 1 through 5 were applied to d0, respectively. Since the reciprocal of n/n0 was d/d0, the
relation between L/d0 and n/n0 shown by Esaka 16), can be converted into it between L/d0 and
d/d0. The relation between L/d0 and d/d0 for π'=0-1 was approximately linear, respectively. The
approximated straight lines for π'=0-1 were shown in Fig. 6. Most of the average γ grain sizes for
the blooms 1 through 5 were found to be around the approximated straight line for π'=1, that is,
the direction of the prioritized γ grain growth. Regarding the γ grain growth direction, π'=1 and
π'=0 correspond to the priority growth direction and the heat flow direction, respectively.
Therefore, it corresponds to the condition that the smaller the value of π' is, the larger heat
extraction from the initial solidification shell to copper mold is. The refinement of the γ grain
under the oscillation conditions of shorter stroke and higher frequency was considered to be due
to the intensified cooling of the initial solidification shell. However, from the viewpoint of the
grain selection, there was no influence of the heat flow direction and no change in the γ grain
growth direction.
3 π'=1 Condition 1
Normalized size of grains, d /d 0
π'=0.8 Condition 2
π'=0.6 Condition 3
Condition 4
2 π'=0.4
Condition 5
π'=0.2
π'=0
1
0
0 5 10 15 20
Normalized growth length, L /d 0
Fig. 5 Relation among <100>, growth direction Fig. 6 Relationship between normalized size of
and heat flow direction 16). grains and normalized growth length.
Influence of the cooling rate during solidification (RLS), and of the average cooling rate in the γ
phase temperature region (Rγ) and solidification rate (V) on the γ grain size were investigated.
RLS at 2 mm inside from the bloom surface is shown in Fig. 7. By the secondary dendrite arm
spacing, the cooling rates at the top and the bottom of OSM were estimated to from 18 to 27 K/s,
and from 7 to 18 K/s, respectively. The cooling rates at the bottom of the OSM for all of the
blooms 1 through 5 were found to be lower than those at the top of OSM for 10 K/s. Moreover,
regarding the bloom 5, the cooling rates not only at the bottom of OSM but also at the top were
higher for 10 K/s than those of bloom 1. It is because the reduction of the OSM depth and its
interval would reduce the influence of the delayed solidification at the bottom of OSM 2) and the
heat transfer in the casting direction from the bottom of OSM to the top.
6
Yoshida et al. 18) derives the relational equation of Rγ and casting γ grain diameter (d) from the
casting experiment with 0.1 mass%C steel and the theoretic calculation of the grain growth
(equation 2).
d=1.52 Rγ-0.5 --- (2)
Fig. 8 shows the relation between the depth from the bloom surface and Rγ, which was calculated
by the average γ grain size shown in Fig. 4, referring the equation 2 18). Regarding Rγ at the top
surface of the bloom, 6K/s for the bloom 1, 9.5 to 11 K/s for the blooms 2 through 4, and 16 K/s
for the bloom 5 were obtained. This cooling rate tendency would be due to the depth reduction
effect of the OSM. Regarding the blooms 2 through 4, the OSM depth was not enough to explain
their differences in Rγ. It is also because of the influence of the OSM intervals as mentioned
above. Specifically speaking, there was no significant difference in the OSM depth between the
blooms 2 and 3, and bloom 4 had larger OSM interval and smaller OSM depth than bloom 3.
Consequently the Rγ for the blooms 2 and 4 would not be much different from that for the bloom
3. Rγ decreased rapidly with the depth from the bloom surface, and the Rγ of from 2 to 3 K/s at 5
mm depth and 1 K/s at 10 mm depth were obtained. Rγ at 2 mm depth was 7 K/s for the bloom 5
and 3 K/s for the bloom 1. In this way, the cooling rate at the 2 mm depth from the surface rose
by shorter stroke and higher frequency, and RLS and Rγ were increased by 10 K/s and 4 K/s,
respectively.
Therefore, the refinement of γ grains was considered to be due to the refinement of the initial γ
grain at the bloom surface. It was found that the initial γ grain refinement was caused by the
decreased solidification delay and the increased average cooling rate at the bloom surface due to
the reduction of the OSM depths and intervals. In consequence of the prediction from γ grain
sizes, it could be estimated that Rγ for Bloom 5 were raised approximately from 1.5 to 2.5 times
of its for Bloom 1.
30 20
Condition 1
Condition 2
-1
-1
Cooling rate,R LS/K·s
15 Condition 3
Cooling rate,R γ /K·s
Condition 4
20
Condition 5
10
10
5
at the top of OSM
at the bottom of OSM
0 0
1 3 5 0 5 10 15
Casting condition Depth from bloom surface, L /mm
Fig. 7 Relationship between casting condition Fig. 8 Relationship between depth from bloom
and cooling rate at the position of 2mm inside surface and cooling rate.
from the surface.
Conclusions
The casting test in the commercial production process was carried out under the oscillation
conditions of shorter stroke and higher frequency to refine cast γ grain at the bloom surface by
reducing the OSM depth. The influence of the cooling rate on the γ grain size and the growth
mechanism of the γ grain were studied with the following conclusions:
(1) Depths and intervals of the oscillation mark were reduced and the γ grains were refined in the
oscillation conditions of shorter stroke and higher frequency, whether at the bottom of OSM or
at the top of it.
(2) The depth from the bloom surface and the average γ grain size had a linear relationship.
7
(3) It was found that the austenite grain growth direction did not vary even when characteristics
of the oscillation mark changed. The austenite grain size below the surface layer was also
determined by austenite grain size at the bloom surface. Refinement of the initial γ grain was
due to higher average cooling rate, which was caused by smaller OSM depths and intervals.
(4) The average cooling rates were estimated to be from 6 to 16K/s in γ phase temperature,
depending on the characteristics of OSM.
References
1) Y.Maehara, K.Yasumoto, Y.Sugitani and K.Gunji: Tetsu-to-Hagane, 71(1985), 1534.

2) E.Takeuchi and J.K.Brimacombe: Metall. Trans. B, 16B(1985), 605.
3) K.Kawakami, T.Kitagawa, H.Mizukami, H.Uchibori, S.Miyahara, M.Suzuki and Y.Shiratani:
Tetsu-to-Hagane, 67(1981), 150.
4) Y.Maehara, H.Tomono and K.Yasumoto: Tetsu-to-Hagane, 74(1988), 151.
5) K.Yasumoto, T.Nagamichi, Y.Maehara and K.Gunji: Tetsu-to-Hagane, 73(1987), 1738.
6) H.Suito, H.Ohta and G.V.Pervushin: CAMP-ISIJ, 13(2000), 752.
7) H.Takeuchi, S.Matsumura, R.Hidaka, Y.Nagano and Y.Suzuki: Tetsu-to-Hagane, 69(1983),
248.
8) Y.Kuroda, H.Esaka, K.Shinozuka and M.Tamura: Tetsu-to-Hagane, 92(2006), 432.
9) A.Suzuki, T.Suzuki, Y.Nagaoka and Y.Iwata: J. Jpn. Inst. Met., 32(1968), 1301.
10) Y.Ohba, I.Takasu, S.Kitade and H.Shimoguchi: Tetsu-to-Hagane, 92(2006), 439.
11) T.Emi, H.Nakato, Y.Iida, K.Emoto, R.Tachibana, T.Imai and H.Bada: Proc. 61st. NOH-
BOSC, (Chicago, 1978), 350.
12) M.Wolf: Tetsu-to-Hagane, 67(1981), S904.
13) H.Takeuchi, S.Matsumura and Y.Ikehara: Tetsu-to-Hagane, 69(1983), 1995.
14) T.Okazaki, H.Tomono, K.Ozaki and H.Akabane: Tetsu-to-Hagane, 68(1982), S929.
15) K.Matsuura, Y.Itoh and K.Matsubara: Tetsu-to-Hagane, 76(1990), 714.
16) H.Esaka, K.Hujita, H.Daimon, M.Tamura and K.Shinozuka: J. Jpn. Inst. Met., 64(2000),
1206.
17) H.Esaka, K.shinozuka and M.Tamura:ISIJ Int.,43(2003), 1751.
18) N.Yoshida, Y.Kobayashi and K.Nagai: Tetsu-to-Hagane, 90(2004), 198.
8
QUALITY ASSESMENT OF CASTING FILLING METHOD

MR Jolly1 and C Reilly1
1
Department of Mechanical Engineering, University Of Birmingham, UK
Keywords: Casting, Froude Number, Quality Assessment, Air Entrainment
Abstract
The reliability of cast components is dependent on the quality of the casting process. This can be
characterised by the robustness (repeatability) and specific fluid flow characteristics within the
running system. During this transient filling phase the prevention of free surface turbulence and
thus oxide entrainment is critical to the mechanical integrity of the component [1,2,3]. Past
research has highlighted that return waves are major causes of free surface entrainment [4]. To
reduce the entrainment occurring during the transitional filling of the runner a steady quiescent
flow must be developed.
Using FLOW-3D 1 , the Froude number was extracted to allow the quantitative assessment of air
entrainment for four different designs of sump at the end of the runner. The results show that, for
the designs used, the addition of a correctly designed sump can be advantageous. However, an
incorrect design may reduce the Froude number but can greatly increase the persistence of the
return wave and entrainment and is therefore extremely detrimental to the cast component.
Additionally, the in-gate design is of utmost importance in controlling the back pressure and thus
the persistence of the back wave between the in-gate and the downsprue exit. This has a direct
effect of the level of oxide entrainment.
Introduction
The return wave [1] is known to be a highly entraining flow regime common in many casting
systems during the period of transient filling. The use of low profile runners, i.e. a height of less
than the sessile drop height of the fluid has been advocated to stop this regime occurring [5,6].
However this is not always possible due to; manufacturing constraints, lack of flow control for
multiple gated systems etc.
Figure 1. Highly entraining return wave

The availability of quantitative data will allow the casting engineer to optimise the running
system design to improve casting integrity. The Froude number has been used in casting
1
FLOW-3D is a CFD software developed by Flow Science Inc; 683 Harkle Rd. Ste A, Santa Fe, NM 87505
9
applications previously for uphill teeming of steel ingots [7]. It has been proposed that it would
be useful in the assessment of the tendency towards the development of waves in the running
system [8]. Planned future work will correlate this criterion with experimental data.
Assessment Criterion
The Froude number (Fr) is defined as the ratio of initial and gravitational forces and can be
represented by Equation 1 & 2:
ρl 2 v 2 v 2
Fr 2 = 3 = (1)
ρl g gl
v
Fr = (2)
gl
Where; ρ is density (kgm-3), l is characteristic length (m), v is characteristic velocity (ms-1), and g
is the gravitational acceleration (ms-2).
The Froude number has commonly been used by civil engineers to assess air entrainment in
hydraulic structures. Research has shown a Froude Number >1.7 entrains air [9] [Figure 2].
Figure 2. Entrainment magnitude schematic [9]
The Froude number has been modified to allow quantitative assessment of return waves as seen
in Equation 3.
v − v2
Fr = 1 (3)
gl
Where v1 is the average entry velocity and v2 is the average return wave velocity as depicted in
Figure 3. A sub-routine has been written for FLOW-3D to allow the extraction of this criterion at
a predetermined time period.
To obtain the Fr number variables are defined for the subroutine in an input file. These are: cell
plane and mesh block in which to undertake the calculation, cell values for both the top and
bottom of the runner, height at which to scan to find the metal front, and the predetermined time
step at which to undertake the operation.
The sub-routine takes the following steps to obtain the Fr number for each predetermined time
step (Figure 3):
1. The cells along the predefined plane at the defined height are scanned until a cell with
fluid is detected.
10
2. The cells in the vertical plane are then scanned to check they are full of fluid. If the cells
in this column are not full of fluid the next column is assessed until the first column of
full fluid cells is found.
3. From the predefined top cell the column is scanned searching for a change in flow
direction. If more than one change of flow direction is found an output of -1 is given to
indicate turbulent flow.
4. The distance from the cell where the flow direction changes to the predefined bottom cell
in the runner is labelled l.
5. The average velocities v1 and v2 are calculated.
6. The Fr number is then calculated using the values of l, v1 and v2 obtained using Equation
3. This is then output to a text file.
Velocity (ms-1)
Figure 3. 2D Return wave showing Fr calculation method
Sumps
The addition of a sump to a casting running system has historically had different levels of
success. Two main reasons for addition have been identified. The first is to capture the initial
fluid volume which is believed to contain the highest concentration of oxide films and other
inclusions, thus stopping this fluid volume entering the casting [10]. For this reason the sump is
often also known as a ‘dross trap’. The second is to dissipate energy so as to reduce free surface
turbulence during the transient filling of the running system [11].
Experimental Design
A simple running system was designed which conformed to known ‘best practice principles’ for
a medium sized aluminium casting using a mass flow rate of 2.54 kgs-1 and a sprue exit velocity
of 3.5 ms-1 [2] (Figure 4). Three different in-gate heights and three different sump heights, in
addition to a “no sump” case were chosen. A full experimental matrix was simulated and the Fr
number data extracted (Table I).
11
As can be seen in Figure 4 not all of the down sprue was modelled. This was to save computation
time. However enough downsprue was modelled to allow a parabolic fluid front to form before
impacting with the runner bar, using a pressure equivalent to a total head height of 0.6 m.
Therefore the results are in no way affected.
Downsprue (not
A
to scale)
Modelled
B
downsprue
C Runner
D In-gate
E Casting volume
E F Sump
A H G In-gate height
600 (Not to scale)
H Sump Height
F
D G
B
Figure 4. Running system designed to best practice

C
principles. (Trial 5)
Results
The extracted Fr number results were integrated with respect to time to give a total damage value
for each trial (Table I).
Table I: Trial Matrix and Results

Sump height In-gate height Running system
Trial Total Fr
(mm) (mm) Filling Time (s)
1 500 25 11646.13 1.93
2 500 50 11420.91 1.85
3 500 100 8170.50 1.48
4 250 25 9892.41 2.03
5 250 50 8520.82 1.73
6 250 100 6498.81 1.42
7 125 25 10230.44 2.00
8 125 50 8888.40 1.75
9 125 100 6058.59 1.27
10 0 25 10071.36 1.76
11 0 50 9368.87 1.65
12 0 100 7695.52 1.36
12
Discussion
These results show the best case to be Trial 9 (125 mm sump & 100 mm in-gate) and the worst
Trial 1 (500 mm Sump & 25 mm In-Gate). The single highest Fr value of 11.96 was in Trial 13
and the single lowest an Fr of 2.57 in Trial 6, therefore all values exceed the 1.7 entrainment
threshold.
The persistence of the wave

has a large effect on the total
damage. The 92% increase in
the damage for Trial 1 when 12000
compared to Trail 9 was
largely due to the increased 11000
persistence (Figure 6).
10000
Statistical Analysis
9000 Total Fr
An ANOVA (Analysis of
Variance) was carried out 8000
which showed both variables
to be significant to a 5% 7000
significance level; the in-gate 25
6000
was shown to be the most 50 0
significant at 0.1% compared
In-Gate Height 125
to the sump at 3.3% (mm) 100 Sump Height (mm)
significance. Low level 250
interactions were also 500
identified.
Figure 5. Response surface: Fr v. sump height v. in-gate height
12
10
8
Fr Number
4 Trial 1 (Worst)
Trial 9 (Best)
2
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8 2
Time (s)
Figure 6. Fr Number Vs Time Plot for best and worst cases
13
Conclusions
1. The design of a casting’s in-gate is of upmost importance, as this controls the rate of back
pressurisation and thus the period required to prime the area between the in-gate and the
down sprue.
2. The design of a sump is critical to its effectiveness as an incorrectly designed sump can
be extremely detrimental to casting integrity.
3. Interaction is present between the sump and in-gate design and casting integrity, so
therefore the system must be designed as a whole.
Acknowledgments
The authors would like to acknowledge the help of the help of Jean-Christophe Gebelin, Prof.
Nick Green and The Department of Mechanical and Manufacturing Engineering, The University
of Birmingham for sponsoring my PhD.
References
1. Green NR & Campbell J, “Statistical Distributions of fracture strengths of cast Al-7Si-Mg

Alloy”, Materials Science and Engineering, A173 (1982), 261-266.
2. Runyaro J, Boutorabi SMA & Campbell J, “Critical gate velocities for film-forming casting
alloys: a basis for process specification” AFS Transactions, 100 (1992), 225-234.
3. Nyahumwa C, Green NR & Campbell J, “Effect of mould-filling turbulence on fatigue

properties of cast aluminium alloys”, AFS Transactions, 106, (1998), 215-223
4.Campbell J, Castings (Butterworth Heinemann, 1991)
5. Campbell J, “Review: developments in filling system design” CIATF Internat. Tech. Forum,
(1997) 17
6. Campbell J, “Ten rules for good castings”, Modern Castings, 87 (1997), 36-39.
7. Robertson AD & Sheridan AT, “Water modelling of liquid steel at Swinden laboratories”,
Journal of the iron and steel institute, 208, (1970), 625-632.
8. Campbell J, “Thin wall castings”, Materials science and technology, 4, (1988), 194-204.
9. Henderson F, Open Channel Flow (New York, Macmillan, 1971), 214-218.
10. Jolly MR, Lo H.S.H, Turan M, Campbell & J, Yang X, “Development of practical quiescent
running systems without foam filters for use in aluminium castings using computer modelling”,
Modelling of casting, welding and advanced solidification processes IX, (Eds. Sahm P,
Hansen P, Conley J, Aachen, Shaker Verlag, 2000) 319-325.
11. Hsu FY, Jolly MR & Campbell J, “Vortex gate design for gravity castings” Shape casting,
the John Campbell symposium (Eds. Tiryakiolglu M & Crepeau P, 2005, Warrendale, TMS),
73-82.
14
Phase field simulation of irregular eutectic solidification
Ruijie Zhang, Mei Li and John Allison

Ford Research and Innovation Center, Ford Motor Company
Dearborn, Michigan 48124, USA
Keywords: Phase field, Anisotropy, Irregular eutectic, Solidification
Abstract
In real multiphase alloy systems, facet phase often appears in the solidification process.
These facet phases are usually the highly anisotropic stoichiometric intermetallic compounds
and solidify as a eutectic phase in solidification process. In this paper, the multiphase phase
field model was extended to describe the solidification of irregular eutectic alloy. The strong
anisotropy in interfacial energy and phase field mobility were considered. As an example, the
simulation of irregular eutectic growth in Al-Si alloy was executed.
Introduction
The phase-field model is becoming a powerful tool which can describe the complex
interface pattern evolution. The phase-field models have been originally developed for
solidification of two phase system [1-5] and then extended to multiphase system [6-11]. In real
multiphase alloy systems, facet phase often appears in the solidification process, such as Si in
Al-Si alloy [12], Mg2Si in Al-Mg-Si alloy [13]. The quenched solid-liquid interface of Al-Si
irregular eutectic [14] was shown in Fig.1. These facet phases are usually the highly
anisotropic stoichiometric intermetallic compounds and solidify as a eutectic phase in
solidification process. Their size, distribution and volume fraction are key factors which
greatly affect the materials mechanical performance [15]. So simulation of the growth of such
phase will be very important for the alloy design and materials performance prediction.
In this paper, the multiphase phase field model [10] was extended to describe the
solidification of irregular eutectic alloy. The strong anisotropy in interfacial energy and phase
field mobility were considered. As an example, the simulation of irregular eutectic growth in
Al-Si alloy was executed.
Multiphase phase field model

In multiphase system, its free energy function can be given by [10]:
⎡ ⎛ ⎞⎤
F = ∫ ⎢f P
+ f T + λ L ⎜ ∑ φi − 1⎟⎥ dV (1)
V
⎣ ⎝ i ⎠⎦
where λ L is the Lagrange multiplier, f P

can be defined by:
⎡ ε ij2 ⎤
f P
= ∑∑ ⎢− ∇φi ⋅ ∇φ j + ω ij φiφ j ⎥ (2)
⎢ 2
j >i i ⎣ ⎦⎥
where ε ij is the gradient energy coefficient and ω ij is the height of the double well
potential. For the thermodynamics potential f T , it can be assumed a rule of mixture:
f T = ∑ φi f i (ci ) (3)
i
15
where f i (ci ) is the free energy density of i phase with composition ci. The composition of
phases coexisting at a given point is constrained by the following equation, i.e. the equal
chemical potential condition:
f c11 [c1 (x, t )] = f c22 [c 2 ( x, t )] = f c33 [c3 ( x, t )] ≡ f c (x, t ) (4)
where the subscripts ci under the free energy density denote the derivatives by them. Average
composition of the mixture is also given by a mixture rule:
c ( x, t ) = ∑ φ i c i (5)
i
The sum of each phase fields at any position in the system is conserved:
∑φi
i =1 (6)
A step function si ( x, t ) = 1 if φi > 0 and si ( x, t ) = 0 otherwise were introduced into the
model, so the phase field equation can be described as:

∂φi 2 n ⎡ δF δF ⎤
= − ∑ s ij M ij ⎢ − ⎥ (7)
∂t n j ≠i ⎣⎢ δφi δφ j ⎥⎦
where
δF ⎡ ε ij 2
⎤
= ∑ ⎢ ∇ 2φ j + ω ij φ j ⎥ + f i (ci ) − ci f c (8)
δφi j ≠i ⎢⎣ 2 ⎥⎦
s ij = s i ( x, t ) s j ( x, t ) (9)
n ( x, t ) = ∑ s i ( x, t ) (10)
i
Mij is the phase field mobility.

The diffusion equation where the mass should be conserved can be written as:
∂c
= ∇ ⋅ D∇c − ∇ ⋅ D ∑ ci ∇φi (11)
∂t i
This equation can also be written as an equivalent, but more compact and convenient form:
∂c
= ∇ ⋅ D ∑ φ i ∇c i (12)
∂t i
There are three unknown model parameters in the evolution equations (7), i.e. anisotropic
phase field mobility M ij (θ ij ) , anisotropic gradient energy coefficient ε ij (θ ij ) and ω, which
relate to materials constants such as interface energy σ ij (θ ij ) , interface thickness 2λij (θ ij )
kinetics coefficient μ ij (θ ij ) . For a quantitative simulation, we must establish the
relationships between these model parameters and materials constants. Analyzing the
equilibrium properties of kinetic equations (7) and (12) via thin interface limit analysis [3], the
relationship among model parameters and materials constants can be obtained:
ε 13 (θ13 )
2λ13 (θ13 ) = π (13)
2ω13
16
π
σ 13 (θ13 ) = ε13 (θ13 ) 2ω13 (14)
8
1 Vm m1σ 13 (θ13 ) m (1 − k1 )ε 13 (θ13 ) e
=− + 1 c13ζ 13 (15)
μ13 (θ13 ) RTM 13 (θ13 )(1 − k1 )ε 132 (θ13 ) 2ω13
1 1 φ (1 − φ )
ζ 13 =
DL ∫ 1 − φ (1 − k ) dφ
0
1
(16)
where the subscript “1” means α phase and “3” means liquid phase, m1 is the liquid slope, k1
is the solute partition coefficient, Vm is the molar volume. For the interface between β phase
and liquid, a similar relationship can also be derived.
In the present work, we assumed that the interface energy of facet phase has cylindrical
symmetry. It can be described as [16]:
⎧1 + Aij + Bij sin(θ ij ), − π / 2 ≤ θ ij ≤ −π / 2 + θ 0
σ ij0 ⎪
σ ij (θ ij ) = ⎨1 + γ ij cos(θ ij ), − π / 2 + θ 0 ≤ θ ij ≤ π / 2 − θ 0 (17)
1 + γ ij ⎪
⎩1 + A ij − Bij sin( θ ij ), π / 2 − θ 0 ≤ θ ij ≤ π / 2
where σ ij0 is the interface energy at θ ij = 0 , γ ij is the amplitude of the anisotropy and
determined by the interface energy at θ ij = π / 2 , Aij = γ ij / sin (θ 0 ) , Bij = γ ij cos(θ 0 ) / sin (θ 0 ) .
θ 0 = π / 200 is chosen as a very small angle to describe two cusps at θ ij = ±π / 2 [17]

.
Because there is no experimental data on the kinetics coefficient, we give the phase field
mobility M ij (θ ij ) the same angular dependence [17, 18] as σ ij (θ ij ) :
⎧1 + X ij + Yij sin(θ ij ), − π / 2 ≤ θ ij ≤ −π / 2 + θ 0
M ij0 ⎪
M ij (θ ij ) = ⎨1 + vij cos(θ ij ), − π / 2 + θ 0 ≤ θ ij ≤ π / 2 − θ 0 (18)
1 + vij ⎪
⎩1 + X ij − Yij sin(θ ij ), π / 2 − θ 0 ≤ θ ij ≤ π / 2
where M ij0 is the phase field mobility at θ ij = 0 , vij is determined by the phase field
mobility at θ ij = π / 2 , X ij = vij / sin (θ 0 ) , Yij = vij cos(θ 0 ) / sin (θ 0 ) . θ 0 is again taken to be
π / 200 .
Application to Al-Si system

Eutectic Al-Si alloys are among the most widely used aluminum foundry alloys today [19].
Its physical parameters have been carefully measured with a reasonable accuracy. In the
simulation, the following parameters were adopted: diffusivity in liquid and solid are
DL = 1.34 × 10 −7 exp(−30000 / RT ) m2⋅s−1 and DS = 1.38 × 10 −5 exp(−117600 / RT ) m2⋅s−1,
respectively [20]. Interface energy between α-Al and liquid is 0.168 J⋅m−2 [21], its anisotropy is
set to be 0.03 [22]. Interface energy between Si and liquid is 0.352 J⋅m−2 [21], an anisotropic
coefficient 10 is adopted [17, 23]. The phase field mobility between α-Al and liquid is assumed
to be no anisotropy and can be determined by the vanishing kinetics coefficient condition [3],
i.e. 1 μα − L → 0 . For the phase field mobility between Si and liquid, it was assumed that
17
phase field mobility at θ Si − L = 0 , i.e. M Si0 − L , was also determined by vanishing kinetics
coefficient condition [3]. An anisotropy coefficient, i.e., vSi − L =1000 was adopted [17, 24]. Then
its phase field mobility can be determined by Eq. (18). The grid size was set to 0.2 μm. The
initial bulk alloy composition was set to the eutectic composition, i.e. 0.113 [25].
Four Si seeds were initially placed at the bottom of the simulation area. Different small
crystallographic angles between y direction were set to these four Si seeds. The simulated
irregular eutectic solidification of Al-Si alloys was shown in Fig. 2. We can see that Si grows
rapidly out from the interface, and the α-Al immediately follows, covering everything behind
the Si tips. We can also see that Si and α-Al can speed up the growth of each other and the
growth of Si is highly anisotropic. These all agree well with the experimental results.
Summary
The multiphase phase field model was extended to describe the solidification of irregular
eutectic alloy. The strong anisotropy in interfacial energy and phase field mobility were
considered. As an example, the simulation of irregular eutectic growth in Al-Si alloy was
executed. It can be observed that growth of Si is highly anisotropic, which agree well with
the experimental results.
Reference
[1] A. Karma. Phys. Rev. Letters, 2001, 87, 115701.
[2] A.A. Wheeler, W.J. Boettinger and G.B. McFadden. Phys. Rev. A, 1992, 45, 7424.
[3] S.G. Kim, W.T. Kim and T. Suzuki. Phys. Rev. E, 1999, 60, 7186.
[4] A.A. Wheeler, W.J. Boettinger and G.B. McFadden. Phys. Rev. E, 1993, 47, 1893.
[5] R. Folch and M. Plapp. Phys. Rev. E, 2005, 72, 011602.
[6] A. Karma. Phys. Rev. E, 1994, 49, 2245.
[7] I. Steinbach and F. Pezzolla. Physica D, 1999, 134, 385.
[8] B. Nestler and A.A. Wheeler. Physica D, 2000, 138, 114.
[9] M. Apel, B. Boettger, H.J. Diepers and I. Steinbach. J. Cryst. Growth, 2002, 237-239,
154.
[10] S.G. Kim, W.T. Kim, T. Suzuki and M. Ode. J. Cryst. Growth, 2004, 261, 135.
[11] B. Böttger, J. Eiken and I. Steinbach. Acta Mater., 2006, 54, 2697.
[12] M. Gündüz, H. Kaya, E. Cadırlı and A. Özmen. Mater. Sci. Eng. A, 2004, 369, 215.
[13] M.L. Santella, T. Engstrom, D. Storjohann and T.Y. Pan. Scripta Mater., 2005, 53, 201.
[14] J.F. Major and J.W. Rutter. Materials Sci. Tech., 1989, 5, 645.
[15] E. Guzik and D. Kopycinski. Metall. Mater. Trans. A, 2006, 37, 3057.
[16] I. Loginova, J. Ågren and G. Amberg. Acta Mater., 2004, 52, 4055.
[17] S.Y. Hu, J. Murray, H. Weiland, Z.K. Liu and L.Q. Chen. Calphad, 2007, 31, 303.
[18] J.M. Debierre, A. Karma, F. Celestini and R. Guérin. Phys. Rev. E, 2003, 68, 041604.
[19] S. Nafisi, O. Lashkari, R. Ghomashchi, F. Ajersch and A. Charette. Acta Mater., 2006, 54,
3503.
[20] Y. Du, Y.A. Chang, B.Y. Huang, W.P. Gong, Z.P. Jin, H.H. Xu, Z.H. Yuan, Y. Liu, Y.H.
He and F.Y. Xie. Mater. Sci. Eng. A, 2003, 363, 140.
[21] M. Gündüz and J.D. Hunt. Acta Metall., 1985, 33, 1651.
[22] R. Kobayashi. Physica D, 1993, 63, 410.
[23] T. Suzuki, S.G. Kim and W.T. Kim. Mater. Sci. Eng. A, 2007, 449-451, 99.
[24] J.J. Hoyt, M. Asta and A. Karma. Mater. Sci. Eng. R, 2003, 41, 121.
[25] H. Feufel, T. Gödecke, H.L. Lukas and F. Sommer. J. Alloys and Comp., 1997, 247, 31.
18
(a)
(b)
Fig.1 Quenched solid liquid interface of directional solidified Al-Si alloys [14]
(a) Pulling speed 10 nm⋅s−1 (b) Pulling speed 20 nm⋅s−1
400
300
200
100
200 400 600 800

Fig.2 Simulated irregular eutectic solidification of Al-Si alloys
19
A NUMERICAL SCHEME FOR SOLVING MICROSEGREGATION FOR

SOLIDIFYING METALLIC ALLOYS
Salah Uddin1 and M. Hasan1

1
Department of Mining and Materials Engineering
McGill University, M.H. Wong Building
3610 University Street, Montreal, QC, Canada H3A 2B2
Abstract
In this study, the microsegregation problem which arises during solidification of an alloy was
analyzed for three different geometrical shapes namely, rectangular, cylindrical and spherical
dendrite arms and for several pertinent parameters. A previously proposed numerical method for
solidification/melting problems was extended in this study to deal with solute diffusion in both
solid and liquid regions. An algorithm is proposed to solve the strongly coupled model transport
equations. The algorithm is based on the control volume finite-difference scheme with an
appropriately transformed gird system. In order to verify the accuracy of the present method with
regard to tracking the solid/liquid interfaces in the microsegregation problem, the well-known
analytical solution of the Stefan problem was used. A good agreement between the model
predictions and the analytical solution was found. The developed computational procedure was
also found to be stable for a wide range of values of the parameters.
Introduction
Microsegregation is a complex phenomenon where heat and mass transport are coupled
with growing dendrites and the thermodynamic conditions of the system. Sometimes multiple
moving boundaries are needed to be tackled during microsegregation particularly this is true in
the case of coarsening and peritectic transformation.
Problem formulation
For phase change problems the conductive-convective heat transfer is governed by

unsteady energy equation and the continuity equation: These equations in one dimensional form
are shown below:
∂ n ∂
( x ρi ) + (ρi fi ) = 0 (1)
∂t ∂x
∂ n ∂ ∂ ∂T
( x ρ i hi ) + ( ρ i f i hi ) = ( x n k i i ) + x n S H i (2)
∂t ∂x ∂x ∂x
Here n = 0, 1 and 2 for planar, cylindrical and spherical geometry, respectively. Phase index
i can vary from 1 to N depending on the number of phases present in the system. Specific
enthalpy and volumetric heat generation terms are denoted as hi and S H i respectively. So,
hi = C Pi Ti , where C Pi is the specific heat. Here, f i = x n ui , stands for 1-D convective motion
which is caused by volume changes between the phases. The governing equation for mass
transport for species A is given below:
21
∂ n ∂ ∂ ∂W Ai
( x ρ iW A i ) + ( ρ i f iW Ai ) = ( x n ρ i Di ) + xnSM i (3)
∂t ∂x ∂x ∂x
Here, W Ai is the weight fraction of species A in phase i which is related to density as follows:
ρ Ai
W Ai = (4)
ρi
The density and diffusivity are denoted as ρ i and Di respectively and S M i represents volumetric
mass source of the system. The thermal condition at the interface and the interfacial energy
balance are shown below [1]:

Tm = Tm +1 = Tm (5)

dX ∂T dX ∂T
ρ m (u m − m )hm − k m m = ρ m +1 (u m +1 − m )hm +1 − k m +1 m +1 (6)
dt ∂x dt ∂x

Here Tm and X m are the phase transition temperature and the position of the interface
respectively. Subscript m and m+1 represent the adjacent phases for the interface where the
phase transformation is taking place. The mass transfer counterpart for equations 5 and 6 can be
written as follows for species A:
W Am = K W Am+1 (7)

dX m ∂W A m dX m
ρ m (u m − ) W A m − ρ m Dm = ρ m +1 (u m +1 − ) W A m +1 −
dt ∂x dt
∂W A m +1
ρ m +1 Dm +1 (.8)
∂x
Here, K is the partition coefficient and is determined from the relationship between the solute
concentrations in the adjacent phases at the interface. The problem has been designed to solve in
a fixed domain in terms of the dimensionless coordinate η i which varies from 0 to 1 and
immobilizes the moving boundaries. It can be expressed as follows [2]:

x − X i −1
ηi = (9)
δi

Here, δ i = X i − X i −1 and x is the distance from the origin which lies between the two interfaces
X i and X i −1 .
The transformed energy equation in this new coordinate system is given below [2]:
∂ ∂V ∂J ∂V
( ρ i hi i ) + i = S H i ( i ) (10)
∂t ∂η i ∂η i ∂η i
∂V
Fi (η , t ) = ρ i ( f i − i ) (11)
∂t
X i n k i ∂Ti
J i (η , t ) = Fi hi − (12)
δ i ∂η i
1
Vi (η , t ) = ( X i (η , t )) n +1 (13)
n +1

X i (η , t ) = η i δ i (t ) + X i −1 (t ) (14)
22

Here X i is the same as the coordinate x and X i −1 ≤ X i ≤ X i . The transformed equation for
mass transport can be written as follows for species A:
∂ ∂V ∂G ∂V
( ρ iW A i i ) + i = S M i ( i ) (15)
∂t ∂η i ∂η i ∂η i
X i n ρ i D i ∂W A i
Gi (η , t ) = FiW A i − (16)
δi ∂η i
Solution procedure
All the equations described above i.e. the diffusion equations, interfacial balances and the
thermodynamic conditions, are coupled to each other and always pose a considerable difficulty
from computational point of view. Many algorithms have been proposed in the literature and a
number of algorithms came up with reasonable results. The algorithm adopted by Kim and
Kaviany [2] to solve the phase change problems without solute diffusion was proposed by
Sparrow and Chuck [3]. But when solute diffusion is present the explicit method of tracking the
moving front as used by Sparrow and Chuck is not applicable. The other algorithms available in
the literature either do not fit with our problem of interest or give unreasonable results and lead
to instability and fluctuations. For this reason an algorithm was developed to solve the above
equations [4]. Type B-grid [5] was used in both phases. The positions of the control volume
faces were fixed in each phases according to the following expression:
pi
⎛ j −1 ⎞
η j = ⎜⎜ ⎟⎟ (17)
⎝ M i −1⎠
Here, M i is the total number of control volume faces in phase i and li is the power
suitable to the problem. In the calculations reported here M 1 = M 2 = 500 . The temperature and
concentration gradients can be very steep surrounding the solid/liquid interface and this is
particularly true when the solidification rate is high. To capture this gradient the grid points were
concentrated close to the interface by using the control parameters p1 = 0.9 and p 2 = 1.1 . The
concentration variations in the phases for different parameters were analyzed for the rectangular,
cylindrical and spherical dendrites. For the following simulations one-half dendrite arm spacing

was arbitrarily set to X 2 = 20μm . Time step was taken as 1 μm in addition to the interface
conditions for energy and mass as described above, the boundary conditions were assumed to be
symmetric at both ends of the system.
Results and discussion
Solute distributions in the solid and liquid side of a growing dendrite arm were calculated
using the above mentioned numerical scheme. Simulations were carried out for the Al-4.5wt%
Cu alloy. The thermophysical properties and thermodynamic parameters used in these
calculations are given in Table 1.
23
Table 1 – Thermophysical properties and phase diagram parameters [6,7]
Properties and phase diagram parameters Al – 4.5wt%Cu
Liquid density (kg/m3) 2460

Solid density (kg/m3) 2750
Liquid specific heat (J/kg K) 1054
Solid specific heat (J/kg K) 958
Latent heat of fusion (kJ/kg) 390
Liquid thermal conductivity (W/m K) 95
Solid thermal conductivity (W/m K) 180
Liquid diffusion coefficient (m2/s) 5.0×10-9
Solid diffusion coefficient (m2/s) 5.0×10-13
Melting point of Al (K) 933.5
Eutectic temperature (K) 821.2
Eutectic composition (wt %) 0.33
Equilibrium partition coefficient 0.171
The primary and secondary dendrites that are normally seen in the mushy zone are close
to a cylinder in shape. That is why this is the most appropriate geometrical system to be
considered in microsegregation modeling. The solute distribution in solid phase was calculated at
different cooling rates for cylindrical dendrites and is shown below:
Figure 1 Variation of concentration with distance inside cylindrical dendrite at 10E-3 sec. in
different cooling rates
At higher cooling rates the solid-liquid interface velocity increases but the time to diffuse
solute atoms decreases. That is why at higher cooling rates the amount of solid portions increases
but due to the small diffusion time the concentration levels at the inner part of the solid remain
almost unchanged as shown in Figure 1.
Distributions of solute concentration in liquid for different partition coefficients for
cylindrical dendrite are shown in Figure 2.
24
Figure 2 Variation of concentration with distance in the melt surrounding a cylindrical dendrite
at 10E-3 sec. and for a 500 K/sec. cooling rate for different partition coefficient
Comparison between different systems
Solute distributions were also compared for three different geometrical shapes of a
dendrite arm. Solute concentration variations with distance in the shrinking liquid at a particular
instant of 10E-3 sec. are shown in Figure 3 for rectangular, cylindrical and spherical dendrites. It
is seen that the growth velocity is the highest for a spherical dendrite then for a cylindrical
dendrite and is the lowest for the rectangular dendrite. Higher cooling rates are associated with
spherical and cylindrical geometries due to the curvature effect. As the growth velocity
increases, the higher amount of solute atoms is rejected from the solid to the liquid. This is the
reason why the surrounding liquid of the spherical dendrite is more enriched with solute and
disappears quickly compared to the other two shapes as is evident in Figure 3.
Figure 3 Variation of concentration with distance in the melt surrounding a rectangular (n = 0),
cylindrical (n = 1) and spherical dendrite (n = 2) at 10E-3 sec. for a 500 K/sec. cooling rate
25
Summary
The problem of microsegregation problem was analyzed for three different geometrical
shapes of a dendrite arm and for several pertinent parameters. A previously proposed numerical
model based on coordinate transformation technique was extended in this study to deal with
solute diffusion in the growing solid and in the shrinking liquid phases. An improved algorithm
was proposed to solve the model equations which are strongly coupled to each other. The
computational procedure developed here was found to be very stable for a wide range of
parametric values. The control volume based finite difference scheme with an appropriate gird
system was employed to discretize the equations and numerically solve the problem. Here, the
power-law scheme was chosen to discretize the convective terms as this scheme is equally
applicable for a low interface velocity to a higher one. The model is also expected to handle
problems involving multiple moving boundaries with solute diffusion in micro- and macro-
domain with and without latent heat generation or extraction.
References
1. V.S. Arpaci and P.S Larsen, Convection heat transfer (New Jersey, NJ: Princeton-Hall,
Englewood Cliffs, 1984).
2. C.-J. Kim and M. Kaviany, “A Numerical Method for Phase-change Problems”, Int. J.
Heat mass transfer, 35 (1990), 2721-2734.
3. E.M. Sparrow and W. Chuck, “An Implicit Explicit Numerical Solution Scheme for
Phase Change Problems”, Numerical Heat Transfer, 7 (1984), 1-15.
4. Salah Uddin, “Semi-analytical and Numerical Modeling of Microsegregation for

Solidifying Metallic Alloys”, M.Eng. Thesis, Department of Ming, Metals & Materials
Eng., McGill University, QC, Canada, August 2007 (submitted).
5. S.V. Patankar, Numerical Heat Transfer and Fluid Flow (Washington, DC: Hemisphere,
1980)
6. C.J. Vreeman and F.P. Incropera, “The Effect of Free-floating Dendrites and Convection
on Macrosegregation in Direct Chill Cast Aluminum Alloys. II. Predictions for Al-Cu
and Al-Mg Alloys”, Int. J. Heat Mass Transfer, 43 (2000), 687–704.
7. G,-X. Wang, V. Prasad and E.F. Matthys, “An Interface-tracking Numerical Method for
Rapid Planar Solidification of Binary Alloys with Application to Microsegregation”,
Materials Science and Engineering, A225 (1997), 47-58.
26
ADVANCES IN NDT TECHNIQUES FOR FRICTION STIR WELDING

JOINTS OF AA2024
Telmo Santos, Pedro Vilaça, Luís Reis, Luísa Quintino, Manuel de Freitas
Technical University of Lisbon, Instituto Superior Técnico, IDMEC;

Av. Rovisco Pais, 1049-001 Lisboa, Portugal
Keywords: Friction Stir Welding, AA2024-T851, Eddy Currents Probe
Abstract
Industrial applications of solid state welding technology have undergone a significant

development with the advent of Friction Stir Welding (FSW). Although the good quality of FSW
joints some defects may arise which are difficult or even impossible to detect with conventional
NDT techniques. This work addresses an innovative NDT Eddy currents probe that was
developed and tested for quality assessment of FSW joints of aeronautic aluminium alloy
AA2024-T351. The influence of defects with different locations and morphology in joint
mechanical efficiency are investigated under fatigue loads. The application potential of the new
NDT Eddy currents probe in detecting the different defects is evaluated and compared with other
NDT techniques. The results show a strong dependence between FSW parameters and defects
formation and the feasibility in using the new NDT Eddy currents probe mainly concerning the
detection of root defects which have a critical role in mechanical joint efficiency.
Introduction
Although the friction stir welding (FSW) joints have a better quality compared to the fusion
techniques, there are still some defects that may arise and which are very sensitive to small
variations in process parameters. The assessment of the role of these defects in the overall
resistance of friction stir welded structures under fatigue loading, typical from any aeronautical
application, is a crucial issue. The aeronautical industry demands not only the feasibility but also
high levels of reliability of the detection procedures for all the FSW defects [1].
Unfortunately, the typical non-destructive testing (NDT) techniques, such as: visual inspection,
magnetic particles, liquid penetrant and X-ray, do not enable the detection or quantification of
the typical FSW defects. The ultra-sounds and eddy currents NDT techniques, even in their most
recent form of evolution: phased array and eddy currents array, allow the detection of most of the
defects in FSW joint. However they are very sensitive to coupling and lift-off conditions
between the probes and the surfaces under inspection [2]. In this work the technological and
physical fundaments of a new probe for NDT inspection are addressed and some experiments are
presented enabling to tests and compare different working parameters of the new proposed IOnic
probe for NDT inspection of FSW joints.
In order to know the relative importance of different defect types in the mechanical behaviour of
FSW structures under fatigue loads, specimens welded by friction stir with two different root
defects and one internal defect were tested and correspondent fracture surfaces investigated.
27
FSW Typical Defects
Typical defects that may arise in FSW joints are represented in Figure 1, resulting from, e.g.,
imperfect stir of the materials during the processing, inadequate surface preparation, lack of
penetration of the pin and non-uniform vertical forging forces along the material thickness. Some
characteristic FSW defects are lack of penetration (typically addressed as kissing-bond), root
flaw (concerning weak or intermittent linking), voids on the advancing side and second phased
particles and oxides alignment under the shoulder.
Figure 1 – Typical defects on butt joint FSW configuration
The geometry, location and microstructural nature of the FSW defects, which bore no
resemblance with defects typical of fusion welding of aluminium alloys, lead to difficulties in
identification when using the common NDT techniques [2].
IOnic Probe
In fact, the high-sensitive lift-off effect of conventional eddy current probes generates a noise
which hides the signal produced by the typical FSW small defects, making the detection of those
defects impossible. In order to avoid this problem, a new NDT eddy current probe called IOnic
Probe was developed, tested and compared with two other eddy current probes: conventional
cylindrical helicoidally coil and spiral plane coil. The preliminary results indicate that the new
probe is more reliable in detecting and evaluating depth defects than conventional probes.
The IOnic Probe [3] consists in two inductors, one exciting coil perpendicular to the surface
material and one sensitive coil characterized by a special patented symmetric coil display and a
relative position to the first one that minimizes the lift-off effect. With this design the detection
of the defects is based in the induced voltage on the terminals of the sensitive coil, rather than in
the usual impedance measurements.
In order to validate the concept a prototype was built and tested for two extreme cases of lift-of
and conductivity (Figure 2).
28
Figure 2 – IOnic probe signal along X and Y directions (f=85 kHz; I=50mA)
Figure 2 shows the typical signal obtained by the IOnic Probe along X and Y directions, starting
from the center of the aluminium plate AA2024-T351 and stopping outside the boundaries of this
plate. The results indicate that both real and imaginary output voltage are kept constant when the
probe is moved along the Y direction, demonstrating the signal independence to the lift-off
effect. On the other hand, in the X direction there is a 400% signal change, which confirms the
high sensitivity of to the probe to the conductivity changes within the material.
The subsequent test consisted in comparing the IOnic probe with conventional cylindrical
probes. An aluminium plate AA2024-T351 with 4mm thickness and a standard hole defect of
1mm diameter in the center was used in the experiment. The probes were put 25mm away from
the hole and then moved towards the hole in a rectilinear direction until they were brought to a
standstill 25mm after the hole. The real and imaginary signal of both probes was acquired along
this displacement and the results are given in Figure 3.
Figure 3 – Real and imaginary signal of IOnic and conventional cylindrical probes
(f=85 kHz; I=50mA)
The amplitude of real and imaginary part of the output voltage for the IOnic probe is respectively
two and five times bigger than for the conventional probe. It means that the IOnic is more
sensitive and therefore more reliable for defect detection.
29
A third experiment was developed, where the lift-off and conductivity changes in the impedance
diagram of the IOnic probe were compared with three different types of planar spiral coils: 20
circular, 10 circular and 10 squared coils (Figure 4). All coils were printed on a circuit board and
have a thickness of 90µm, a height of 30µm and a distance between two successive coils of
90µm. These types of probes have been suggested to have a high potential for several NDT
applications, due to their close proximity to the surface material and the possibility of being
printed on a flexible sheet.
Figure 4 – Conductivity and lift-off curves on the impedance plane.

a) Planar spiral coils; b) Ionic Probe
The lift-off noise tests were conducted on standard thin film polymers of different thicknesses on
top of the material surface and the conductivity tests were carried out on four different materials:
Cu, AA2024, AA5083 and 99.94-wt% Pb with 100%, 37.8%, 29.9% and 8.1% of the IACS
respectively. The results depicted in Figure 4 reveal that the signal of the planar spiral coils is
much more sensitive to the lift-off effect than to the conductivity changes (Figure 4a), while the
IOnic probe signal has a much greater response to the conductivity change when compared with
the lift-off signal (Figure 4b).
The reliability of the eddy current probes for NDT applications is strongly dependent on a
superior response to the conductivity changes than to the lift-off. Therefore the IOnic probe is a
considerable improvement to the spiral plane coil probes.
Assessment of the Influence of Typical FSW Defects in Fatigue Behaviour
In order to assess the influence of some of the most typical defects in FSW joints, non-defective
and defective weld joints, with three different defect types, were produced in aeronautic
aluminium alloy AA2024-T351 with a thickness of 4mm. The characterization of these defect
types is described in Table 1. Two different tools (a combination of one shoulder with two
different pins) were implemented to produce the 4 different FSW joint conditions (Defect Type:
0, I, II and III), as shown in Figure 5. The shoulder with 2 spiral striates has an outer diameter of
14mm and the 2 pins are about 5mm in diameter. Other process parameters were rotation speed
of 710rpm, travel speed of 224mm/min and tilt angle of 0.5degrees.
In summary, the two different root defects: Defect Type I and Defect Type II, were obtained by
decreasing the pin length from the non-defective weld joint (Defect Type 0). The internal defect
(Defect Type III) was obtained by the application of a cylindrical smooth surface pin, with 3
30
small helicoidal groves at the tip of the pin, which along with the correct pin length enabled to
prevent root defects.
Defect Type
0 I II III
Code
Not Root Defect Type I Root Defect Type II Internal defects
Description
Defective (Particles Alignment) (Kissing-Bond) (Voids)
Table 1 – Establishment of the 4 different Defect Types included in the FSW joints produced
Figure 5 –Two different FSW tools used to produce the 4 different Defect Types
In order to investigate the fatigue behaviour of the AA2024-T351, base material and friction stir
welds specimens, including the 4 different defect types, were prepared in the as welded
condition. The fatigue tests are performed on an Instron, model 8874, with a load cell of 25kN.
Stress ratio R is 0.1. Oscillation frequency was typically set to 10Hz. The S-N curve results
obtained are presented in Figure 6.
Figure 6 – Fatigue resistance results for base material and 4 different defect type conditions.
a) S-N curve; b) Number of cycles efficiency relatively to the base material performance
31
Figure 7 – SEM fractography’s illustrating the localization of cleavage planes in the vicinity of
Defect Types I, II and III. a) Root Defect Type I; b) Root Defect Type II; c) Internal Defect
Type III; d) Detail of c)
The analysis of the fatigue results (Figure 6) both emphasizes the good quality of the Defect
Type 0 FSW joints, with a behaviour very near to the base material, and the important role that
all the three defect types play in the loss of mechanical resistance. Among the three different
analyzed defects, root defects are definitely the ones that show higher loss of properties under
fatigue loading.
In Figure 7, it is possible to confirm the higher length of the root Defect Type II, when compared
to the root Defect Type I resulting in lower life under fatigue loading. Figure 7 also shows the
deformation pattern in the vicinity of the internal void of the specimens with the Defect Type III.
Conclusions
The three experiments presented in this paper show that the results of the IOnic probe exceed the
performance of conventional probes. These results are encouraging but still preliminar and
further studies are currently being conducted to assess the potential of the IOnic probe to detect
FSW defects.
The influence of the root defects in the loss of mechanical strength of friction stir welded
structures under fatigue load, typical from any aeronautic application, is very significant.
Moreover these types of defects are the ones that are more difficult to identify from the
application of previous NDT techniques very sensitive to coupling and lift-off conditions.
Acknowledgments
The authors would like to acknowledge the financial support from the Fundação para Ciência e
Tecnologia (FCT) via: project POCTI/EME/60990/2004 (acronym NDTStir) and the PhD
scholarship FCT – SFRH/BD/29004/2006.
References
[1] Vilaça, P., Pedrosa, N., Quintino, L., Experimental Activities and Computational
Developments of FSW at IST – Technical University of Lisbon, Proceeding of Romania Welding
Society (ASR), International Conference: “Welding in Romania on the Edge of Joining the
European Union”, Galati – Romania, 28-30th, Timisoara, pp.62-77, Set. 2005.
[2] Santos, T., Data Fusion with Fuzzy Logic in Non-Destructive Testing of Friction Stir
Welding, MSc Thesis, IST, Technical University of Lisbon, Portugal, 2006.
[3] Santos, T., Vilaça, P., Patent PT 103854, 2007 (Submitted)
32
A Thermal Model of Friction Stir Welding Applied to Aluminum 7136-

T76511 Extrusions
C. Hamilton1, S. Dymek2, M. Blicharski2 and I. Kalemba2
1
Department of Mechanical and Manufacturing Engineering
Miami University, Oxford, OH
2
Faculty of Metals Engineering and Industrial Computer Science
AGH University of Science and Technology, Kraków, Poland
Keywords: Friction Stir Welding, Thermal Model, Slip, Aluminum, Mechanical Properties
Abstract
A thermal model of friction stir welding is developed that utilizes an energy-based scaling factor
to account for tool slip. The proposed slip factor is derived from an observed, empirical
relationship between the ratio of the maximum welding temperature to the solidus temperature
and energy per unit length of weld. The thermal model successfully predicts the maximum
welding temperatures over a range of energy levels and supports the concept that the relationship
between the temperature ratio and energy level is characteristic to aluminum alloys with similar
thermal diffusivities. The thermal model is applied to aluminum 7136-T76511 extrusions that
were joined through friction stir welding at six different RPM and evaluated for residual
properties. Residual mechanical properties of the alloy correlated with the energy per length of
weld, i.e. the highest joint efficiency was achieved at the highest welding temperature.
Introduction
Friction stir welding (FSW) is a solid-state joining process that is gaining popularity in the
manufacturing sector and, in particular, the aerospace industry [1, 2]. The welded joint is
fundamentally defect-free and displays excellent mechanical properties when compared to
conventional fusion welds [3, 4, 5]. Since its introduction, numerous investigations have sought
to characterize the principles of FSW and to model the microstructural evolution and temperature
behavior. Despite the complex flow of material during FSW, researchers have found success in
modeling the heat transfer characteristics of FSW. Frigaard et al. developed a finite difference
thermal model for a moving heat source and correlated the predicted temperature profile with the
measured temperature profile for friction stir welded 6082-T6 and 7108-T79 extrusions [6].
Utilizing a three dimensional visco-plastic model, Ulysee studied the impact of varying weld
parameters on the temperature distribution in 7050-T7451 thick plate [7]. Khandkar et al.
introduced a more comprehensive model of heat input based on the torque of the FSW tool that
they successfully utilized to model the temperature history of friction stir welded aluminum
6061-T651 plate [8]. Each of these thermal models solves the heat transfer equation for the alloy
and welding conditions of interest in order to determine the thermal profile and the maximum
welding temperature. The current investigation, however, utilizes Khandkar’s torque-based heat
input model to develop characteristic temperature curves that correlate temperature data from
various aluminum alloys and welding conditions into a relationship based on the solidus
temperature and the energy per unit length of weld. With this empirical relationship, an energy
based slip factor is defined and introduced into a thermal model to predict maximum welding
temperatures.
Aluminum 7136-T76511 extrusions with a thickness of 6.35 mm and a width of 101.6 mm were
obtained from Universal Alloy Corporation. Aluminum 7136 contains higher levels of zinc than
33
typical 7XXX alloys (8.4 – 9.4 wt%) and utilizes both zirconium (0.10 – 0.20 wt%) and
chromium (0.05 wt%) to control grain growth and recrystallization [9]. The density of 7136 is
2789 kg/m3. The extrusions were friction stir welded by the Edison Welding Institute in a butt-
weld configuration, utilizing an FSW tool with a shoulder diameter of 17.8 mm, a pin diameter
of 10.3 mm at the tool shoulder that tapered to 7.7 mm at the tip and a pin depth of 6.1 mm.
Specific details of the tool design are proprietary to EWI, but Mishra and Ma have reviewed
many of the common FSW tool designs that are indicative of that utilized in this investigation
[5]. With a weld velocity of 2.1 mm/s and an applied force of 26.7 kN, unique welds were
produced at 175, 225, 250, 300, 350 and 400 RPM.
From the welded panels, full thickness (6.35 mm) tensile samples were excised perpendicular to
the friction stir weld with the weld centered within the reduced section. Tensile coupons of the
same geometry and dimensions were also excised from an area distant from the weld region for
baseline property comparison. All tensile tests were performed in accordance with ASTM E 8.
Specimen extension was measured by means of an extensometer attached to the reduced section
that spanned the width of the weld. The extensometer remained attached to the specimen through
yielding, but was removed prior to specimen failure to prevent damage to the equipment. The
yield strength, σy, was obtained by the 0.2% offset method, and the elastic modulus, E, was
determined by fitting a linear regression to the elastic region of the stress-strain curve.
Results and Discussion
Figure 1 – Finite element model of the friction stir welding process
Figure 1 diagrams the friction stir welding process and specifies the parameters of interest. Since
the weld velocity (vw), tool rotation speed (ω) and applied force (F) all influence the total energy
imparted to the work pieces, the total heat input more appropriately indicates the welding
conditions than any individual welding parameter. From Khandkar’s model, therefore, the energy
per unit length of weld can be calculated from the total torque and utilized as a quantitative
measure of the heat input. The total torque, Ttotal, can be expressed as the sum of torque
contributions from the tool shoulder against the work piece (Tshoulder), the bottom of the tool pin
against thickness material (Tpinbottom) and the pin surface against thickness material (Tpinsurface),
such that:
34
2
ro ri
Ttotal = 2 μF (
+ h) (1)
3 ro 2
where ro is the radius of the tool shoulder, ri is the radius of the pin (taper ignored), h is the pin
height, F is the applied force and μ is the coefficient of friction between the tool and the work
pieces. The energy per unit length of weld, El, is found by dividing the average welding power
by the weld velocity to ultimately yield the expression in Equation 2:
ω
El = Ttotal (2)
vw
The coefficient of friction between aluminum (the work piece) and steel (the tool) depends on
the temperatures produced by the welding conditions. As the welding temperature approaches
the solidus temperature of the alloy, the interface between the tool shoulder and work piece
softens, causing the tool to slip, effectively lowering the coefficient of friction [6, 10]. Frigaard
et al. reasoned that the coefficient of friction between aluminum and mild steel should be set as
the average value between 0.5 for sticky friction and 0.25 for dry sliding, while Soundararajan et
al. allowed μ to vary between 0.5 and 0.4 depending on the welding conditions. This
investigation used a coefficient of friction of 0.5 for all calculations.
A literature search for temperature data on aluminum alloys produced the information gathered
in Table 1, where α is the thermal diffusivity of the alloy (α = k/cp·ρ: ρ – density, cp – heat
capacity, k – thermal conductivity). In each case, the researchers experimentally measured the
maximum temperature to verify their thermal model and included the welding parameters and
tool geometry, such that energy per unit length calculations could be made for their work. This
information is also presented in Table 1.
Table 1 - Energy per Unit Length of Weld and Measured Maximum Temperature
α Solidus Tool Geometry Welding Parameters Meas.
Thick.
Alloy (x10-5 Temp. ro ri h vw F E Max. T
(mm) RPM
m2/s) (K) (mm) (mm) (mm) (mm/s) (kN) (J/mm) (K)
6061-T6
6.4 6.9 855 12.0 9.5 6.0 344 2.2 13 1639 698
[10]
6061-
8.13 6.9 855 12.7 5.0 8.0 390 2.4 22 1896 739
T651 [8]
1500 5.0 7 696 594
6082-T6
6.0 7.1 879 7.5 2.5 6.0 1500 8.0 7 435 548
[6]
1500 12.0 7 290 523
180 0.85 20 1845 628
180 1.3 25 1513 623
7050-
180 1.7 28 1273 593
T7451 6.4 6.5 761 10.2 3.6 6.1
[11] 360 1.7 24 1978 673
540 2.5 34 2464 663
810 3.8 39 2868 703
520 1.0 18 3053 493
520 1.9 24 2410 448
7050-
19.1 6.5 761 9.5 3.2 6.4 700 1.0 13 3710 533
T7451 [7]
700 1.9 16 2403 493
700 2.6 18 2229 483
1500 5.0 7 696 648
7108-T79
6.0 5.2 748 7.5 2.5 6.0 1500 8.0 7 435 563
[6]
1500 12.0 7 290 523
Figure 2a plots the measured maximum temperature, Tmax, as a function of El for the data in
Table 1. As seen in the figure, the data groups according to alloy type and product thickness.
Thus, the maximum temperatures for the 6061 and 6082 alloys show a common linear
relationship with El, while the two 7050 data sets reveal unique relationships between
35
temperature and energy due to their difference in product thickness. Since 6061 and 6082 share a
similar chemical composition and thickness, their common relationship between temperature and
energy is expected. Even though, 7050 has a distinct chemistry from the 6XXX family of alloys,
its thermal diffusivity is comparable to both 6061 and 6082; therefore, for the same product
thickness, the 7050 data from Reynolds investigation would be expected to show a similar
temperature/energy relationship as that of 6061 and 6082. The 7050 relationship in Figure 2a
shows a similar slope to that of 6061 and 6082, but the curve is shifted to the right, indicating
that lower maximum temperatures are realized in 7050 at the same energy levels.
800 1
a 0.9 b
700
0.8
Maximum Temperature (K
600
0.7
500
0.6
Tmax/Tsolidus
400 0.5
6061-T6 [10] 0.4 6061-T6 [10]
300
6061-T651 [8] 6061-T651 [8]
6082-T6 [6] 0.3 6082-T6 [6]
200
7050-T7451 [11] 0.2 7050-T7451 [11]
100 7050-T7451 [7] 7050-T7451 [7]

0.1
7108-T79 [6] 7108-T79 [6]
0 0
0 500 1000 1500 2000 2500 3000 3500 4000 0 500 1000 1500 2000 2500 3000
Energy/Length (J/mm) Energy x (rh/t) (J/mm)
Figure 2 - a) Maximum temperature as a function of energy per weld length, b)

temperature ratio as a function of effective energy per weld length
Recall, however, that as the welding temperature approaches the solidus temperature, Ts, the
material will soften, slip will occur and less energy will be transferred into the work piece.
Because the solidus temperatures of 6061 and 6082 are greater than that of 7050, the transfer of
energy between the tool and the work piece is more efficient at equivalent energy levels in the
6XXX alloys than 7050. Thus, the maximum temperature at a given energy level will increase
with increasing solidus temperature. If the temperature ratio, Tmax/Ts, is plotted as a function of
El, then the data groups according thermal diffusivity and product thickness. The effect of
product thickness, however, should be viewed in terms of the depth of penetration of the welding
tool. As the pin length increases relative to the thickness, the efficiency of heat transfer into the
volume of material surrounding the tool also increases. For a given alloy and thickness,
therefore, the maximum welding temperature at a given energy level will rise as the pin length
increases. To account for the influence of tool penetration, the transfer efficiency, β, is defined as
the ratio of the pin length, h, to the product thickness, t. The effective energy per weld length,
(El)eff, then becomes the energy per weld length multiplied by the transfer efficiency.
Figure 2b plots Tmax/Ts as a function of (El)eff, and Ulysee’s 7050 data now reveals the same
temperature ratio/energy relationship as the 6061, 6082 and Reynolds’ 7050 data. The distinction
between this relationship and that of 7108 lies in the difference between the thermal diffusivities
of the data sets. The thermal diffusivity of 7108 is 5.2 x 10-5 m2/s, while that of the 6XXX and
7050 data set is approximately 6.75 x 10-5 m2/s. Both linear regressions in Figure 2b converge
near the same Tmax/Ts ratio for an energy level of zero, the 7108 data set intercepting at 0.58 and
the 6XXX and 7050 data set intercepting at 0.54. If this value is taken as 0.56 and the
relationship between the slope and α is interpolated from the experimental data, then an
empirical relationship between the temperature ratio and the effective energy level is developed
that is applicable to each of the aluminum alloys:
Tmax
= (0.00129 − 16.6α )( El ) eff + 0.56 (3)
Ts
36
Equation 3 describes a relationship between the welding energy and the maximum welding
temperature that is characteristic across numerous aluminum alloys. If the thermal properties and
solidus temperature for a given aluminum alloy are known, then the maximum welding
temperature during FSW may be estimated from the welding parameters, work piece thickness
and tool geometry utilizing Equation 3.
From the governing heat equation for a moving heat source, the heat flux, q, during FSW at the
tool/work piece interface may be derived and is given by the following expression [12]:
q = δμPN ωr (4)
where δ is the slip factor, PN is the normal pressure relative to a tool face and r is the radial
distance from the tool axis as shown in Fig. 1. From the relationship in Equation 3, the maximum
effective energy, (El)max, is defined as the energy level for which the maximum welding
temperature is equal to the solidus temperature of the alloy (i.e. Tmax/Ts = 1). The following
energy dependent expression for the slip factor is then proposed:
( E l ) eff
δ E = exp(− ) (5)
( E l ) max
In Equation 5, δE effectively represents the efficiency of frictional heat transfer, such that, when
δE = 1, sticky friction dominates. As (El)eff increases, the tool/work piece interface softens, and
the extent of slip increases, lowering the heat transfer efficiency. At the limit of (El)eff = (El)max,
δE = 0.37. The thermal model for friction stir welding developed in this investigation utilizes the
slip factor presented in Equation 5 and the average heat flux on the pin bottom, qpinbottom, and tool
shoulder, qshoulder, derived from Equation 4.
Using the thermal module of the NX 5.0 software, a thermal model of friction stir welding was
developed that included tool articulation. Fig. 1 shows the three-dimensional, finite element
model of the FSW process. The backing spar, as opposed to a full backing plate, reduces the
number of equations to be solved, shortens the computer processing time and still captures the
essential nature of heat flow between the work piece and backing plate. The width of the backing
spar is equal to the diameter of the tool, and the height is 25.4 mm. The model assumes that
perfect contact exists between the two work pieces along the weld line and between the tool
shoulder and the work pieces. A gap thermal conductivity of 157 W/m·K, the average thermal
conductivity of aluminum 7050 between 300 K and 700 K, is applied between the pin bottom
and the bottom of work pieces. For the boundaries exposed to ambient conditions, the convective
coefficient is set to 15 W/m2·K. Heat dissipation due to radiation is ignored. The remaining
boundary conditions and thermal couplings were determined by calibrating the thermal model
against the experimental data provided by Khandkar et al. [8], as summarized in Table 1. For the
tool top and spar bottom, a convection coefficient of 200 W/m2·K is applied, and for the area
outside of and adjacent to the backing spar, a convective coefficient of 100 W/m2·K is used to
represent the dissipation of heat into the backing plate. Lastly, a heat transfer coefficient of 250
W/m2·K defines the conductance between the bottom of the work pieces and the backing spar.
Utilizing Equations 3 and 5, the slip factor for 7136 can be determined for various energy levels.
Though the zinc content of 7136 is higher than that of 7050, the chemical composition of both
alloys is similar, and the solution heat treat temperatures are both approximately 743K; therefore,
the solidus temperature and thermal properties of 7136 were estimated with those of 7050. With
this slip factor and the heat fluxes on the tool shoulder and pin bottom, the thermal model
predicts the maximum welding temperatures for given welding conditions. Table 2 summarizes
37
the welding conditions for 7136-T76511 and the predicted maximum welding temperatures from
the thermal model.
Table 2. Summary of mechanical properties for each weld condition
Max.
Temp.
Load (El)eff σTS σy e Eff.
RPM (K)
(kN) (J/mm) (MPa) (MPa) (%) (%)
Thermal
Model
L -- -- -- 641 614 10.5 --
LT -- -- -- 635 607 10.9 --
175 24.3 828 531 443 354 5.5 69.1
225 29.0 1272 589 449 354 5.3 70.0
250 20.9 1019 560 448 340 4.1 69.9
300 29.4 1721 619 465 355 5.2 72.5
350 26.5 1807 622 478 362 6.6 74.6
400 21.1 1641 616 454 352 5.4 70.8
Table 2 also summarizes the mechanical test results for the 7136-T76511 parent material and
each weld condition. The welding conditions that correspond to 350 RPM achieved the highest
joint efficiency, 74.6%, while those conditions that correspond to 175 RPM produced the lowest
joint efficiency, 69.1%. For 175, 250 and 225 RPM, the tensile strength appears somewhat
insensitive to the maximum welding temperature as the tensile strength rises only 6 MPa as the
temperature increases from 531K to 589K. For energy levels corresponding to 400, 300 and 350
RPM, the tensile strength is more sensitive to the temperature with the tensile strength rising 24
MPa as the temperature increases from 616K to 622K. The first step of the 7136-76511 aging
process is performed at 523K, and the second step is performed at 598K. The rise in tensile
strength, therefore, may be due to the nucleation and growth of strengthening phases with
increasing tool rotation speed and the greatest sensitivity occurring near the second step age
temperature. The relationship between the yield strength and temperature is not as clearly
defined, though the highest yield strength is still achieved at the highest temperature examined.
For 175, 250 and 225 RPM, the yield strength appears insensitive to temperature, showing no net
increase as the temperature rises from 531K to 589K. For 400, 300 and 350 RPM, however, the
yield strength, much like the tensile strength, rises sharply (10 MPa) over a 6K increase in
temperature. Again this behavior may be explained by the nucleation and growth of secondary
phases as the welding temperature approaches the aging temperatures of 7136-T76511.
38
Figure 3 – Mechanical properties as a function of predicted maximum welding temperature
Conclusions
From Khandkar’s torque-based heat input model of friction stir welding, the energy per unit
length of weld was calculated for numerous investigations on various aluminum alloys. The data
revealed a characteristic linear relationship between the temperature ratio, the maximum welding
temperature divided by the solidus temperature of the alloy, and the effective energy per length
of weld. The thermal diffusivity of the alloy determined the slope, and from this relationship, an
estimate of the slip between the tool and work pieces was developed. Using the proposed energy-
based slip factor, the maximum welding temperatures were estimated for 7136-T76511
aluminum extrusions joined at six different rotation speeds. Mechanical testing revealed that the
highest joint efficiency occurred at an estimated temperature of 622K, corresponding to 350
RPM. The correlation between the mechanical properties and temperature demonstrates that the
tensile strength is relatively insensitive to temperatures below 600K, but rises sharply with
temperatures beyond this threshold. This increase in tensile strength is driven by the nucleation
and growth of the secondary phases under the tool.
Acknowledgements
The authors acknowledge the Polish Ministry of Science and Higher Education (Grant No. N 507
094 32/2648) for their support of this research.
References
1. W. M. Thomas et al., Great Britain Patent Application No. 9125978.8, December 1991.
2. C. Dawes, W. Thomas, TWI Bulletin 6, November/December (1995) 124.
3. M. A. Sutton, B. C. Yang, A. P. Reynolds and J. H. Yan, Banded microstructure in 2024-
T351 and 2524-T351 aluminum friction stir welds, Material Science and Engineering A
364 (2004) 66 – 74.
4. C. Hamilton, S. Dymek, M. Blicharski, Comparision of mechanical properties for 6101-T6
extrusions welded by friction stir welding and metal inert gas welding, Archives of
Metallurgy and Materials 52 (2007) 67 – 72.
5. R. S. Mishra and Z. Y. Ma, Friction stir welding and processing, Material Science and
Engineering R 50 (2005) 1 – 78.
39
6. O. Frigaard, O. Grong and O. T. Midling, A process model for friction stir welding of age
hardening aluminum alloys, Metallurgical and Materials Transactions A 32 (5) (2001) 1189
– 1200.
7. P. Ulysee, Three-dimensional modeling of the friction stir-welding process, International
Journal of Machine Tools and Manufacture 42 (2002) 1549 – 1557.
8. M. Z. H. Khandkar, J. A. Khan and A. P. Reynolds, Predictions of temperature distribution
and thermal history during friction stir welding: input torque based model, Science and
Technology of Welding and Joining 8 (3) (2003) 165 – 174.
9. I. Gheorghe and D. Malejan, Universal Alloy Corporation, Anaheim, CA, 2006.
10. V. Soundararajan, S. Zekovic, R. Kovacevic, Thermo-mechanical model with adaptive
boundary conditions for friction stir welding of Al 6061, International Journal of Machine
Tools and Manufacture 45 (2005) 1577 – 1587.
11. T. U. Seidel and A. P. Reynolds, A 2-D friction stir welding process model based on fluid
mechanics, Science and Technology of Welding and Joining 8 (3) (2003) 175 – 183.
12. R. Nandan, G. G. Roy, T. J. Lienert and T. Debroy, Three-dimensional heat and material
flow during friction stir welding of mild steel, Acta Materialia 55 (2007) 883 – 895.
40
EFFECT OF ULTRASONIC VIBRATION ON SOLIDIFICATION

STRUCTURE OF TCS STAINLESS STEEL
Jian-Ping Liang1, Li-Xin Wang1, 2, Chang-Jiang Song1, Li-Hua Liu1, Qi-Jie Zhai1
1
Center for Advanced Solidification Technology (CAST), Shanghai University; Yanchang Road
149, ZhaBei District; Shanghai, 20072, P.R. China
2
Technology Center, Taiyuan Iron & Steel (Group) Ltd., Taiyuan 030003, P.R. China
Keywords: TCS Steel, Ultrasonic Vibration, Solidification Structure
Abstract
The effect of ultrasonic vibration on solidification structure of TCS steel was investigated in this
work. Ultrasonic vibration was injected into molten alloy along the horizontal direction.
Experimental results show that when the ultrasonic vibration is imposed on the melt, the chill
zone is extended, columnar crystals zone become narrow and dense, and equiaxed crystal zone
also is refined. Though ultrasonic attenuates very rapidly, the effect of refinement does not
decrease markedly. Based on the experimental and theoretical analysis, it is confirmed that
ultrasonic energy makes the crystal accrete on the wall of mould desquamate, and the acoustic
streaming makes the desquamated crystal flow into the liquid zone of cast. Desquamation of
nucleus and acoustic streaming play an important role in metal structure refinement.
Introduction
TCS stainless steel has low-chrome, low-carbon and low-nitrogen, which was recently developed
to be used for production of railroad vehicle. Application of TCS steel would significantly
decrease the cost of railroad vehicle. Ultrasonic vibration has many special functions, and can be
applied in many industry fields. For example, ultrasonic cleaning, plastic welding and ultrasonic
inspection are already operating in factory. Many studies show that ultrasonic vibration can
refine the solidification structure and improve the mechanical property [1-6]. But applications of
ultrasonic vibration to refine the solidification structure still remain in laboratory or die casting.
Main problem is the amplitude transformer horn can not work for a long time at high temperature
[7-10].
The macrostructure of cast ingots generally consists of three distinct zones: the chill, columnar,
equiaxed zone. Employing the lateral ultrasonic leading-in experimental apparatus developed by
self-group, the effects of ultrasonic vibration on three zones of solidification structure, and the
influence mechanism was discussed in detail.
Experimental procedures
Figure 1 shows the schematic illustration of lateral ultrasonic leading-in experimental apparatus.
Amplitude transformer horn and contacted steel were attached closely in order to introduce
ultrasonic vibration. Steel was heated to 1720°C in a medium-frequency furnace and then poured
into the mould with the size of 60X60X160 mm ingot. The mould was preheated to 500°C
beforehand. During solidification, the molten metal was treated by the ultrasonic vibration with
the power of 0W, 600W, for 7 minutes then cooled to room temperature.
41
Fig 1. Schematic illustration of experimental equipment
(1) Ultrasonic vibration, (2) Amplitude transformer horn, (3) Contacted steel, (4) Melt, (5)
Mould
Experimental material was TCS stainless steel, and the composition was shown in Table 1. The
samples were longitudinally cut along the direction of ultrasonic leading-in direction. Optical
metallographic observations were carried out after polishing and etching in
18gFeCl3+30mlHCl+100mlH2O solution about 20min.
Tab 1. Composition of TCS stainless steel (wt.%).

C Si Mn S P Cr Ni Nb Ti N Fe
0.008 0.28 1.09 0.004 0.024 11.83 0.75 0.096 0.04 0.011 balance
Results
Figure 2 is the structure of TCS steel without and with ultrasonic treatment. Because of great
cooling ability of water-cooled magnetostrietive transducer, three classical crystal zones only
appear in one side of the mould. Chill zone in surface, columnar crystal zone in middle and
equiaxed crystal zone in center appear orderly (Figure 2). For convenience of result analysis,
some parameters are defined as shown in schematic illustration of Figure 2, which including:
width of chill zone (a), width of columnar crystal zone (b), width of equiaxed crystal zone (c),
height of columnar crystal zone (d), flare angle of columnar crystal zone (α).
Figure 2 shows the change of solidification structure when ultrasonic vibration is injected into
the melt. When ultrasonic power is 0W, chill zone is scarcely found, only about 1mm. Coarse
columnar crystal distributes radiately, and its flare angle is 78°. Width of columnar crystal zone
is 35mm, and its height is 65mm. The width of equiaxed crystal zone is 4mm. When ultrasonic
vibration with 600W is injected into melt, some change occurs for chill zone. Flare angle and
height of columnar crystal zone increase to 88° and 74mm, then the width of it decrease to
30mm. when ultrasonic power is up to 700W, width of chill zone enlarges greatly, up to 15mm.
For columnar crystal zone flare angel and height is 97° and 81mm, while the width decrease to
20mm, and the width of equiaxed crystal zone increase from 8mm to 15mm. In a word, the
ultrasonic vibration make chill zone and equiaxed zone enlarge, width of columnar crystal zone
decrease, but height and flare angle increase.
Ultrasonic vibration not only enlarges the chill zone, but also refines the columnar crystal zone
and equiaxed crystal zone. These can be seen in Figure 3. Crystal size of chill zone is below
0.5mm at 700W, but area of chill zone is very small at 0 and 600W. Average width of columnar
crystal in columnar crystal zone is calculated along vertical direction 20mm at middle of
columnar crystal zone. Results show that width of columnar crystal is 2mm at 0W, and decreases
42
to 1.7mm and 1.25mm for casting with ultrasonic power of 600W and 700W. In equiaxed zone,
the crystal size is about 3mm without ultrasonic vibration. When ultrasonic is injected in melt at
600W and 700W, the size of equiaxed crystal is 2.4mm and 1.3mm. Consequently, though
ultrasonic attenuates very rapidly, but the effect of refinement does not decrease markedly.
Fig 2. Structure of TCS steel without and with ultrasonic treatment and schematic illustration for
analysis: (a) 0W, (b) 600W, (c) 700W, (d) schematic illustration for analysis.
43
Fig 3. Structure evolvement of TCS steel in ultrasonic lead-in direction at different power:
(a) 0W, (b) 600W, (c) 700W
Discussion
Propagation of the change for stress, particle velocity and particle displacement in elastic
medium is sound wave. When frequency is beyond sound wave, we call it ultrasonic. The
principal characteristics of ultrasonic waves are particle displacement, particle velocity and
sound pressure etc [11]. In ordinary cast process, homogeneous nucleation is more difficult than
heterogeneous nucleation, so the enlargement of chill zone under ultrasonic treatment is because
the increase of heterogeneous nucleation. After pouring, ultrasonic vibration affect on the
nucleus, and the power attenuates. On the other hand, desorption of nucleus adhered on the wall
of mould need some energy. Effects of ultrasonic vibration on the nucleus will be analyzed as
following.
Figure 4 is the schematic illustration of desorption process under ultrasonic treatment of

heterogeneous nucleation. Interfacial strength consists in the interface between nucleus and wall
of mould. In the view of physics and chemistry, interface strength can be expressed by force
44
between molecule and atom, exponent of solubility, and free energy of interfacial. Interfacial
strength can be described by adhesion power as [12]:
WSW = σ S L + σ W L − σ SW
(1)
where σ SL , σ W L , σ SW is the free energy of interface between nucleus and liquid, wall of
mould and liquid, nucleus and wall of mould respectively. That means if getting this energy the
interface will be broken, and the nucleus will desquamate.
Along the direction of ultrasonic vibration, the ultrasonic intensity I(x) is a function of the
transmitted position x, given by [11, 13]:
I(x) = I 0 e −2αx (2)
where I0 and It(x) are the input and target intensities, respectively, and α the attenuation
coefficient.
Suppose ds be an infinitesimal area on ultrasonic lead-in direction and the energy loss coefficient
α is viewed as constants. So, ultrasonic energy on ds can be represented by:
dW=I（x）ds (3)
Surface area of nucleus can be express as S = 2πRh .
So the total power of ultrasonic vibration in the surface of nucleus is:
W = ∫ I( x )ds
S
h
= ∫ I( x )d (2πRx )
0
πRI 0
= (1 − e − 2αh )
α (4)
Therefore, in the time of t, the total acoustic energy absorbed is:
ΔWt = ( W0 − W)t
πRI 0 t
= I 0S0 t − (1 − e − 2αh )
α
πRI 0 t
= πI 0 t [R 2 − (R − h ) 2 ] − (1 − e − 2αh )
α (5)
where R is the radius of curvature; h is the height of nucleus.
So when the ultrasonic energy absorbed is greater than adhesion power, nucleus will
desquamate. That is ΔWt ≥ WSW . In actual solidification process, the solidification time of some
small area is very short, so the time remained for ultrasonic treatment is limited. Consequently,
enhancing the power of ultrasonic vibration is helpful to increasing desorption of nucleus.
Nucleuses desorbed flow into the molten metal by acoustic streaming. Some are remelted, and
the others are remained. The nucleuses remained refine columnar crystal zone and equiaxed
zone. Acoustic streaming accelerates the flow of molten metal, makes the temperature field
uniform, and contributes to the form of equiaxed crystal [14].
45
Fig 4. Schematic illustration of desorption process under ultrasonic treatment of
heterogeneous nucleation
Conclusion
The effect of ultrasonic vibration on TCS steel was investigated employing lateral ultrasonic
leading-in experimental apparatus. Experimental results show that ultrasonic vibration can
enlarge the chill zone and equiaxed zone, and make width of columnar crystal zone decrease, but
height and flare angle increase. Though ultrasonic attenuates very rapidly, but the effect of
refinement does not decrease markedly. It is deemed that desorption of nucleus and acoustic
streaming play an important role in the solidification.
Acknowledgement
This work was supported by National Natural Science Foundation of China (NO.50701030 &
NO. 50734008), China Postdoctoral Science Foundation (NO.20070410716), Scientific Research
Special Program of Shanghai Excellent Youth Teacher and Taiyuan Iron & Steel (Group) Ltd.
We expressed our sincere thanks for their financial support.
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46
121-125.
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Mass Transfer, 48 (3-4) (2005), 703-718.
47
Effect of tin Content on the Magnetic properties and Recrystallization

Behaviors of Grain-Oriented Electrical Steels
Chun-Chih Liao1, Chun-Kan Hou2

1
Graduate student, Graduate School of Engineering Science and Technology, National Yunlin
University of Science and Technology; 123 University Road, Section 3; Douliou, Yunlin 64002,
Taiwan, R.O.C.
2
Professor, Department of Mechanical Engineering Technology, National Yunlin University of
Science and Technology; 123 University Road, Section 3; Douliou, Yunlin 64002, Taiwan,
R.O.C.
Keywords: Grain Oriented Electrical Steel, Tin, Secondary Recrystallization
Abstract
Fe-3% Si with a sharp Goss orientation has a good magnetic property suitable for the core
material of transformers. In order for secondary recrystallization to occur, the growth of other
primary grain must be restrained. Tin is easy to segregates at grain boundary and on the surface
that pinning the grain boundary mobile. This study was changing the tin content range from 0 to
0.31wt%, and investigating the effects of SRT (secondary recrystallization annealing
temperature) on the recrystallization behaviors and magnetic properties of oriented electrical
steel sheets.
It was found that the pinning effect of tin was very strong as the SRT below to 900°C. The
specimens containing 0wt% and 0.05wt% tin reached secondary recrystallization completing at
900 and 1100°C, respectively. As tin content higher than 0.05wt% the specimens without
nitriding treatment have pool secondary recrystallization, and specimen containing 0.05wt% tin
has maximum flux density and minimum iron loss. After nitriding treatment, flux density
increases slightly with increasing the tin content was observed. The specimen without tin has the
best magnetic properties when nitriding 60sec. The magnetic flux densities increase with
increasing the nitriding time while the tin content higher than 0.01wt%.
1. Introduction
Grain oriented electrical steel is an important function material used as lamination core in
transformers. Its magnetic properties affect the energy efficiency of electrical machines. In order
to save the energy and decrease operation cost, the study of grain oriented electrical steels aims
at using acquired inhibitor method that decreasing the slab reheating temperature [1]. Grain
oriented electrical steel has high magnetic flux density, low coercive force and low core loss.
However, secondary recrystallization to develop good magnetic properties was affected by the
primary microstructure such as grain size, texture, and size and distribution of inclusions [2].
And those microstructures are influenced by prior process variables.
During recrystallization process, tin atom is easy to segregate to grain boundary or surface to pin
down the grain boundary mobility. However, it also decreased the surface energy of crystal
grains selectively and also selectively increased the mobility of some grain boundaries [3]. The
segregation of tin increased the grain growth of (100) grain lying in the plane of the sheet and at
the same time decreased the growth of (111) [4]. Furthermore, the intensities of (111) and (411)
texture were decreased by adding tin in the grain oriented electrical steel after decarburizing
annealing to improved the secondary grain development [5,6]. Because the precipitates in the
49
specimens with tin were more uniformly dispersed in finer size than specimens without tin [7,8].
Therefore, the effect of tin on the dispersion of the precipitates may be the main reason for the
stable secondary recrystallization with rather small primary grain size after decarburizing
annealing.
This study investigates the effects of tin content range from 0 to 0.31wt% on the primary,
secondary recrystallization behaviors, and magnetic properties of grain-oriented electrical steels
by acquired inhibitor method.
2. Experimental Procedure
The compositions of the five grain oriented electrical steels and listed in Table I. The ingots,
containing 0~0.31wt% tin, were reheated to 1100°C for two hours, and hot-rolled in two steps by
a two-high pilot hot rolling mill with intermediate annealing at 1200°C for one hour. The
thickness of hot bands after rough rolling was 15.4mm, and after finishing rolling was 2.5mm.
After air cooling to room temperature, hot-rolled bands were annealed at 900°C for 5 minutes in
a fluidized bed furnace. The specimens were processed using a one-stage cold rolling method
[5]. Hot bands were cold rolled to 0.35mm in thickness with a total reduction of 86%. Then, the
cold-rolled sheets were cut into 60mm x 30mm coupons in longitudinal direction to the rolling
direction, and annealed for primary recrystallization. Primary recrystallization annealing process
included nitriding treatment and decarburization annealing. In order to prepare the specimens
with various inhibitor quantities, nitrogen was injected into the sheets through nitriding treatment
(keeping 0~60sec at 700°C in N2+H2+NH3 atmosphere). The total nitrogen contents varied by
change the nitriding time. Following the nitriding treatment, the specimens were annealed in a
wet 25% N2 and 75% H2 atmosphere with 20°C dew point for decarburization. The
decarburization annealing temperature was 800°C for 5 min. Secondary recrystallization
annealing was carried out under a 5% N2 and 75% H2 atmosphere with the heating rate of
12°C/h up to 1200°C and keeping for 12h at 1200°C under a 100% H2 atmosphere for
purification.
However, to study the effects of tin on the grain growth during the secondary recrystallization,
the intermediate SRT was carried out under a 5% N2 and 75% H2 atmosphere with the heating
rate of 12°C/h up to 700~900°C and cooling at the room temperature.
After the heat treatment, the magnetic flux density was measured at a magnetizing force of
800A/m (B8). The ac core loss was tested at 15kG induction and 50Hz. Then, the specimens
were pickled to remove the surface oxide layer. The macrostructure of the specimens were
observed. Total nitrogen content was measured by chemical analysis method. Grain size of the
steel sheets after primary recrystallization annealing and intermediate SRT was analyzed by the
intercept method based on ASTM standard E-112.
Table I. Chemical compositions of grain oriented electrical steels (wt%)

Heat No. Code C Si Mn P S Al N Sn
V2-2631B A 0.046 3.18 0.09 0.012 0.007 0.020 0.003 -
V2-2638A B 0.042 3.20 0.09 0.010 0.007 0.018 0.003 0.05
V2-2638B C 0.042 3.15 0.09 0.010 0.007 0.017 0.003 0.10
V2-2637A D 0.044 3.30 0.09 0.010 0.007 0.016 0.003 0.21
V2-2637B E 0.044 3.30 0.09 0.010 0.007 0.016 0.003 0.31
50
3. Result and discussion
3.1 Nitriding treatment

The relationship between tin content and nitrogen content was shown in figure1. It can be seen
that the nitrogen content increases with increasing nitriding time. In this case, the specimens
were heated to 700°C and NH3 was injected into furnace for various nitriding time. At the initial
time, all specimens contain 50ppm nitrogen without nitriding treatment. The specimen without
tin content is easy to nitriding, and it contains approximate 260ppm nitrogen while nitriding 60
seconds. The specimen containing 0.05wt% tin has only 110ppm nitrogen at the same nitriding
condition. The nitrogen content was below 110ppm while the tin content more than 0.1wt%. It
well known that NH3 gas is commonly used for the nitriding of steel. When steel sheets were
heated to above approximately 500~550°C and exposed to ammonia gas, NH3 dissociated into
nitrogen and hydrogen atomic ( 2NH3 Æ 2N+6H ). The reaction was catalyzed by the hot steel
surface. Thus, the nitrogen produced is nascent, and as such either may be absorbed by steel
surface or may combine in the gas phase to form the inactive molecular nitrogen. Nitrogen is
supplied to the absorbing steel surface in the nascent form. Based on the above discussion, it is
clear that nitrogen content decreased with increasing tin content. However, tin is a segregation
element that could segregate to the grain boundary, and the grain boundary is the easiest motion
route to the nitrogen atom. The above result may be that tin segregate to the grain boundary to
retard the diffusion of the nitrogen atom.
Figure1. Effect of tin and nitriding time on Figure2. Effect of tin on the grain size at
the nitrogen content after nitriding various heat treatment condition. Primary
treatment at 700°C. annealing, intermediate SRT 700°C and
900°C, respectively.
3.2 Effect of tin on recrystallization.

The effect of tin content on the grain size of oriented electrical steels after primary
recrystallization annealing was shown in figure2. Grain size after primary recrystallization
annealing were 10~12μm, and it didn’t alter distinctly on increasing tin content. Then the
specimens were heated by intermediate secondary recrystallization annealing, and measured the
grain size. While the SRT is 700°C, the grain size is similar to the primary grain size. But, the
grain size of specimens decreases with increasing tin content as the SRT is 900°C. The pinning
effect of tin was very strong as the SRT below 900°C. When the tin content less then 0.05wt%,
the grain size is approximate 18μm. Then, it quickly decreases to 15μm as the tin content more
then 0.1wt%. As discussed previously, grain size of the steel without tin is largest. It decreases
with increasing tin content after annealing at 900°C. Due to tin is a segregation element that is
51
easy to segregate at grain boundary and pins down the grain boundary mobility during the
recrystallization annealing. It implies that add tin retard grain growth during secondary
recrystallization.
3.3 Macrostructure after secondary recrystallization annealing

The effect of SRT and tin content on secondary recrystallization of grain oriented electrical steel
without nitriding treatment was shown in figure 3. Abnormal grains become coarser with
increasing SRT. However, the specimens without tin have large grains and finishes secondary
recrystallization when the SRT is higher than 900°C. The specimens containing 0.05wt% tin
finishes secondary recrystallization as the SRT is above 1100°C. Poor secondary
recrystallization occurs while the SRT is below 1000°C. By comparison, the specimens that
contains more than 0.1wt% tin have poor secondary recrystallization at whole secondary
recrystallization annealing conditions. The development of secondary recrystallization was
affected by changing SRT and amount of precipitations in grain oriented electrical steel. Too
high or too low SRT can’t develop coarse abnormal grain. But, it is difficult to obtain Goss grain
growth while there aren’t enough precipitations in the matrix. Based on above result, secondary
recrystallization was inhibited by adding tin in the oriented electrical steel.
Figure3. Effect of tin and SRT on macrostructure of grain oriented electrical steels
without nitriding treatment.
While the SRT was 1000°C, the effects of nitriding time and tin content on secondary
recrystallization of oriented electrical steel were shown in figure 4. It can see that specimens
without tin have full secondary recrystallization in whole nitriding condition. As tin content
increases to 0.05wt%, the steel without nitriding treatment has only occurred fine grains inside
the specimen. But, secondary recrystallization occurred while nitriding time more than 30sec.
The secondary recrystallization of the specimen containing 0.1wt% Sn is similar to the specimen
containing 0.05wt%. But its grains are smaller. While the specimens containing more than
0.21wt% tin, secondary recrystallization didn’t occur. In this study, tin impedes the grain growth.
In addition to tin, the nitrides are formed by nitriding treatment and retard the grain growth, too.
The nitrides were identified to MnSiN2 and Si3N4. They are very effective in inhibiting the
grain growth. For above reasons, optimum tin content and quantity of nitride are able to obtain
for abnormal grain growth during secondary recrystallization. Therefore, secondary
recrystallization is completed by effect of tin and nitride when the tin content is less than
52
0.1wt%. However, tin is too strong to make secondary recrystallization incompletely when tin
content is higher than 0.2wt%.
Figure4. Effect of tin and nitriding time on macrostructure of grain oriented

electrical steels as the SRT is 1000°C.
3.4 Magnetic properties

The effect of SRT and tin content on magnetic properties of oriented electrical steel without
nitriding treatment was shown in figure 5. It is found that the higher flux density and lower iron
loss in the same tin content of the specimens when SRT is 1100°C. Comparing tin content and
magnetic properties, the specimen without tin has best flux density when SRT is 900°C. As the
SRT is higher than 1000°C, the specimens containing 0.05wt% tin have best magnetic
properties. Then, flux density decreases and iron loss increases with increasing tin content.
Figure5. Effect of tin and SRT on magnetic properties of grain oriented electrical
steel without nitriding treatment, (a) Flux density B8, (b) Iron loss W15/50.
While SRT was 1000°C, the effect of nitriding time and tin content on magnetic properties on
secondary recrystallization of oriented electrical steel was shown in figure 6. Flux density
increases slightly with increasing the tin content was observed. The specimen without tin has the
best magnetic properties when nitriding 60sec. However, the magnetic flux densities increase
with increasing the nitriding time while the tin content higher than 0.01wt%.
53
Figure6. Effect of tin and nitriding time on magnetic properties of grain oriented
electrical steel as the SRT is 1000℃, (a) Flux density B8, (b) Iron loss W15/50.
4. Conclusion
The effect of tin on secondary recrystallization of grain oriented electrical steel has been
investigated. After nitriding, it is clear that nitrogen content decreases with increasing tin
content. The pinning effect of tin content on grain growth was very strong as the intermediate
SRT is 900°C. After secondary recrystallization annealing, the specimens containing 0 and
0.05wt% tin finished secondary recrystallization at 900 and 1100°C, respectively. As tin content
was higher than 0.05wt%, specimen has poor secondary recrystallization. It implies that tin
restrain the grain growth during secondary recrystallization. The specimen without tin has best
flux density when SRT is 900°C, and the specimens containing 0.05wt% tin have maximum flux
density and minimum iron loss as the SRT is higher than 1000°C. After nitriding treatment, flux
density increases slightly with increasing the tin content was observed. The specimen without tin
has the best magnetic properties when nitriding 60sec. The magnetic flux densities increase with
increasing the nitriding time while the tin content higher than 0.01wt%.
Reference
1. N. Takahashi, J. Harase, “Recent Development of Technology of Grain Oriented Silicon

Steel”Materials Science Forum, Vols. 204-206 (1996), 143-154.
2. M.F. Littman, IEEE Trans. on Magnetics, vol.MAG-7, (1971), pp.48.
3. M.GODEC, M JENKO, “Sn segregation and its influence on electrical steel texture
development”, ISIJ International, vol.39, No.7, (1999), 742-746.
4. M.Godec,M.Jenko,R.Mast, “Texture measurements on electrical steels alloyed with tin”,
Vacuum, 61 (2001), 151-155.
5. U. YOSHIYUKI, N. SHUICHI, S. YUKIO, “Method for producing bidirectionally oriented
silicon steel sheet having high magnetic flux density”, PAJ 2002-069532, (2002).
6. U. YOSHIYUKI, N. SHUICHI, Y. NORIHIRO, “Method for manufacturing grain oriented
silicon steel sheet having excellent magnetic property”, PAJ 2002-069595, (2002).
7. S. Nakashima, K. Takashima, K. Kuroki, “0.23 mm thick high permeability grain oriented
Si-steel”, IEEE Trans.Magn., MAG-18(1982),1511-1513.
8. N. Shozaburo, T. Kunihide, H. Jiro, “Effect of Tin Addition on Process of Secondary
Recrystallization of Fe-3%Si”, The journal of the Iron and Steel Institute of Japan, Vol.80,
No.2 (1994), 137-142.
54
Mechanical Properties and Microstructure

of Friction Stir Welded Ultra-High-Strength Automotive Steel
1
M.P. Miles, 1E. Olsen, 1T.W. Nelson, 2M. Gallagher
1
Brigham Young University, 265 CTB, Provo, UT 84602
2
ArcelorMittal, 3001 E. Columbus Dr., East Chicago, IN 46312
Keywords: Friction Stir Welding, UHSS, Formability, Microstructure
Abstract
Several ultra high strength steels were friction stir welded and then mechanically tested to
evaluate formability. Tooling feeds and speeds had a significant impact on the mechanical
properties and microstructures of the welds. At a given tool speed higher feed rates produced
softer welds with large amounts of primary ferrite, compared to lower feed rates which produced
harder welds and a greater fraction of martensite. These results illustrate the potential of
targeting good weld properties and favorable microstructures by friction stir welding in ultra
high strength automotive steel sheets.
Introduction
Dual-phase (DP) and TRIP steels can exhibit poor weld ductility for applications involving a
post-weld forming operation. Laser and mash-seam welding are currently used to join steel
sheets for tailored blank applications and these fusion processes can create high peak hardness
and poor formability in high strength automotive steels [1-3]. Dual-phase steels are high
strength, formable alloys which have microstructures of 20-60% martensite distributed
throughout a ferrite matrix, depending on the grade. These steels have good formability and
much higher tensile strength than standard drawing quality steels, and are therefore being
developed for automotive applications where lower gauge material can reduce the weight of
automotive stampings [4]. Prior work demonstrated that along-weld formability of laser-welded
DP 590 steel was about 20% less than that of the base material [5]. By contrast, the same study
showed that formability of friction stir welded sheets was as good as that of the base material.
Transverse tension performance was shown to be acceptable for both welding methods, with
failures occurring away from the weld and heat affected zone (HAZ).
TRIP steels have better formability than DP steel thanks to a precise two-step heat treating
process which results in a controlled fraction of retained austenite, which enhances formability
and improves strength after a forming operation. These alloys have microstructures consisting of
ferrite, bainite, and retained austenite, which is transformed to martensite during plastic
deformation [6].
This paper presents friction stir welding (FSW) results of DP 590, TRIP 590, DP 780, and DP
980 steels and shows the effect of welding process conditions on weld properties and
microstructures of these ultra high strength steel (UHSS) alloys.
55
Experimental Procedures
Welding trials were done to determine the best parameters for friction stir welding of DP 590,
TRIP 590, DP 780, and DP 980 steels. Tool speeds ranged from 324 rpm to 1000 rpm, while
feed rates were varied from 15 cm/min to 152 cm/min. Load control was used to control the
vertical travel of the spindle, at a level of approximately 9 kN. A PCBN (polycrystalline cubic
boron nitride) tool with a convex, scrolled shoulder was used for welding (see Figure 1).
Figure 1. Cross section drawing of the friction stir welding tool. The shoulder is
convex with scroll features on the shoulder to improve heat generation (scrolls
not shown explicitly). Dimensions are in millimeters.
Tensile specimens were cut from welded sheets with the weld in the center of the reduced section
of the specimen, transverse to the tensile axis, as shown in Figure 2.
Figure 2. Tensile specimens were cut with the weld in the middle of the
reduced section, transverse to the tensile axis.
Tensile specimen geometry followed the ASTM E8 specification and testing was done at a speed
of 25 mm/min. Failures that occurred in the weld or HAZ were considered unacceptable.
Microhardness testing was done on a line across the weld, using a 300 gram weight and a 9
second dwell time. This data allowed for evaluation of the amount of heating that occurred
during welding, based on the degree of softening in the HAZ and the hardness of the weld
nugget.
56
Results
The tensile properties of the base materials, shown in Table 1, were used as a basis for evaluating
welded specimen performance.
Table 1. Tensile properties of UHSS alloys.

Testing Results on Base Materials
Material YS (Mpa) UTS (MPa) Elongation Microhardness
TRIP 590 443 627 31% 210
DP 590 370 630 24% 220
DP 780 503 793 17% 270
DP 980 703 1009 16% 330
Numerous welding trials provided data on the tooling feeds and speeds that provided the best
tension testing results. A summary of these parameters is shown in Table 2.
Table 2. Best tensile results for different welding parameters and for various alloys
and combinations of alloys.
Best results for each material or combination
Thickness Travel Speed Acceptable UTS vs. Elongation
Material (mm) (cm/min) welds base vs. base
TRIP 590 1.6 15-20 20/20 99% 83%
DP 590 - TRIP 590 1.6 15 9/9 98% 98%
DP 590 - TRIP 590 1.8 - 1.6 15 10/10 102% 120%
DP 590 1.4 - 1.2 102 4/4 93% 127%
DP 590 1.8 - 1.4 89-102 5/6 95% 139%
DP 780 1.4 76-102 0/15 78% 37%
DP 980 1.4 76-127 0/15 74% 36%
The TRIP 590 and DP 590 steels had good results, with essentially no failures in the weld or the
HAZ, including a dissimilar combination of DP 590 and TRIP 590. However, DP 780 and DP
980 alloys had many failures primarily in the HAZ. During the course of these experiments, the
hardness profiles of welds that were produced under different conditions of feed and speed
resulted were observed to vary significantly. For example, when DP 590 was welded at 102
cm/min and at tool speeds of 800 and 1200 rpm, the hardness values in the weld were much
greater for the faster speed. The likely reason for the difference is caused by the cooling rate,
where a higher tool speed results in a faster cooling rate while the feed rate is held constant. The
hardness profiles for two different tool speeds are shown in Figure 3.
57
Friction Stir Welded DP 590
330
310
290
270
250
230
210
190
170
150
-15000 -10000 -5000 0 5000 1000 1500
800 rpm 1200 rpm
Figure 3. Hardness profiles for friction stir welded DP 590 at a feed rate
of 102 cm/min and for tool speeds of 800 rpm and 1200 rpm.
Based on the phase diagram for DP 590, the temperature reached when welding at 102 cm/min
and 1200 rpm was great enough to austenitize the material, which transformed to martensite
during cooling. For DP 590 it is possible to achieve a phase fraction of about 20% martensite,
where the balance is ferrite. At the lower speed of 800 rpm, it is likely that the material did not
reach the austenite temperature, and that the existing martensite was tempered, resulting in a
weld nugget which was softer than the base material. Micrographs of the welds in these two
cases are shown in Figure 4.
DP 590 – 1200 rpm DP 590 – 800 rpm

Figure 4. Micrographs of the weld zone for two different tool speeds. The feed rate was the
same in both cases (102 cm/min). Magnification was 2500X.
58
Based on the micrographs, the weld zone for the 800 rpm tool speed contains martensite, primary
ferrite, and possibly other low transformation temperature products like bainite, Widmanstatten
ferrite, or acicular ferrite. By contrast, at the 1200 rpm tool speed the weld zone contains a large
amount of primary ferrite with grain boundary carbides and bainite. Clearly the FSW process is
capable of producing a range of weld properties in DP 590 steel, where heat input could be
adjusted by changing tool speeds and feed rates.
In DP 780 and DP 980 welding parameters were 800 rpm at 102 cm/min. These alloys both
exhibited a significant amount of softening in the weld and in the HAZ. Smoothed hardness
profiles of the friction stir welded specimens are shown in Figure 5, with profiles from laser
welds of the same alloys displayed for comparison.
DP 780 Microhardness – Laser vs

450
780 FSW
400 780 Laser
350
300
250
200
150
-15000 -10000 - 0 5000 10000 15000
Distance from center (microns)

a)
DP 980 Microhardness - Laser vs FSW
550
980 FSW
500
980 Laser
450
400
350
300
250
200
-15000 -10000 -5000 0 5000 10000 15000
Distance from center (microns)
b)
Figure 5. a) Hardness profile of friction stir welded DP 780, compared to laser-welded
DP 780, and b) hardness profile of friction stir welded DP 980 compared to laser-welded
DP 980.
59
Both of these alloys softened in the weld and HAZ, especially the DP 980, possibly due to
martensite tempering. Because of this, transverse tension specimens failed 100% of the time in
the HAZ for both alloys, while laser welded specimens resulted in HAZ failures about 50% of
the time.
Conclusions
Friction stir welding was shown to be capable of producing acceptable welds in DP 590 and
TRIP 590 based on transverse tension testing results. Different weld properties were obtained,
depending on the welding parameters used, resulting in harder or softer weld zones. FSW of DP
780 and 980 resulted in soft welds which caused systematic failures in the HAZ during
transverse tension testing. By comparison, laser welded specimens of the same materials failed in
the HAZ about 50% of the time during transverse tension testing. Based on the results obtained
in DP 590 and TRIP 590, it may be possible to adjust the FSW process to improve weld
properties in DP 780 and 980, which is planned for future efforts.
Acknowledgements
The authors thank Mike Li, of TWB company, Monroe, MI, for performing laser welding
experiments.
References
1. P.K. Ghosh, P.C. Gupta, and B.K. Jha, “Weldability of Intercritical Annealed Dual-Phase
Steel with the Resistance Spot Welding Process”, Welding Journal, 70 (1) (1991), 7s-14s.
2. M. C. Stasik and R.H. Wagoner, “Forming of Tailor-Welded Aluminum Blanks”, Aluminum
and Magnesium Automotive Applications, ed. J.D Bryant, (Warrendale, PA:The
Metallurgical Society of AIME, 1996), 69-83.
3. K.B. Min, K.S. Kim, and S.S. Kang, “A Study on Resistance Welding in Steel Sheets Using
a Tailor-Welded Blank (1st Report): Evaluation of Upset Weldability and Formability”,
Journal of Materials Processing Technology, 101 (2000), 186-192.
4. K.K. Bhatt and M. Eisenmenger, “Formability of mash seam welded blanks: effects of
welding set-up conditions”, Automotive Stamping Technology, 1995, 183-189.
5. M.P. Miles, J. Pew, T.W. Nelson, M. Li, “A Comparison of Friction Stir Welded and Laser
Welded Dual-Phase 590 Steel Sheets”, Science and Technology of Welding and Joining, 11
(4) (2006), 384-388.
6. L. Cretteur, A.I. Koruk, and L. Tosal-Martinez, “Improvement of weldability of TRIP steels
by use of in-situ pre- and post-heat treatments”, Steel Research, 73 (6-7) (2002), 314-319.
60
INTEGRATED FABRICATION OF FUNCTIONALLY GRADED Ti3SiC2–

TiC BINARY PHASE ROD BY TRAVELING ZONE SINTERING
METHOD
Shuji Tada, Keizo Kobayashi
National Institute of Advanced Industrial Science and Technology

2266-98 Anagahora Shimoshidami Moriyama-ku Nagoya, Aichi 463-8560, JAPAN
Keywords: Hard Material, Titanium Silicon Carbide, Titanium Carbide, Functionally Graded
Material, Synthesis, Traveling Zone Sintering
Abstract
Ti3SiC2–TiC binary phase material was synthesized from raw powder compound of Ti, Si and
TiC at molar ratios of 1:1:x (x = 1.8-7.0) with the aim of developing a new hard product. The
product obtained by the sintering of the above compound was single phase Ti3SiC2 when x was
2.0 or less, while a Ti3SiC2–TiC binary phase structure was synthesized from the powder
compound with larger x and the mass fraction of TiC in this structure increased with increasing
x. The optimum sintering temperatures for densification were different between the synthesized
structures. Ti3SiC2 single phase structure was well densified at up to 1673 K, whereas higher
temperature was required to dinsify the binary phase structure. The traveling zone sintering
method enables integrated sintering of materials at variable temperatures. Functionally graded
Ti3SiC2 single phase and Ti3SiC2–TiC binary phase rod was synthesized by the traveling zone
sintering method with changing the sintering temperature. The synthesized structure was
successfully graded and TiC mass fraction in the product varied from 0 to 50%.
Introduction
Tungsten carbide is now widely used in industry as the material for cutting tool and die assembly
due to its excellent hardness, and it is one of the most important materials in sustaining Japanese
industry. Almost all the tungsten that is consumed in Japan, however, has to be imported into
Japan, and its uneven distribution in the world as a mineral resource is a major problem for the
country. Misgivings about stable supply of tungsten in future necessitate the urgent development
of new hard materials as tungsten carbide substitute. Titanium carbide, TiC, is one candidate for
replacing tungsten carbide. It has, however, not yet completely substituted for tungsten carbide
because of problems of thermal shock and high-temperature plasticity.
The ternary phase compound Ti3SiC2, which combines the good engineering properties of both
metals and ceramics, has been recently discovered [1]. This relatively new material shows high
thermal and electric conductivities, a high thermal stability, good corrosion resistance and
excellent machinability. Ti3SiC2 is therefore expected to be useful as an engineering material.
Some studies [2–3] have been devoted to the synthesis of Ti3SiC2 and it has been reported that
the pulse discharge sintering process was effective in the synthesis of high purity Ti3SiC2 [4–6]
but the structure of synthesized Ti3SiC2 was sensitive to the compounding ratio of the raw
material powder mixture of Ti, Si and TiC [7]. In present study, the relationship between the
mixing ratio of the raw material powder and the structure of the synthesized Ti3SiC2–TiC was
61
investigated with the aim of developing a new hard product. The functional grading of Ti3SiC2–
TiC binary phase material was also studied to give it interesting properties, such as a
combination of a high hardness from a TiC rich structure and excellent machinability from the
presence of Ti3SiC2, by utilizing the ability of the traveling zone sintering method [6–7] which
enabled to sinter materials with a variable temperature distribution.
Powder Preparation
Ti, Si, and TiC powders were used to synthesize the Ti3SiC2–TiC binary phase material. All the
material powders used in this study had purities of over 99% and particle sizes in the range 2–45
μm. The stoichiometric reaction between the three raw material powders is as follows,
Ti + Si + xTiC = Ti3SiC2 + (x-2)TiC (1)
According to this equation, single phase Ti3SiC2 will be synthesized from a powder mixture of
Ti, Si and TiC in a molar ratio of 1:1:2, whereas a Ti3SiC2–TiC binary phase structure will be
produced from compounds with higher contents of TiC. Therefore, as shown in Table I, several
powder mixtures with different TiC molar ratios between 1.8 and 7.0 were prepared while
keeping both Ti and Si molar ratios to 1.0 to evaluate the effect of powder compounding ratio on
the synthesized structure.
Table I. Compounding Conditions for Raw Material Powder Mixtures.
Sintering
Each powder mixture was sintered individually in the temperature range 1643–1733 K to
examine the effects of the mixing ratio on the structure of the product. An integrated sintering of
layered material powders was also carried out to produce a functionally graded Ti3SiC2–TiC rod
by a traveling zone sintering method [6–7]. As shown in Figure 1, a mold was charged with 4.5 g
of TSC18 (see Table 1) at first and 0.5 g of each of the other raw material powders, from TSC20
to TSC70, was stacked sequentially on top of it. Figure 2 indicates a schematic illustration of the
traveling zone sintering method. The height of the electrode delineates the heating zone. The
electrode is able to travel along the side wall of the mold while remaining in continuous contact
with it. The moving narrow heating zone provides the sintering temperature freely at each
position. TSC18 and TSC20 were sintered at 1643 K, whereas the sintering temperature was
raised to 1733 K for the other compounds. The moving rate of the stage was set at 0.01 mm/s.
All the sintering tests were carried out in a vacuum environment of about 5 Pa. The graphite
62
mold used for the sintering had a bore diameter of φ8 mm. The hardness was measured by using
a Vickers hardness tester under a load of 9.8 N with a holding time of 15 s.
Figure 1. Powder loading to produce a functionally Figure 2. Schematic illustration of

graded Ti3SiC2–TiC binary phase material. traveling zone sintering method.
Effect of Powder Composition on Synthesized Structure

Figure 3 shows the X-ray diffraction patterns for the
structures obtained by sintering of the each powder
mixture. It is obvious that single phase Ti3SiC2 was
obtained when x, the molar proportion of TiC, was 2.0
or less, whereas a Ti3SiC2–TiC binary phase structure
was produced when x exceeded 2.0. The relative mass
fractions of Ti3SiC2 (WTSC) and TiC (WTC) in a
Ti3SiC2–TiC binary phase material can be calculated
according to the following equations [5],
WTSC = K / (K+ITC/ITSC)
WTC = (ITC/ITSC) / (K+ITC/ITSC) (2)
where ITSC and ITC are the intensities of the Ti3SiC2

(104) and TiC (200) peaks, respectively. K is a
constant, equal to 1.8 in present study. Figure 4 shows Figure 3. X-ray diffraction patterns of
the TiC mass fraction in the synthesized product plotted Ti3SiC2–TiC binary phase materials.
against the molar ratio of TiC in the material powder
mixture. The solid line is a least-square approximate curve and the broken one is the
stoichiometric estimate from equation (1). It can be seen that the experimental values fall slightly
below those predicted from the stoichiometric calculation. This discrepancy has not yet been
clearly explained, but the partial formation of a solid solution may cause this result. In any case,
it was confirmed that the mass fraction of TiC in the synthesized Ti3SiC2–TiC binary phase
structure can be controlled by adjusting the proportion of TiC in the raw material powder.
63
The effect of the sintering temperature on the density of the synthesized body is shown in Fig. 5.
Single phase Ti3SiC2 (x=1.8) was satisfactory densified at up to 1673 K, whereas the sintering
temperature had to be increased to 1733 K to produce a fully densified Ti3SiC2–TiC binary phase
structure (x=2.5). Other Ti3SiC2–TiC binary phase materials synthesized from TSC30 to TSC70
mixtures were also fully densified at 1733 K. It is therefore concluded that the optimum sintering
temperature is 1673 K for single phase Ti3SiC2 but 1733 K for Ti3SiC2–TiC binary phase
materials, regardless of their phase ratio.
Figure 4. TiC mass fraction of Ti3SiC2-TiC Figure 5. The relation between the sintering
binary phase materials synthesized from temperature and the density of synthesized
various material powder mixtures. Ti3SiC2–TiC binary phase materials.
Integral Production of Functionally Graded Ti3SiC2-TiC Binary Phase Rod

The above results suggest the possibility of producing a functionally graded Ti3SiC2–TiC
material. Functionally graded materials have been produced by sintering processes, but it is very
difficult to give intentional temperature differences within a material powder compact during
sintering by conventional processes since the entire compact body is heated at the same time in
such processes. Compared with the conventional sintering processes, the traveling zone sintering
method [6–7] permits the precise control of the sintering temperature at any position and enables
sintering to be performed with a variable temperature distribution.
Figure 6 shows the changes of the TiC mass fraction in a synthesized functionally graded
Ti3SiC2–TiC rod. The abscissa of this figure represents the distance from the end of the TSC18
side. The produced rod was 43 mm long. It was estimated that 4.5 g of TSC18 accounted for
nearly 20 mm of this rod and 0.5 g each of the other material powders (TSC20–70) corresponded
to a 2.1 mm long segment. It can be seen that almost all the first 20 mm of the rod consisted of
single phase Ti3SiC2, but subsequently a TiC structure appeared. The proportion of TiC
increased with approaching to the other end of the rod. The broken curve shows a least-square
approximation of the results from individual syntheses from each raw material powder. It is
obvious that the two series of results correspond well with each other. It is therefore concluded
that the traveling zone sintering method enables the integral production of a functionally graded
material that requires a varying sintering temperature.
The density distribution of the functionally graded Ti3SiC2–TiC rod is shown in Figure 7. The
functionally graded rod was cut in widths that were nearly equivalent to each of the raw material
powders and the density was measured for each fraction. The broken curve in this figure
indicates the estimated density, calculated by the rule of mixtures from the theoretical densities
of Ti3SiC2 (4.52x103 kg/m3) and TiC (4.92x103 kg/m3). The experimental results generally
correspond to the calculated values, although some dispersion is observed. This dispersion might
64
be caused by a chemical reaction between the raw material powder compact and the graphite
mold, leading to sticking to the mold, since a rather high sintering temperature (1733 K) was
employed in this synthesis. It is possible that this chemical reaction may have hampered the
densification of the rod, especially near its central section.
Figure 6. The transition in TiC mass fraction in a Figure 7. The density distribution in a
synthesized functionally graded Ti3SiC2–TiC rod. functionally graded Ti3SiC2–TiC rod.
To prevent prevent chemical reaction between the material powder and the mold, a boron nitride
solid lubricant was applied on the inner surface of the mold. Figure 8 indicates the density
distribution of the functionally graded Ti3SiC2–TiC rod produced through the above modification.
The experimental values are well corresponding to the theoretical densities calculated by the rule
of mixtures. This means that the produced functionally graded rod was well densified over its
entire body, since the solid lubricant successfully prevented material powder compact from
sticking to the mold during high temperature sintering.
Figure 8. The density distribution in a graded Figure 9. The hardness distribution in a

rod sintered with solid lubricant. functionally graded Ti3SiC2–TiC rod.
The hardness distribution of this functionally graded rod is shown in Figure 9. The broken curve
was calculated according to the rule of mixtures for the individual theoretical values of Ti3SiC2
(4 GPa) and TiC (31 GPa). It can be seen that the hardness near the both ends were close to the
calculated values and the hardness attained the same level as that of tungsten carbide (12–17
GPa) near the TiC rich end where the mass fraction of TiC was about 56%. However, the
hardness remained relatively low in the central section where the molar proportion of TiC in the
raw material powder was between about 4.0 and 6.0, which was equivalent to the TiC mass
fraction between 30% and 50% (see Fig.5). It remains possible that the hardness of the Ti3SiC2–
TiC binary phase material is dominated by the Ti3SiC2 structure which is not so hard and the rule
65
of mixtures does not apply in this range. It is important to consider this phenomenon when we
design Ti3SiC2–TiC binary phase products from the viewpoint of hardness.
Concluding Remarks
In this study, Ti3SiC2–TiC binary phase material was examined with the aim of developing a new
hard product. The traveling zone sintering method was applied to the synthesis of functionally
graded rod. The results are summarized as follows.
1) A Ti3SiC2–TiC binary phase structure was synthesized by sintering of a powder mixture

consisting of Ti, Si and TiC. The mass fraction of TiC in the binary phase product could be
controlled by adjusting the proportion of TiC in the raw material powder mixture.
2) The traveling zone sintering method enabled the integral production that necessitated the
sintering to be performed with a variable temperature distribution. A functionally graded rod
comprising both a Ti3SiC2 single phase and a graded Ti3SiC2–TiC binary phase in the same body
was successfully produced by this process. Boron nitride solid lubricant was effective to produce
a well densified Ti3SiC2–TiC binary phase rod, since this lubricant could prevent material
powder compact from sticking to the mold during high temperature sintering.
3) It remains possible that the rule of mixtures does not apply to the hardness of the Ti3SiC2–TiC
binary phase material in the range of TiC mass fraction between 30% and 50%. It is important to
consider this phenomenon when we design Ti3SiC2–TiC binary phase products from the
viewpoint of hardness.
REFERENCES
1. W. Jeitschko and H. Nowotny, “Die Kristallstruktur von Ti3SiC2 – ein neuer Komplexearbid-
Typ”, Monath. Chem. 98(1967) 329-337.
2. M. W. Barsoum and T. El-Raghy, “Synthesis and Characterization of a Remarkable Ceramic:

Ti3SiC2”, J. Am. Ceram. Soc. 79(1996) 1953-1956.
3. T. El-Raghy and M. W. Barsoum, “Processing and Mechanical Properties of Ti3SiC2: I,

Reaction Path and Microstructure Evolution”, J. Am. Ceram. Soc. 82(1999) 2849-2854.
4. Z. F. Zhang et al., “A new synthesis reaction of Ti3SiC2 through pulse discharge sintering
Ti/Si/TiC Powder”, Scr. Mater. 45(2001) 1461-1467.
5. Z. F. Zhang, Z. M. Sun and H. Hashimoto, “Rapid Synthesis of ternary Carbide Ti3SiC2

through Pulse-Discharge Sintering Technique from Ti/Si/TiC Powders”, Metallurgical and
Materials Transactions A 33(2002) 3321-3328.
6. S. Tada et al., “A Concurrent Process for the Synthesis and Fabrication into Rods of the
Ternary Compound Ti3SiC2 by means of a Traveling-Zone Sintering Method”, Mater. Trans.
47(2006) 302-305.
7. S. Tada et al., “Fabrication of a Dense Long Rod through Pulse Discharge Sintering Assisted
by Traveling Zone Heating”, Mater. Trans. 44(2003) 1667-1670.
66
STUDY ON DEFORMATION OF LARGE-SCALE HYDRAULIC

TURBINE BLADE DURING THE CASTING PROCESS
Zhang Jiafeng1, Kang Jinwu1, Wu Ying2, Zhang Jiashu2,

Rong Zichen2, Zhang Chengchun2, Liu Baicheng1
1
Key Laboratory for Advanced Materials Processing Technology, Ministry of Education,
Department of Mechanical Engineering, Tsinghua University, Beijing, China
2
Harbin Electric Machinery Co., Ltd, Harbin, China
Keywords: Hydraulic Turbine Blade, Reverse Deformation, Casting, Numerical Simulation
Abstract
Deformation is one of the most common defects during the casting process of large-scale
hydraulic turbine blade because of the complex curved 3-D surface geometry. To finally obtain
the exact surface contour, reverse deformation is usually applied in making wooden pattern in
foundries. Numerical simulation is carried out to calculate the deformation of a blade casting
used for the Three Gorges Power Plant. The reverse deformation is acquired by the comparison
of the deformed casting shape and the original designed shape. Then, the reverse deformation is
fed back to the original casting design. After several iterations, the casting design with the latest
reverse deformation results the proper casting shape, i.e., finally obtained casting conforms to the
required shape and even and appropriate machining allowance is realized. The calculated inverse
deformation is approximately in agreement with the actual values.
Introduction
In the production of large-scale hydraulic turbine blade, inverse deformation has to be

determined to compensate the deformation resulted by its thin and curved contour [1-3]. In
foundries, the inverse deformation is still determined by experience. Then, it is hard to finally
obtain net-shape casting production.
Fig. 1a shows the usual deformation contours of a hydraulic turbine blade. It is can be seen that
the plus and minus maximal displacements occur in the two corner areas lying on blade outlet
edge respectively. The directions of deformation in these two corner areas are designated by the
red arrows showed in Fig. 1b. Seen from the bottom, the 2-D shape of blade outlet edge is drawn
in Fig. 2. The red line figures out the shape with deformation and the black line is the original
one. The blade becomes flatter after deformation but the original shape is what we wanted.
Usually, inverse deformation is applied to make the wooden pattern for molding [3, 4], as Fig. 2
shows. However, the problem is that the exact value of inverse deformation is hard to be
determined by experience [5, 6].
67
Top
Outlet edge
Bottom
(a) deformation distribution (b) directions of deformation at corners

Fig. 1 usual deformation distribution of a blade casting
Fig. 2 The deformation of blade outlet edge
Numerical simulation is more and more widely used in industry area because of its unique
advantages, low-cost and effective. The development of computer science also improves its
reliability and acceptability. The purpose of this paper is to develop a method of determining the
inverse deformation for the design of wooden pattern by thermal stress analysis of casting. The
final reverse deformation values can realize even and appropriate machining allowance of the
whole casting. The calculated inverse deformation is compared with the actual values.
Numerical Method
The numerical simulation was carried out by an integrated FDM/FEM system for thermal stress
analysis of castings [7, 8]. Fig. 3 shows the flow chart of the system. FT-star, developed by
Tsinghua University, is based on FDM method. In this paper this software was used to calculate
the temperature fields during the casting process. Thermal stress and deformation were
calculated by ANSYS. By adding the calculated deformation to the original casting, the shape of
deformed casting is obtained. It is compared to the final required component shape after
machining, then, the machining allowance will be acquired. If the distribution of calculated
machining allowance is not even or enough, for example, somewhere has no machining
allowance or negative machining allowance, then the current deficiency is fed back to the
original casting design and the deformation is going to be calculated again. The iteration will
stop when even and enough machining allowance is obtained. The criteria for machining
allowance is estimated by the formulation below:
M max − M min ≤ δ
68
Where, M max is the maximal value of machining allowance, M min is the minimal value of
machining allowance, δ is a critical value for even judgement. If the uniformity of the machining
allowance is less than δ , the iteration of the analysis would be considered successful and end.
Fig. 3 Flow chart of the FDM/FEM system
Materials
The casting alloy ZG0Cr13Ni4Mo is a stainless steel alloy that widely used in hydraulic turbine
blade production. The chemical composition of the alloy is given in Table 1. The thermal and
mechanical properties of ZG0Cr13Ni4Mo used in the simulation are shown in Table 2 and Table
3 respectively.
Table 1 Chemical composition of ZG0Cr13Ni4Mo alloy(%)

Alloy Si Mn P S Ni Cr Mo Ca Al Fe
3.5- 12.0- 0.4- 0.25-
ZG0Cr13Ni4Mo ≤1.0 ≤1.0 ≤0.025 ≤0.008 ≤0.06 Bal
4.5 13.5 1.0 0.35
69
Table 2 Main thermal properties used in the simulation
Alloy λ (W / m ⋅ K ) c p ( J / kg ⋅ K ) ρ ( kg / m )
3
h f ( J / kg ) T ( C)
l
°
Ts ( ° C )
ZG0Cr13Ni4Mo 24.36 6.38×102 7.8×103 2.73×105 1470 1440
Table 3 Main mechanical properties used in the simulation

Temperature(℃) 25 600 800 1000 1200 1400
Young’s
186.0 14.0 8.3 7.2 4.5 1.3
modulus(×103MPa)
Tangent modulus
100.00 36.00 2.60 0.08 0.02 0.01
(×102MPa)
Displacement
The casting process of original model was firstly modeled and calculated displacement result on
Y-axis direction is shown in Fig. 4a. Y-axis is on the vertical direction of much more flat area on
blade surface and is basically the vertical direction for machining. The plus and minus maximal
displacements occur at the two corner areas and the deformation values on these two corner
points are -63.8mm and 44.6mm, respectively. The new model with inverse deformation was
also simulated and the displacement result is shown in Fig. 4b. Correspondingly, the deformation
values on the two corner points are -62.7mm and 46.7mm. The distribution of displacement of
the new model is similar to the original one and the deformation values just have little difference
with the original ones.
(a) original casting design without reverse (b) new casting design with reverse
deformation deformation
Fig. 4 Calculated displacement results on Y-axis direction
Machining allowance
70
In this case, the factor δ was set to 1mm. The analysis finished after 2 cycles. The machining
allowances of the original and new blade models are shown in Fig. 5. In the front side, the
machining allowance at the left corner area of the original model is negative, which is not
allowed in practice. From -20.3mm to 32.9mm, the distribution of the machining allowance is
not even enough either. These problems were solved by applying reverse deformation. After 2
cycles, there is no negative value of machining allowance in the new model and the distribution
of machining allowance of the new model is even enough. The difference of the maximal value
and the minimal value is just only 0.05mm.
(a) front side-original model (b) front side-cycle 1 (c) front side-cycle 2
(Max.: 32.9mm, Min.: -20.3mm) (Max.: 13.3mm, Min.: 11.3mm) (Max.: 12.03mm, Min.: 11.98mm)
(d) back side-original model (e) back side-cycle 1 (f) back side-cycle 2
(Max.: 44.3mm, Min.: -8.9mm) (Max.: 12.7mm, Min.:10.7mm) (Max.: 12.02mm, Min.: 11.97mm)
Fig. 5 The distribution of machining allowance
Fig. 6 The application of final reverse deformation
71
Fig. 6 shows the distribution of final calculated reverse deformation. The new blade with reverse
deformation was founded in factory. The actual inverse deformation taken in the production is
basically in good agreement with the calculated values.
Conclusions
The numerical simulation during casting process of large-scale hydraulic turbine blade was
carried out by a FDM/FEM system. By comparing the final 3-D blade surface with the ideal
model the machining allowance of blade casting was calculated. It is used for the criteria for the
design of casting. If it is not even and sufficient, then it is fed back to modify the casting design,
and the deformation will be calculated again to check the machining allowance. The iteration
will stop until the final machining allowance meets the requirement. Therefore, the last
modification of the casting design is the proper inverse casting. It can be found that the
deformation of the original blade occurs at the two corner areas lying on blade outlet edge
respectively. By the proposed method, the final casting design is obtained with the proper inverse
deformation given. The calculated inverse deformation is basically in good agreement with the
actual values taken in the production. And finally, the machining allowance is predicted too.
Acknowledgements
The Project is supported by the Foundation of Key Laboratory for Advanced Materials
Processing Technology, Ministry of Education, P. R. China.
References
1. B. C. Liu, T. Jing, 2001, China Machine Press.

2. W. Xue, Z. Y. Chen, “Study on Blade Cracks of Hydraulic Turbine Runner and Preventing
Methods”, Large Electric Machine and Hydraulic Turbine, 2002(5), 42-45.
3. F. Y. Li, Q. Y. Wang, “Technical Measures to Improve Casting Accuracy of Blades”, Power
System Engineering, 2007, 23(2), 71-72.
4. M. LI, T. Tao, P. C. Zhou, “Study on Casting Process of Improving the Runner Blads
Contour Quality”, Large Electric Machine and Hydraulic Turbine, 2006(6), 59-62.
5. Y. Zheng, S. Li, “Study on Measurement of Hydraulic Turbine Blade”, Heilongjiang Science
and Technology of Water Conservancy, 2005, 33(2), 1-4.
6. YANG Jin_hua; LI Shu_wei, “The Computer Aided Measuring Technology for Turbine
Blade”, Large Electric Machine and Hydraulic Turbine, 2000(3), 55-61.
7. J. W. Kang, 1998, PHD Theses of Tsinghua University.
8. X. G. Liu, J. W. Kang, T. Y. Huang, “Thermal Stress Simulation Considering Mechanical
Interaction Between Casting and Mold”, Advances in Computational Materials Science and
Engineering Methods, TMS, 2007, 11-18.
72
Multi-Temperature Uniaxial Compression Testing of Sintered ZrN and

(Zr,Ti)N Pellets as Surrogates for PuN and (Pu,Zr)N Fuels
K. Wheeler1, P. Peralta1, and K. J. McClellan2

1
Arizona State University
Department of Mechanical and Aerospace Engineering, Tempe, AZ 85287
2
Los Alamos National Laboratory, MST-8, Mail Stop G755, Los Alamos, NM 87545
Keywords: Ceramics, Compression, Microstructure, Damage, Temperature, Actinide
Abstract
In this work, ZrN and (Zr,Ti)N were studied as possible surrogates for PuN and (Pu,Zr)N. The
mechanical properties of sintered ZrN and (Zr,Ti)N pellets were examined to investigate the
effects that sintering temperatures and composition have on structural integrity. Uniaxial
compression testing was performed on ZrN and (Zr,Ti)N pellets sintered at either 1375°C
1475°C or 1600°C. Testing was performed in an ultra-high purity Argon atmosphere at two
temperatures: 25°C and 800°C. Post-Mortem fractography was performed using scanning
electron microscopy (SEM). In most cases elevated temperature testing resulted in a reduction in
compression strength by nearly 50%, an increase in compressive strain and an introduction of
non-critical cracking prior to catastrophic failure as compared to ‘identical’ samples tested at
room temperature. It was determined that (Zr,Ti)N solid solution samples have similar or higher
specific strength (strength divided by density) when tested at intermediate temperatures as
compared to pure ZrN samples due to their smaller grain size, higher porosity, and because of
increased crack arrest mechanisms and elastic energy dissipation sites. It is believed that the
strength and fracture behavior of these solid solution samples would be desirable in a multi-
element transmutation fuels application. Work supported under the Global Nuclear Energy
Partnership (GNEP) and the Advanced Fuel Cycle Initiative (AFCI), DOE/NE Agreement # DE-
FC07-05ID14654.
Introduction
Nuclear fuels based on actinide nitrides, particularly plutonium mononitride and other
possible solid solution variations, have considerable potential for advanced applications,
including nuclear power sources and nuclear-thermal propulsion for space applications [1-4].
Research carried out so far indicates that nitride fuels have a series of desirable properties,
including high thermal conductivity, high melting point, high actinide atomic density, low
swelling and low fission gas release, among others [3-5]. Interest on nitride based fuels for
advanced applications has arisen within GNEP and AFCI projects of the US Department of
Energy (DOE), since these materials are potential candidates for the development of a fuel that
could potentially enhance proliferation resistance in the next generation of nuclear reactors, and
for waste reduction via transmutation of transuranic fission products [6], thus reducing the
environmental impact of nuclear energy production by reducing long-lived radiation sources by a
factor of 10 and radiotoxicity by a factor of 100 [1].
Due to the high cost associated with the development, testing and characterization of
transuranic fuels, ZrN has been proposed as a surrogate material based on the fact that it is
isostructural with many actinide mononitrides (NaCl structure) [3], its ability to form a solid
73
solution with PuN [7], the similarities observed between its microstructure and that of actinide
nitrides [7], as well as being a possible inert matrix material to host minor actinide (Np, Am,
Cm) materials during transmutation [8-11]. (Zr,Ti)N was selected as a surrogate material for
(Pu,Zr)N due to the comparable difference in atomic radii, similar lattice parameter mismatch,
and similar crystal structure [7, 12, 13] all of which should result in similar transport during
sintering and a realistic approximation of the behavior of actinide solid solutions.
The addition of transuranics complicates the structural requirements of sintered fuel
pellets for a few reasons. The fact that Am may vaporize under typical sintering conditions [14,
15] has called for the development of alternative sintering parameters to reduce Am loss.
Furthermore 241Am can produce a relatively large quantity of helium during irradiation via α-
decay [16]. This extra gas could increase swelling [17], raise compressive stresses in the fuel
due to excessive cladding interaction, increase cracking and accelerate the degradation of the
mechanical integrity due to damage accumulation. In an effort to facilitate the release of the
excess helium, pellet microstructures need to have an increased percentage of connected
porosity, which unfortunately can lead to a decrease in strength and structural reliability.
In order to help develop a fuel form with the desired mechanical properties,
microstructure, acceptable percentage of open porosity and to evaluate the response of these
possible surrogate materials at different working temperatures, test samples of ZrN and (Zr,Ti)N
were prepared using a variety of sintering conditions. Relationships between the resulting
microstructure, processing parameters and mechanical properties were established and correlated
with potential fuel performance. These correlations can be useful in assisting the development of
nitride fuels for next generation reactors, space reactors and other advanced applications.
The sintered ZrN and (Zr,Ti)N pellets used for this study were prepared at Los Alamos
National Laboratory (LANL) at various sintering temperatures that were selected to achieve
specific sample densities based on sintering curves for ZrN that have been previously developed
for this project [18]. All of the powders were prepared in a glove box with a nitrogen-controlled
environment. The ZrN used for this study was from the same batch of commercial stock -325
mesh powder. Each of the samples, ZrN (100 wt% ZrN) and (Zr,Ti)N (60 wt% ZrN, 40 wt%
TiN) were mixed with an organic lube and binder (0.2 wt% Zn Stearate and 0.3 wt% PEG).
Each mixture was Spex milled for 45 minutes then pressed at 250 MPa. These pellets were cold-
pressed in a 4.16 mm diameter die and then sintered in a gettered UHP argon atmosphere at
either 1375°C, 1475°C or 1600°C for 10 hours plus thermal ramp time. Each of the pellets was
cut in half along a radial plane and diamond ground into a cube (≈ 2.5mm). Two test samples
were produced from each pellet in order to establish temperature dependant results from the
same specimen, one half tested at room temperature and the other half tested at an “intermediate”
temperature (800°C). Electron Microscopy was performed in an FEI XL-30 environmental
scanning electron microscope operating at 15kV. Uniaxial compression was performed using an
Instron 1331 servo-hydraulic load frame with a custom made fixture that is self-aligning and
allows testing under controlled atmospheres and high temperatures.
Uniaxial Compression
Uniaxial compression tests were conducted on ZrN and (Zr,Ti)N pellet sections to
catastrophic failure. The characteristics of the pellet sections examined are listed in Table 1.
74
Table 1: Characteristics of Sintered ZrN and (Zr,Ti)N Pellets
Pellet Code ZrTi-06-05 ZrTi-06-10 ZrTi-06-16 ZrN-06-35 ZrN-06-85 ZrN-06-63
Sintering Temp. 1375 °C 1475 °C 1600 °C 1375 °C 1475 °C 1600 °C
% TD SINT 69.51 78.68 79.99 84.49 92.04 93.15
Open Porosity% 17.83 4.59 7.47 10.78 0.38 1.17
Closed Porosity % 12.66 16.73 17.54 4.73 7.58 5.68
≈ Grain Size [µm] 0.5-5 1-5 1-5 1-2.5 5-10 20
The image sequence of a full ZrN pellet undergoing compressive loading shown in Fig.1
illustrates the longitudinal cracking that developed in all samples tested during uniaxial
compression at room temperature. It should be noted that the three frames in Fig. 1 are each only
0.1 seconds apart. Unfortunately, the failure sequence of pellets tested at intermediate
temperatures could not be imaged due to the physical limitations of the environmental chamber,
but similar behavior was confirmed by recovering pellet fragments after the tests. The results of
both ambient and intermediate temperature compression tests are shown in Fig.2a. In addition,
the compressive specific strength (strength divided by density) was also calculated and shown in
Fib. 2b, because of differences in sample density.
(a) (b) (c)

Figure 1: A 0.3 sec. failure sequence of sample ZrN-06-31:(a) uncracked; (b) initial crack
(indicated by the arrow); (c) catastrophic failure
Compressive Specific Strength [kNm/kg]
Compressive Ultimate Strength [MPa]
ZrN @ 25ºC ZrN @ 25ºC

(ZrTi)N @ 25ºC (ZrTi)N @ 25ºC
2500 ZrN @ 800ºC 400 ZrN @ 800ºC
(ZrTi)N @ 800ºC (ZrTi)N @ 800ºC
350
2000
300
1500 250
200
1000 150
100
500
50
0 0
(a) (b) 1375 C
1375 C 1475 C
1475 C 1600 C
1600 C
Figure 2: Comparison of ZrN and (Zr,Ti)N pellets tested at 25°C and 800°C: (a) Ultimate Stress
(b) Specific Strength
Samples sintered at 1375°C and 1475°C exhibit a trend of increasing specific strength
with increasing sintering temperature. It can be seen that the specific strength of (Zr,Ti)N is
comparable to that of the more dense pure ZrN samples when tested at 25°C, but it is slightly
higher when tested at 800°C. These trends, however, do not hold for samples sintered at
1600°C. The break down of strength of the pure ZrN sample is due to very large grain size, large
pores located on grain boundaries and relatively weak grain adhesion [19]. The reduction of
strength of the (Zr,Ti)N sample sintered at 1600°C could be due to a reduction in the dual phase
75
structure of the solid solution samples sintered at lower temperatures. It was shown via EDS
(not included in this work) that mixing of the ZrN and TiN components of the solid solution
increased with increasing sintering temperature. This clearly did not have an adverse effect on
the strength of the sample when tested at 25°C, but it could be a factor in the reduction of
strength at intermediate temperatures.
Stress-Strain curves (Figure 3) illustrate the typical behavior of all samples, where
specimens tested at 800°C display an increase in failure strain and noticeable curvature, both of
which indicate an increase in non-linear stress-strain behavior, due to either a small level of
plastic deformation or enhanced compliance caused by micro-cracking. The latter has been
noticed in other quasi-brittle materials [20]. It is currently unclear if plastic deformation was a
contributing factor of catastrophic failure as is the case for other high strength ceramics [21], in
which plasticity was shown to nucleate micro-cracks or if the increase in strain was due solely to
percolation, advancement and arrest of small cracks, as indicated by the introduction of small
drops in stress during loading prior to failure [20, 22], These load drops are a clear indication of
increased damage tolerance at elevated temperatures [22]. Transmission Electron Microscopy
(TEM) is currently being performed to help elucidate this matter and determine if plasticity is
present in the bulk material.
(a) (b)
Figure 3: Engineering Stress-Strain curves of (a) ZrN and (b) (Zr,Ti)N pellet sintered at 1475°C
and tested at 25°C and 800°C
Fractography of Compression Samples
The fracture surfaces of all the samples tested were evaluated via SEM (Figures 5 and 6)
and show a clear distinction between samples tested at 25°C and 800°C. Room temperature
results indicate failure is caused from a mixture of transgranular and intergranular cracking as
compared to almost entirely transgranular cracking for elevated temperature tests. Fractographic
images also show a significant increase of non-catastrophic damage, either in the form of
arrested long cracks or dispersed microcracking. The ability of the these materials to release
elastic energy at elevated temperatures without resulting in catastrophic failure is a desirable trait
in a nuclear fuel since it would enhance the fuel’s resistance to damage caused by pellet
swelling, cladding interactions and radiation induced defects.
The increased specific strength of the solid solutions tested at elevated temperatures can
be attributed to their smaller grain size, slightly increased fracture toughness of TiN compared to
ZrN [23], dual phase structure and higher porosity, since the larger number of grain boundaries
and pores in the solid solution will provide additional sites for energy dissipation, probably via
crack arrest or deflection, thus allowing for more damage accumulation before catastrophic
failure [22]. The extreme opposite is the case for pure ZrN samples sintered at 1600°C where the
larger grain size, high density, and relatively large pores located typically on grain boundaries
results in a material with very few energy dissipations sites [22], which in turn produces a
76
material with relatively low ultimate compression strength and with very little change in
compressive strength when tested at elevated temperatures.
(a) (b)
Figure 5: Compression test fracture surface of 1475°C ZrN: (a) 25°C test, 2000x, 10μm scale;
(b) 800°C test, 2000x, 10μm scale
(a) (b)
Figure 6: Compression test fracture surface of 1475°C (Zr,Ti)N: (a) 25°C test, 2000x, 10μm
scale; (b) 800°C test, 2000x, 10μm scale
Conclusions
In most cases elevated temperature testing resulted in a reduction in compression strength

by nearly 50%, an increase in compressive strain and damage tolerant behavior in the form of
non-critical cracking prior to catastrophic failure as compared to ‘identical’ samples tested at
room temperature. In addition, the presence of curvature in the stress-strain curve suggests the
presence of non-linear material behavior at intermediate temperatures. It was also determined
that (Zr,Ti)N samples have a higher specific strength (strength divided by density) when tested at
“intermediate” temperatures compared to pure ZrN samples due to their smaller grain size,
higher porosity, slightly increased fracture toughness of TiN compared to ZrN, dual phase
structure, and because of increased crack arrest mechanisms and elastic energy dissipation sites.
Acknowledgements
This project was funded by the Department of Energy under the Global Nuclear Energy
Partnership (GNEP) and the Advanced Fuel Cycle Initiative (AFCI) under contract #DE-FC07-
05ID14654 at Arizona State University, in addition to resources provided by LANL
77
References
1. DOE, AFCI Program Plan. 2005.

2. Kiforenko, B.N. and I.Y. Vasil'ev, How we will go to mars. Acta Astronautica, 2002. 54: p. 61-
67.
3. Ma, B., Nuclear Reactor Materials and Applications. 1983, New York: Van Nostrand Reinhold
Publishing.
4. Matthews, R.B., et al., Fabrication and testing of uranium fuel for space power reactors. Journal
of Nuclear Materials, 1988. 151(3): p. 334-344.
5. Minato, K., et al., Fabrication of nitride fuels for transmutation of minor actinides. Journal of
Nuclear Materials, 2003. 320(1): p. 18-24.
6. Koch, L., Formation and recycling of minor actinides in nuclear power stations. Handbook on
the Physics and Chemistry of the Actinides, 1986: p. 457-489.
7. Arai, Y. and K. Nakajima, Preparation and characterization of PuN pellets containing ZrN and
TiN. Journal of Nuclear Materials, 2000. 281(3): p. 244-247.
8. Burghartz, M., et al., Some aspects of the use of ZrN as an inert matrix for actinide fuels. Journal
of Nuclear Materials, 2001. 288(2-3): p. 233-236.
9. Konings, R.J.M., et al., Transmutation of actinides in inert-matrix fuels: fabrication studies and
modelling of fuel behaviour. Journal of Nuclear Materials, 1999. 274: p. 84-90.
10. Streit, M., et al., Zirconium nitride as inert matrix for fast systems. Journal of Nuclear Materials,
2003. 319: p. 51-58.
11. Walker, C.T. and G. Nicolaou, Transmutation of neptunium and americium in a fast neutron flux.
Journal of Nuclear Materials, 1995. 218(2): p. 129-138.
12. Tennery, V.J. and E.S. Bomar, Lattice Parameters of (U, Pu)N Solid Solutions. Journal of the
Americal Ceramic Society, 1971. 54(5): p. 247-249.
13. Yamada, T., M. Shimada, and M. Koizumi, Fabrication and Characterization of Titanium Nitride
by High Pressure Hot Pressing. Ceramic Bulletin, 1980. 59(6): p. 611-616.
14. Ogawa, T., et al., Vaporization behaviour of (Pn,Am)N. Journal of Alloys and Compounds, 1995.
224: p. 55-59.
15. Spirlet, J.C. and W. Muller, The preparation and purification of americium metal by evaporation.
Journal of the Less-Common Metals, 1973. 31: p. 35-46.
16. Sobolev, V., et al., Modelling the behaviour of oxide fuels containing minor actinides with
urania, thoria and zirconia matrices in an accelerator-driven system. Journal of Nuclear
Materials, 2003. 319: p. 131-141.
17. Olander, D.R., Fundamental Aspects of Nuclear Fuel Elements. 1976: Technical Information
Center, Office of Public Affairs, Energy Research and Development Administration.
18. Wheeler, K., et al., Effect of sintering conditions on the microstructure and mechanical properties
of ZrN as a surrogate for actinide nitride fuels. Journal of Nuclear Materials, 2007. 366: p. 306-
316.
19. Rice, R.W. and R.C. Pohanka, Grain-Size Dependence of Spontaneous Cracking in Ceramics.
Journal of the Americal Ceramic Society, 1979. 62(11-12): p. 559-563.
20. Blechman, I., Brittle solids under compression. Part 1: Gradient Mechanisms of Microcracking.
International Journal of Solids and Structures, 1997. 34(20): p. 2563-2581.
21. Lankford, J., et al., The role of plasticity as a limiting factor in the compressive failure of high
strength ceramics. Mechanics of Materials, 1998. 29: p. 205-218.
22. Kingery, W.D., Introduction to Ceramics. 2nd ed. 1976: John Wiley & Sons, New York.
23. Kuwahara, H., et al., Mechanical properties of bulk sintered titanium nitride ceramics. Materials
Science and Engineering, 2001. 319-321: p. 687-691.
78
A Nano-Indentation Study of Surface Plasticity in Zirconium Nitride
K. Wheeler1, P. Peralta1, G. W. Egeland2, and K. J. McClellan3

1
Arizona State University
Department of Mechanical and Aerospace Engineering, Tempe, AZ 85287
2
New Mexico Institute of Mining and Technology
Department of Materials and Metallurgical Engineering
3
Los Alamos National Laboratory, MST-8, Mail Stop G755, Los Alamos, NM 87545
Keywords: Nano-Indentation, Surface Plasticity, Zirconium Nitride, Yield Event
Abstract
ZrN was studied as a possible surrogate material for PuN under the Global Nuclear Energy
Partnership (GNEP) and the Advanced Fuel Cycle Initiative (AFCI) programs. In particular, this
work was carried out to examine the dislocation activity on the surface of monolithic ZrN and
establishes the ground work of current activities to determine the variation of plasticity and
fracture in specific grains of a dense sample of 1600°C sintered ZrN using nano-indentation.
Samples of monolithic ZrN were carefully polished using colloidal silica suspensions
(chemo-mechanical polishing) to produce a relatively strain free surface. It was found that the
load-penetration curves from nano-indentation on the polished surface displayed a displacement
jump of 31±3 nm at an average load of 1100±200 µN. The presence of this jump indicated a
permanent indentation in the sample, whereas loads below the critical resulted in elastic
behavior. This behavior has been observed in metallic materials and has been related to a sudden
“avalanche” of dislocations at the point of contact between the sample surface and the indenter
tip. Indentation experiments were then repeated after mechanical polishing of the surface with
1200 grit SiC paper. There was a clear increase in the surface roughness and the nano-
indentation experiments indicated that the jump in the load penetration curve disappeared
completely. This strongly suggests that the rough polishing produced a population of dislocations
on the sample surface, which precluded the need to induce a dislocation avalanche at the indenter
tip, making the jump disappear. In addition, seven grains with different crystallographic
orientations were selected via Electron Backscattered Diffraction (EBSD) from a sample of ZrN
sintered at 1600°C and isolated with fiducial markings using a Focused Ion Beam (FIB) to
perform nano-indentation measurements as a function of orientation. Post indentation
characterization and indent cross sectioning will be performed using a FIB.
Introduction
Nuclear fuels based on actinide nitrides, particularly plutonium mononitride and other
possible solid solution variations, have considerable potential for advanced applications,
including nuclear power sources and nuclear-thermal propulsion for space application [1-4].
Research carried out so far indicates that nitride fuels have a series of quite desirable properties,
including high thermal conductivity, high melting point, high actinide atomic density, low
swelling and low fission gas release, among others [3-5]. Interest on nitride based fuels for
advanced applications has arisen within the Global Nuclear Energy Partnership (GNEP) and
Advanced Fuel Cycle Initiative (AFCI) projects of the US Department of Energy (DOE), since
these materials are potential candidates for the development of a fuel that could potentially
enhance proliferation resistance of next generation nuclear reactors, and for waste reduction via
79
transmutation of transuranic fission products [6], thus reducing the environmental impact of
nuclear energy production by reducing long-lived radiation sources by a factor of 10 and
radiotoxicity by a factor of 100 [1]. ZrN has been proposed as a surrogate material based on the
fact that it is isostructural with many actinide mononitrides (NaCl structure), its ability to form a
solid solution with PuN [7], the similarities observed between its microstructure and that of
actinide nitrides [7], as well as being a possible inert matrix material to host minor actinide (Np,
Am, Cm) materials during transmutation [8-11]. Structural reliability of fuel is important for in-
pile performance, since cracking leads to the deterioration of effective thermal conductivity and
the increased probability of Pellet-Cladding Interactions (PCI) due to broken pieces of material
[12]. Therefore, it is very important to fully characterize the mechanical behavior of any
material that has the potential to be used in a reactor application.
Certain physical traits are known about ZrN that place it in a different class than most
ceramic materials. While this material is both very hard and brittle, which is typical of most
ceramic materials, it also has high thermal and electrical conductivity, which is typically a trait
of metallic materials. In addition, it has recently been shown that plasticity can be induced on
the surface of ZrN at room temperature [13]. Cross-sectional Transmission Electron Microscopy
(TEM) observations have shown surface dislocation formations produced from typical grinding
and polishing operations, over a region close to the surface that increases with depth with the
size of the polishing particles, to a rate of about 100nm per µm of diamond media used.
In this work, plastic deformation of monolithic ZrN has been evaluated directly via nano-
indentation and variations of plastic deformation have been characterized based on different
surface treatments to correlate with observed TEM variations in surface plasticity induced by
polishing mentioned above. In addition, preliminary steps of a study to characterize plasticity
and fracture variations of individual grains in sintered ZrN pellets are discussed.
Monolithic ZrN was produced by hot isostatic pressing powder (CERAC +200/325 mesh)
at 1800°C for 2 hours at 207 MPa. The HIPed sample density was measured via the Archimedes
method to be > 99% theoretical density. Chemical content showed some increase in oxygen
during processing to approximately 5 atomic %, much of which is constrained in a glassy phase
observed between particles. This HIPed slug was sectioned using a diamond-wafering blade,
then polished using a progression of SiC papers (600, 800, 1200 grit). The same sample was
then exposed to a variety of surface preparations for three different nano-indentation tests. After
each of the three surface treatments, the sample was exposed to air and ambient temperatures for
24 hours, to insure a uniform oxide layer thickness. First the sample was finished with 0.05µm
colloidal silica (chemo-mechanical polishing) for one hour followed by the first nano-indentation
test. The sample was then polished with 0.05µm colloidal silica for an additional 1.5 hours
followed by the second nano-indentation test. Finally the sample was re-polished using SiC
paper (600, 800, 1200 grit) before the last round of nano-indentation experiments.
Sintered ZrN pellets were prepared in a glove box with a nitrogen-controlled
environment. The ZrN powder used for this study was from commercial stock (-325 mesh)
powder and was mixed with an organic lube and binder (0.2 wt% Zn Stearate and 0.3 wt% PEG).
Each mixture was spex milled for 45 minutes then cold-pressed in a 4.16 mm diameter die at 250
MPa. These green pellets were sintered in a gettered UHP argon atmosphere at 1600°C for 10
hours plus thermal ramp time. The longitudinal plane of this test pellet was polished using SiC
papers (600, 800, 1200 grit) and finished with a 0.05µm colloidal silica solution for 3 hours.
Grain crystallography was obtained via EBSD, which was performed in order to locate grains
with specific crystallographic orientations using a Camscan scanning electron microscope with
80
an EDAX/TSL OIM system. Each of the desired grains was marked with circular fiducial marks
using a Focused Ion Beam (FIB) on a FEI Nova 200 SEM/FIB.
Nano-indentation was performed using a Triboscope III® system from Hysitron with a
diamond Berkovich indenter. This indenter is a three-sided triangle with total included angle of
142.5° and a tip radius ~200nm. The same tip was used to image the surface before and after
indentation using Atomic Force Microscopy (AFM).
Nano-Indentation of Chemo-Mechanically Polished Monolithic ZrN
The results presented by Egeland [13] showed that the depth of the near-surface region with
higher dislocation concentration is proportional to the particle size of the polishing media in
monolithic ZrN: therefore, several nano-indentation experiments were performed on a sample of
monolithic ZrN in order to evaluate the effects of very low initial dislocation densities compared
to higher dislocation concentrations produced intentionally. Figure 1 illustrates a typical indent
on a chemo-mechanically polished sample of monolithic ZrN as ‘imaged’ via AFM
(a) (b)
Figure 1: (a) Nano-Indentation (3000µN load, 1µm image width) and (b) line profile of chemo-
mechanically polished monolithic ZrN
The presence of sink-in and a small amount of pile-up around the indent suggests that
plasticity ‘may’ be active around the indent due to the similarity of these deformation modes to
the hardening behavior of elastic-plastic materials [14]. Nevertheless, the sink-in is likely to be
the result of the stiffness of the material in the elastic regime pushing the material into the bulk.
To examine this in more detail, load-penetration (P-δ) curves were obtained for wide range of
loadings, from 700µN to about 10,000µN, as shown in Fig. 2. Note that at around 1000µN, a
rapid yield event occurred. The wide range of loads used made it possible to study the
reproducibility and variability of both the load level and the displacement jump of this event.
(a) (b)
Figure 2: Family of load-penetration curves at different maximum loads.
81
Regarding the tests resulting in a yield event, the amount of displacement jump was fairly
uniform, i.e., 31±3nm, indicating similar deformation behavior for all cases. The load, on the
other hand, presented more variability, resulting in an average value of 1100±200µN. This
variability in the load was likely due to the presence of local asperities and irregularities in the
surface, as pointed out by Kramer et al [15]. In addition, small variations in local orientation,
composition and oxide layer morphology could also have contributed to the scatter in the load.
The load-penetration curves of indents producing displacement jumps were analyzed to
corroborate that the behavior was indeed elastic before the yield point by fitting the load-
penetration data to a power law function. Two different power laws are obtained for data before
and after the jump. The exponent in the power law is ≈1.45 before the jump, quite close to the
value of 1.5 expected for Hertzian elastic contact [16]. The exponent is 1.63 after the curve,
which is more consistent with plastic behavior, although lower than the value of 2 observed in
many materials [16].
A value of effective Young’s modulus, Er [16], was measured from the unloading slopes
of the curves shown in Fig. 2, resulting in a value of Er = 279 GPa, which is lower than the value
of 336 expected for ZrN (EZrN = 460 GPa, EDiamond = 1100GPa). This is likely due to the
presence of zirconium oxide crystallites in a layer close to the surface of the sample, as observed
in sintered specimens via cross-sectional TEM [13].
This experiment indicates that with many of the dislocations removed from the surface by
chemo-mechanical polishing this material produces a distinctly elastic response at loads below a
threshold of about 900µN and beyond this threshold there is a sudden rush of displacement, or
‘avalanche effect’, suggesting the onset of dislocation motion and multiplication.
The second phase of this experiment, after additional polishing with colloidal silica,
shows an increase in the critical load required to produce the dislocation avalanche effect up to
approximately 1600µN. This strongly suggests that continued polishing removed additional pre-
existing surface dislocations and as such the jumps required higher loads to nucleate and move
dislocations. The results for the “rough” surface condition are discussed next.
Nano-Indentation of Mechanically Polished Monolithic ZrN
To illustrate the effect of an increased concentration of dislocations at the surface of the material
prior to indentation testing, the surface of the same sample that was highly polished was re-
polished using SiC paper (600, 800, 1200 grit) and the nano-indentation test was conducted
again. The surface topography surrounding the indent and the load-penetration curve was quite
different in this case as shown in Fig. 3.
(a) (b)
Figure 3: (a) Nano-Indentation and (b) Load-Penetration curves of mechanically polished
monolithic ZrN
The presence of pile-up is indicative a material with low work hardening capabilities, as would
be the case of a material that has been deformed plastically [14]. An interesting observation is
82
that the load-penetration curves in all tests for this surface condition (Fig. 3b) did not show the
same displacement jump. It is believed that the sudden avalanche of dislocation activity
responsible for the displacement jumps in the first two tests is linked to a low dislocation density
in the vicinity of the indenter tip. The chemo-mechanical polishing using colloidal silica
solution will reduce the number of dislocations found near the surface of the sample. The lack of
available dislocations will result in a nearly perfectly elastic loading until the load is large
enough to create additional dislocations, which will then move suddenly into the sample,
producing the observed ‘avalanche effect’ [17].
Nano-Indentation of Sintered ZrN
Presented in this section are the first steps of a study to establish variations in plasticity and
fracture toughness based on variations of crystal orientation of individual grains. This study is
based on a ZrN pellet that was sintered at 1600°C. Fiducial markings were created around
individual grains to facilitate finding them at each step of the procedure needed to perform this
experiment, i.e., nano-indentation, imaging via AFM and SEM and establishing crystallographic
orientation using EBSD. In this sense, the polished sample was first imaged and given a few
large fiducial marks using a FIB to establish a reference location for EBSD characterization as
shown in Fig. 4a. Using the EBSD scan, seven grains were selected based on their orientation
and position on the stereographic triangle, one near each of the corners, one on the edge of the
triangle near the mid-point between each of the corners and one near the center of the triangle. A
trench was then made around each of these grains using the FIB once again, as shown in Fig. 4b.
(a) (b)
Figure 4: (a) EBSD image of numbered test grains, (b) Optical microscopy image of sample with
fiducial marks isolating desired grains.
Conclusions
Work was carried out to examine the dislocation activity on the surface of monolithic ZrN and
establishes the ground work of current activities to determine the variation of plasticity and
fracture in specific grains of a dense sample of 1600°C sintered ZrN using nano-indentation.
Load-penetration curves on relatively strain free monolithic ZrN displayed a displacement jump
of 31±3 nm at an average load of 1100±200 µN. The presence of this jump resulted in a
permanent indentation in the sample, whereas loads below the critical resulted in elastic
behavior. This clearly indicates that the jump is related to a yield event, where dislocation
motion is activated suddenly. Indentation experiments were then repeated after mechanical
polishing with 1200 grit SiC paper. There was a clear increase in the surface roughness and the
nano-indentation experiments indicated that the jump in the load penetration curve disappeared
completely. This strongly suggests that the rough polishing produced a population of dislocations
on the sample surface, which precluded the need to induce a dislocation avalanche at the indenter
83
tip, making the jump disappear. All these results show clearly that ZrN is fairly susceptible to
surface plasticity induced by sharp contact, as expected in polishing and nano-indentation,
despite the fact that it displays brittle behavior in bulk form.
Acknowledgements
This project was funded by the Department of Energy under the Global Nuclear Energy
Partnership (GNEP) and the Advanced Fuel Cycle Initiative (AFCI) under contract #DE-FC07-
05ID14654 at Arizona State University, in addition to resources provided by LANL
References
1. DOE, AFCI Program Plan. 2005.

2. Kiforenko, B.N. and I.Y. Vasil'ev, How we will go to mars. Acta Astronautica, 2002. 54:
p. 61-67.
3. Ma, B., Nuclear Reactor Materials and Applications. 1983, New York: Van Nostrand
Reinhold Publishing.
4. Matthews, R.B., et al., Fabrication and testing of uranium fuel for space power reactors.
5. Minato, K., et al., Fabrication of nitride fuels for transmutation of minor actinides.
6. Koch, L., Formation and recycling of minor actinides in nuclear power stations.
Handbook on the Physics and Chemistry of the Actinides, 1986: p. 457-489.
7. Arai, Y. and K. Nakajima, Preparation and characterization of PuN pellets containing
ZrN and TiN. Journal of Nuclear Materials, 2000. 281(3): p. 244-247.
8. Burghartz, M., et al., Some aspects of the use of ZrN as an inert matrix for actinide fuels.
Journal of Nuclear Materials, 2001. 288(2-3): p. 233-236.
9. Konings, R.J.M., et al., Transmutation of actinides in inert-matrix fuels: fabrication
studies and modelling of fuel behaviour. Journal of Nuclear Materials, 1999. 274: p. 84-
90.
10. Streit, M., et al., Zirconium nitride as inert matrix for fast systems. Journal of Nuclear
Materials, 2003. 319: p. 51-58.
11. Walker, C.T. and G. Nicolaou, Transmutation of neptunium and americium in a fast
neutron flux. Journal of Nuclear Materials, 1995. 218(2): p. 129-138.
12. Review of Fuel Failures in Water Cooled Reactors. Technical Reports Series #388. 1998:
International Atomic Energy Agency.
13. Egeland, G.W., Radiation Damage and Fission Product Release in Zirconium Nitride, in
Department of Materials and Metallurgical Engineering. 2005, New Mexico Institute of
Mining and Technology: Socorro, New Mexico. p. 394.
14. Giannakopoulos, A.E. and S. Suresh, Determination of elastoplastic properties by
instrumented sharp indentation. Scripta Materialia, 1999. 40(10): p. 1191-1198.
15. Kramer, D.E., K.B. Yoder, and W.W. Gerberich, Surface constrained plasticity: oxide
rupture and the yield point process. Philosophical Magazine A, 2001. 81(8): p. 2033-
2058.
16. Johnson, K.L., Contact Mechanics. 1985: Cambridge University Press.
17. Gerberich, W.W., et al., Indentation induced dislocation nucleation: the initial yield
point. Acta Materialia, 1996. 44(9): p. 3585-3598.
84
INFLUENCE OF HIGH-INTENSITY ULTRASONIC TREATMENT ON

THE PHASE MORGPHOLOGY OF MG-9.0wt.%AL BINARY ALLOY
Zhiqiang Zhang , Qichi Le, Shijie Guo, Jianzhong Cu
The Key Laboratory of Electromagnetic Processing of Materials, Ministry of Education,

P. O. Box 314, Northeastern University, Shenyang, Liaoning, 110004, P. R. China
Keywords: Magnesium Alloys, Microstructure, Ultrasonic Treatment, Phase Morphology
Abstract
Phase morphology is one of the most important microstructural characteristics determining the
mechanical properties and therefore the service performance of polycrystalline materials. The
effect of ultrasonic treatment on theβ-phase(Mg17Al12) morphology of Mg-9.0wt.%Al alloy is
studied in this paper. The result shows that with high-intensity ultrasonic vibration employed
during the solidifying of Mg-9.0wt.%Al, the β-phase in the entire cross section of the billet is
significantly refined and also changed from continuous to discontinuous morphology.
Sphericalβ-phase is formed during solidification of billet treated with high-intensity ultrasonic
vibration..
Introduction
Mg-based alloys have attracted attention because of their low density, high damping capacity,
high specific strength and specific stiffness, excellent machinability, good electromagnetic
shielding characteristics and good castability [1,2]. In fact, Mg-based alloys, especially those
based on Mg-Al, have been used in a variety of industrial fields, such as the aerospace,
automobile industries and 3C (communication, computer, consumption electronic). Mg-Al alloys
are the most common and economic commercial Mg alloys [3]. However, magnesium alloys are
not yet used to the same extent as their competitors such as aluminum alloys and plastics,
partially due to the difficulty to control their microstructure. To enlarge the usage of Mg-based
alloys, further improvements of the mechanical properties including ductility and strength are
being demanded. Grain refinement and phase morphology modification are therefore required to
improve the mechanical properties of as-cast components.
Secondary phase morphology is one of the most important structural characteristics
determining the mechanical properties and therefore the application and service performance of
metal components. Most commercial magnesium casting alloys contain 2-9wt.% aluminums.
The Mg rich section of the binary phase diagram reveals a maximum solid solubility of 12.9%
wt.% Al at the eutectic temperature of 437°C. Under equilibrium conditions, the Mg-Al casting
alloys should solidify as a single phase α-Mg solid solution and further cooling should lead to the
solid-state precipitation of Mg17Al12 (β-phase) within the α-grains [3]. The microstructure of
Mg-Al alloys in the as-cast condition, however, differs significantly from this prediction. Non-
equilibrium, metastable eutectic is present in the as-cast microstructure of Mg-Al alloys
containing more than about 2wt.% Al [3]. The presence of the brittle eutectic phase Mg17Al12
has a significant influence on the mechanical properties of Mg-Al alloy casting. The
modification of β-phase is of general interest since fine β-phase along with fine primary
magnesium grains improve mechanical properties and ductility. Three well-known secondary
phase modification methods have been developed thus far. These methods include chemical
modification[4,5], quench modification[6], and superheating modification[7]. In this paper, the
85
novel processing of high-intensity ultrasonic treatment is used to study the effect of ultrasonic
vibration on theβ-phase morphology of Mg-9.0wt.% Al alloys which is one of the most common
binary magnesium alloys.
In this paper, binary magnesium alloy Mg-9.0wt.%Al was used as the experimental material.
According to the Mg-Al binary phase diagram, the liquidus temperature of the alloy is about
590°C and the solidus temperature is 470°C.
The experimental apparatus for high-intensity ultrasonic treatment is shown in Figure1. The
ultrasonic system used for this research consisted of a metallurgic ultrasonic system, a resistant
furnace and an iron crucible. The ultrasonic system consisted of a ultrasonic generator with the
frequency of 20±2KHz, a magnetostrictive transducer made of high purity nickel sheets, and a
acoustic radiator made of mild steel. Output power of the unit could be adjusted from 0 to 2kW.
During the treatment procedure, the temperature of melt, the preheating temperature of the
radiator and the applying time of ultrasonic field were precisely controlled.
2
U ltrasonic W ater Cooling
G enerator System
3
6
Tem perature
Control
7 System
Figure 1. Schematic of Experiment Arrangement

1-ultrasonic transducer; 2-thermocouple; 3-ultrasonic radiator; 4-resistance heater; 5-iron
crucible; 6-Mg-9.0wt.Al%; 7-ceramic tube; 8-water; 9-tank
During the experiment, the melting of Mg-9.0wt.%Al alloy was carried out in the iron crucible
with the diameter of 40 mm and with the height of 110 mm heated by a laboratory resistance
furnace and protected by CO2+0.5% SF6 atmosphere. Mg-9.0wt.%Al alloy was melted at 700°C,
and held for 30min at this temperature to allow the complete dissolution of aluminum and to
obtain a uniform temperature field, and subsequently cooled to 670°C(about 80°C higher than
the liquidus) for ultrasonic treatment, and then the preheated ultrasonic radiator at 670°C was
introduced into the melt from the top of the crucible. Ultrasonic vibration with a power of 600W
86
was started right. When the temperature of the melt was reduced to 585°C,ultrasonic vibration
was stopped. During treatment, to evaluate the influence of ultrasonic treatment, all conventional
parameters were held constant and CO2+SF6 gas was used to minimize oxidation. For
comparison reasons, samples were also made without ultrasonic vibration. These untreated
castings were similar in shape with those treated castings.
In order to evaluate the influence of high-intensity ultrasonic vibration on the β-phase
morphology of Mg-9.0wt.%Al alloy. The specimens from the quenched alloys were mounted
and polished and then the etched with a solution of 96mL ethylene glycol and 4mL nitric acid for
metallographic analysis. Microstructures of the as-polished samples were characterized by an
optical microscope, Leica DMR and SSX-50 scanning electron microscope (SEM) with energy
dispersive spectroscopy (EDS). The area fraction ofβ-phase was carried out from the pictures
taken using software SISCIA S8.0.
Results
For Mg-9.0wt.% Al magnesium alloy, the solidification structures were composed of primary
dendrites and eutectic phases, which were formed in non-equilibrium cooling conditions. Figure2
shows the optical micrographs (100×) of the samples from the casting made with and without the
ultrasonic treatment. The casting process determines shape and distribution of the different
phases. The casting samples solidified in the conventional conditions exhibited primary α-Mg
dendrites with the eutectic β-phases and supersaturatedα-Mg solid solution. The average grain
size of the primaryα-Mg grains was 120~300μm. The continuous and non-uniformβ-phases were
segregated along the grain boundaries, which was shown in Figure2 (a). However, after the
ultrasonic treatment, the Mg-9.0wt.% Al made with high-intensity ultrasonic treatment exhibits a
more uniform microstructure and theβ-phase segregated at grain boundaries are more thinner and
smaller than that obtained without ultrasonic treatment. The primary magnesium grains enclosed
these uniform and fine β-phase become spherical. The average grain size of these globular
primary magnesium grains is 70~100μm.
a b
Figure 2. β-phase modification observed by optical metallurgical microstructure at low

magnification, (a) without ultrasonic vibration and (b) with ultrasonic vibration
Both Mg-9.0wt.Al% samples from casting made with and without high-intensity ultrasonic
vibration were characterized with SEM at a high magnification of 1000×, as shown in Figure3.
The coarse, continuous and non-uniform β-phases observed on the untreated Mg-9.0wt.Al%
87
magnesium alloy agreed with those of low magnification observation. However, in the samples
made from ultrasonic treatment, very uniform, fine and discontinuousβ-phase was observed.
a b
Figure 3. β-phase modification observed by SEM at 1000× magnification, (a) without ultrasonic
vibration and (b) with ultrasonic vibration
In order to study the effect of ultrasonic treatment on theβ-phase morphology, the quantitative β-
phase area fraction was also studied by software SISCIA S8.0. The statistical value of area
fraction of β-phase is shown in Figure4. It is clear that the area fraction of β-phase in the samples
solidified with the ultrasonic treatment is less than that of samples solidified in the conventional
conditions. That is to say, the ultrasonic treatment decreases the area fraction of β-phase at grain
boundaries in some degree (from about 11% to 8.5%), which is very significant for hot-tearing,
corrosion and subsequent handling.
12
10
Area fraction of Μg17Al12 %
0
Untreated treated
Figure 4. Area fraction of β-phase
SEM with EDS was used to investigate the distribution of Al elements in the cross-section of the
casting. Figure5(a) shows that Al segregates at grain boundaries with a net-work without the
ultrasonic treatment. However, the ultrasonic treatment refined and spheroidized the primaryα-
Mg crystal and distributed Al elements uniformly over the cross-section of the casting. Most ofβ-
phase in the grain boundaries were disconnected and broken after the ultrasonic treatment, as
shown in Figure5(b).
88
a b
Figure4 The distribution of Al elements on the cross-section of sample of Mg-9.0wt.% Al

alloy by SEM with EDS, (a) without ultrasonic vibration and (b) with ultrasonic vibration
Discussions
When high intensity ultrasonic is introduced into the molten magnesium alloy, two basic
phenomena of acoustic cavitation and acoustic streaming will occur, which play an important
role in the solidification behavior [8,9]. In the cavitation area, the tinny bubbles and violent
shock waves appeared during the collapse of the cavitation bubbles, causing the initial crystal
nucleus and β-phase formed during solidification to break down and homogenize throughout the
melt. In addition to breaking down the initial crystal nucleus and β-phase, the ultrasonic has also
lead to the nucleation rate of β-phase. Cavitation activates the initial crystal nucleus and β-phase
that exist in the melt, and were delivered into the solidification sites, and the gas start to diffuse
from the melt into the cavitation bubbles with the formation of cavitation when the ultrasonic
field is applied. Some of the cavitation bubbles oscillate at a frequency of the imposed ultrasonic
field and the gas content inside them remains constant, while other cavitation bubbles rapidly
increase in size under tensile stresses and the liquid evaporates inside the cavitation bubble. Yet
some other cavitation bubbles that are not completely filled with gas start to collapse as the
alternating compression and rarefaction phases of the sound wave pass through the melt [10].
The growth of cavitation bubbles will absorb energy from the melt around cavitation bubbles and
the size of small cavitation bubbles will increase. As a result, undercooling occurs on the surface
of the cavitation bubbles, which facilitates the formation of a lot of nucleus and β-phase, and
hence the probabilities of nucleation for primary crystals and β-phase are increased. The formed
nuclei and β-phase can be distributed throughout the melt by the acoustically induced streaming.
In this way, a large number of nuclei and β-phase can be produced during the expansion stage.
Moreover, the collapsing of the cavitation bubbles would results in an instantaneous high
temperature, high pressure and violent impact wave in the local zone of the melt, which would
also multiply the nuclei by crushing the secondary arms of primary crystals. Furthermore,
ultrasonic melt treatment established a more uniform temperature field, nucleation and growth
can take place almost simultaneously as mentioned previously. Thus, after the ultrasonic
treatment, the β-phase refinement and spheroidizing performance of the Mg-9.0wt.%Al are
improved to a large extent. In order to thoroughly understand the mechanisms for β-phase
modification with the ultrasonic treatment, further research need to be done.
89
Conclusions
In this study, the effect of ultrasonic treatment on the solidification of Mg-9Al alloy has been
measured. The experimental results are shown as follows:
(1) When the alloy was solidified in the conventional conditions, the morphology of β-phase in
the alloy was coarse, continuous and non-uniform. After the high-intensity ultrasonic treatment,
the phases are fine, discontinuous and uniform throughout the sample.
(2) Ultrasonic treatment can significantly refine the solidifying structure and decrease the
boundary segregation of Al.
Acknowledgements
The authors gratefully acknowledge the support of the National Basic Research Program of
China (No. 2007CB613701 and No. 2007CB613702), the Naultional Natural Science Foundation
of China (No. 50574028 and 50374025), the National Key Technology R&D Program of China
(No. 2006BAE04B01-5 and No. 2006BAE04B02-5) and the 111 Project of China (No. B07015).
References
[1] Y.Z. LU et al., “Fracture Behavior of AZ91 Magnesium Alloy,” Mater Lett 44(5)(2000) 265-
268.
[2] T.S. Srivatsan, L. Wei, and C.F. Chang, “The Tensile Behavior of Rapidly Solidified
Magnesium Alloys” J Mater Sci 30(7)(1995) 1832-1838.
[3] D.J. Sakkinen, SAE. Warrendale, 1994, 71-82.
[4] D.C. Jenkinson, L.M. Hogan, “The Modification of Aluminum-Silicon Alloys with
Strontium,” J Cryst Growth 28(1975) 171.
[5] K. Nogita, A.K. Dahle, “Effects of Boron on Eutectic Modification of Hypoeutectic Al-Si
Alloys,” Scripta Mater 48(2003) 307.
[6] G.Heiberg et al., “Columnar to Equiaxed Ttransition of Eutectic in Hypoeutectic
Aaluminium-Silicon Alloys,” Acta Mater 50 (10)(2002) 2537-2546.
[7] M.M. Haque,. Ahmad F. Ismail, “Effect of Superheating Temperatures on Microstructure and
Properties of Strontium Modified Aluminium–Silicon Eutectic Alloy,” J Mater pro tech
162(2005) 312-316.
[8] O.V. Abramov, “Non-Llinear Effects of Acoustic Generation in Solids,” ultrasonics 25(1987)
73-82.
[9] G.I. Eskin, Y.P. Pimenov, G.S. Makarov, “Effect of Cavitation Melt Treatment on The
Structure Refinement and Property Improvement in Cast and Deformed Hypereutectic Al-Si
Alloys,” Mater. Sci. Forum 242(1997) 65-69.
[10] G.I. Eskin, “Broad Prospects for Commercial Application of The Ultrasonic (Cavitation)
Melt Treatment of Light Alloys” Ultrason. Sonnochem, 8(3)(2001) 319-325.
90
EFFECT OF ELECTRIC CURRENT PULSE ON SOLIDIFICATION

STRUCTURE OF BEARING STEEL WITH LOW VOLTAGE
AND HIGH DISCHARGING FREQUENCY
Li Jie, Gao Yulai, Ma Jianhong, Zhai Qijie
Center for Advanced Solidification Technology(CAST), Shanghai University,

149 Yanchang Road, 200072 Shanghai, P.R. China
Keywords: Bearing Steel, Electric Current Pulse, Dendritic Structure, Segregation
Abstract
An experiment with respect to the influence of electric current pulse (ECP) on solidification
structure of bearing steel with low voltage and high discharging frequency during solidification
has been carried out. The results show that with the constant voltage and the pulse current peak,
the primary dendritic arm shortened and the rate of equiaxed crystal increased with increasing
the discharging frequency, but the secondary dendritic arm gets coarse. It is suggested that the
transverse temperature gradient of ingot is reduced attributed to the broadened mushy zone by
the agitation of ECP, and meanwhile the distribution of solutes gets more homogeneous in virtue
of interaction on electric and magnetic field, which also result in refinement of structure. In
addition, the refined dendritic grains and the increased rate of equiaxed grain will obviously
improve the central carbon segregation.
Introduction
Electromagnetic processing of materials (EPM) has been widely studied in last three decades[1],
and also some techniques have been applied in the metallurgical industry such as
electromagnetic stirring, electromagnetic casting etc. Nowadays, some novel control
technologies of solidification process are developed, as exemplified for the pulse magnetic
field[2-4], the pulse magneto oscillation[5] and the electric current pulse(ECP)[6-11]. All these
techniques have been successfully used to improve the quality and properties of materials, such
as grain refinement, macrosegregation improving etc., among which these techniques, the ECP
treatment is easy operation and readily utilized in practice. Thus, this technique is promising in
industrial applications, whatever in ingot casting or continuous casting, especially Liao and
Zhai[12]testified experimentally the grain refinement mechanism of ECP(up-down electrode
mode), showing that the grain refinement occurs when ECP makes the crystal nucleus depart
from the mould wall and drift into the melt, leading to a multiplication of the crystal nuclei and
grain refinement. This mechanism will establish experimentally and theoretically the foundation
for the further application of the ECP in the metallurgy industry.
However, in recent years, more investigations were mainly focused on the solidification process
of the experimental materials with low melting point and simple alloys under the influence of the
ECP. Little attention has been devoted to the effect of the ECP on solidification structure of the
iron and steel materials due to their high melting temperature, it is difficult to employ for
research. Moreover, high carbon and chromium bearing steel is an important structural material
used in ballbearing applications. Therefore, the effect and mechanism of ECP on refining
solidification structure of high carbon and chromium bearing steel was investigated in this paper.
91
Experimental Details
The experimental setup consists of a pulse generator with a capacity of 1500 μF, sand mould.
The discharging frequency and voltage range of the pulse power supply are 100Hz-1000Hz and
12.5V-3000V, respectively.
High carbon and chromium bearing steel as the experimental material was melted by median-
frequency induction furnace and its composition used in this study is listed in Table 1. After
deoxidization with Al at 1700±10°C, The melt was poured respectively into the cylindrical sand
mould of with the ECP of the parallel electrode modes as shown in Figure.1. The mould was
preheated to 200°C before the pouring. For comparison reason, under the same cooling
conditions, one specimen was subjected to an ECP with the same pulse current peak of 100kI A,
the same discharging voltage of 6vI V and the different discharging frequency while the other
was not treated. After solidification, casts cooled to the room temperature. Each specimen was
Ø50mm×180mm in size. The 70mm-piece specimens were sectioned transversely from the
bottom of ingot.
Table 1. Composition of the high carbon and chromium bearing steel (wt.%)
C Mn Si Cr Ni Cu Ti Al P S O Balance
1.01 0.34 0.22 1.47 0.05 0.06 0.0012 0.003 0.007 0.007 0.0008 Fe
Electrode
400
300 Wave shape of ECP 20mm
Pulse
Current I (A)
200
power
100
source
0
-100
-200
0 2 4 6
Time t (ms)
Sand mould
Molten metal
Figure.1 The schematic setup of the ECP with parallel electrodes
The specimens were ground, polished, and etched by the reagent of supersaturated picric acid for
microstructure examination. The microstructure was examined by an optical microscope. In
order to objectively analyze the change of microstructure, several images were recorded and
saved from the surface to the inner zone of the ingot, and ultimately put them together. The rate
of equiaxed crystal was described quantitatively by traditional area arithmetic.
Results and Discussions
The effect of ECP on the microstructure of bearing steel

The microstructures are shown in Figure.2, Apparently, without the ECP, the columnar dendrite
in the specimen showed a strong preferred crystallographic orientation as shown in Figure.2(a),
and the primary dendritic arm was very long and in the inner zone the dendrite reduced the
directionality for growth. With the ECP, the columnar dendrite region was shortened with an
increase in pulse discharging frequency as shown in Figure.3, it can be seen that the rate of
equiaxed zone increase from 7.4% without ECP to 61% with 100kI A and 400hI Hz ECP (here hi
92
is proportional constant), and the dendrite in the central equiaxed zone coarsened to a certain
extent, implying that under the ECP the mushy zone was widened. In addition, the columnar
dendritic region is shortened by the ECP. This structure evolution should undoubtedly improve
the macrosegregation of ingot especially for the high carbon and chromium bearing steel, which
generally produces severe central carbon segregation[13].
(a)
(b)
(c)
(d)
(e)
Surface Growth direction Inner

Figure.2 The microstructure of high carbon and chromium bearing steel without (a) and with
ECP of various parameters (b) 100kI A,100hI Hz (c) 100kI A,200hI Hz (d) 100kI A,300hI Hz (e)
100kI A,400hI Hz
In general, the shrinkage porosity defect is observed in the last solidification region of
castings(shown in Fig.2). Remarkably, the shrinkage porosity in the samples gradually improved
with an increase in pulse discharging frequency of the ECP(Figure.2(b)-(e)), indicating that
application of the ECP can enhance the liquid flow or decrease the temperature gradient ahead of
the solid-liquid interface.
The ECP promotes the columnar to equiaxed dentrite transient

Another phenomena from Fig.3 is that the ECP can give rise to the transition from columnar to
equiaxed dendrite, and the columnar to equiaxed transition (CET) will occur and therefore the
columnar region is correspondingly shortened with increasing the pulse discharging frequency. It
is well known that various mechanisms have been proposed to try to explain the local interaction
of columnar grain growth and equiaxed grain formation, which gives rise to a CET. These
consider, to varying extents, the solute and temperature fields, fluid flow and the growth of
equiaxed grain nuclei. Whatever the mechanism, a transition will only occur when the equiaxed
grains are sufficient in size or number to halt columnar grain growth. A CET will occur if the
equiaxed grains cannot be pushed ahead of the growing columnars and the columnars are
incapable of growing between the equiaxed grains[14].
93
70
60
The rate of euqiaxed zone(%) 50
40
30
20
10
0
-100 0 100 h 200 h 300 h 400 h 500 hI
I I I I
The frequency(Hz)
Figure.3 The relationship between the frequency and the rate of equiaxed zone
The effect mechanism of the ECP on the solidification structure

According to the above analysis and experimental results, the effect mechanism structure
refinement by employing ECP is proposed. It is deemed that the ECP gives rise to the agitation
of the upper melt surface, leading to formation of large number of nuclei in the undercooled zone
at or near the top melt surface and showering down into the undercooled melt head of the
columnar zone, and growing as they descended. Consequently, the CET occurs by the
impingement of the columnar dendritic interface upon the dendritic skeleton of floating equiaxed
crystals. Therefore, with increasing the pulse discharging frequency, the more nuclei shower
down into the melt, the greater impingement takes place ahead of columnar dendrite. It shows
that the mushy zone is broadened, resulting in the ripening of the dendrites. On the other hand,
though the Joule heat induced by the ECP[15] may delay the freezing time, yet the large
temperature difference between the melt and air is still able to lead to the quick cooling and thus
the solidified shell forms in a short time on the upper melt surface. However, once the stable
solidified shell forms, the effect of the ECP on the solidified structure is weakened[12], thus, the
total of showering nuclei is limited, which makes the equiaxed dendrite grow freely and coarsely
in the mushy zone.
Conclusions
1. Keep the voltage and peak value of the utilized ECP unchanged, the primary dendritic arm can
be shortened and the rate of equiaxed crystal is increased with increasing the discharging
frequency, but the secondary dendritic arm coarsened.
2. The shrinkage porosity is improved with increasing the discharging frequency of the ECP.
3. The ECP with parallel electrodes can give rise to the columnar to equiaxed transition.
Acknowledgement
The authors gratefully acknowledge the financial support from the National Natural Science
Foundation of China (Grant No. 50674064 and Grant No. 50734008).
94
References
[1]Q.J Zhai, Y.L Gao, in: Q.Y. Han, Gerard Ludtka, Q.J. Zhai(Eds.), Materials Processing Under
the Influence of External Fields, A Publication of TMS, Orlando, 2007, pp. 45-54.
[2]Z.L. Zhao, R. Zhang, L. Liu et al., “Unidirectionally solidified Al-Cu eutectic alloy under
high intensity pulsed magnetic field,” Materials Science Forum, 475-479 (2005), 2619-2622.
[3]Y.L. Gao, Q.S. Li, Q.J. Zhai et al., “Comparative study on structural transformation of low-
melting pure Al and high-melting stainless steel under external pulsed magnetic field,” Materials
Letters, 61 (2007), 4011-4014.
[4]Q.S. Li, C.J. Song, Q.J. Zhai et al., “Effect of pulsed magnetic field on microstructure of
1Cr18Ni9Ti austenitic stainless steel,” Materials Science and Engineering A, 466 (2007), 101–
105.
[5]Y.Y. Gong, J.X. Jing, Q.J. Zhai et al., in: Q.Y. Han, Gerard Ludtka, Q.J. Zhai(Eds.), Materials
Processing Under the Influence of External Fields, A Publication of TMS, Orlando, 2007, pp.55-
60.
[6]Nakada M, Shiohara Y, Flemings M C, “Modification of solidification structures by pulse
electric discharging,” ISIJ International, 30 (1990), 27-33.
[7]Branak J P, Sprecher A F, Conrad H, “Colony (grain) size reduction in eutectic Pb-Sn castings
by electroplusing,” Scripta Metallurgica et Materialia. 32 (1995), 879-884.
[8]L.N. Brush, Richard N. Grugel, “The effect of an electric on rod-eutectic solidification in Sn-
0.9wt%Cu alloys,” Materials Science and Engineering A, 238 (1997), 176-181.
[9]F. Li, L.L. Regel, W.R. Wilcox. “The influence of electric current pulses on the
microstructure of the MnBi/Bi eutectic,” Journal of Crystal Growth, 223 (2001), 251-264.
[10]Y.S. Yang, Q. Zhou, Z.Q. Hu. “The influence of electric current pulses on the microstructure
of magnesium alloy AZ91D,” Material Science Forum, 488-489 (2005), 201-204.
[11]X.L. Liao, Y.L. Gao, Q.J. Zhai et al., in: Q.Y. Han, Gerard Ludtka, Q.J. Zhai(Eds.),
Materials Processing Under the Influence of External Fields, A Publication of TMS, Orlando,
2007, pp.189-194.
[12]X.L. Liao, Q.J. Zhai, J. Luo et al., “Refining mechanism of the electric current pulse on the
solidification structure of pure aluminum,” Acta Materialia, 55 (2007), 3103-3109.
[13]T. Kato, H. Jones, D. H. Kirkwood, “Segregation and eutectic formation in solidification of
Fe-1C-1.5Cr steel,” Materials Science and Technology, 19 (2003), 1070-1676.
[14]J. A. Spittle, “Columnar to equiaxed grain transition in as solidified alloys,” International
Materials Reviews, 51 (2006), 247-269.
[15] X.L. Liao, Q.J. Zhai, C.J. Song et al., “Effects of electric current pulse on stability of
solid/liquid interface of Al–4.5 wt.% Cu alloy during directional solidification,” Materials
Science and Engineering A, 466 (2007), 56–60.
95
A CALCULATION MODEL FOR THERMAL PERFORMANCE DURING

PARTICLE COOLING IN THE SUBSTATE-COATINGS SYSTEM BASED
ON PLASMA SPRAYING PROCESS
Li-Ping Niu1, Ting-an Zhang2, Ji-Cheng He3, Zhi-He Dou4

1
Li-Ping Niu (School of Materials&Metallurgy, Northeastern University);
Shenyang, Liaoning 110004, China
2, 3,4
Ting- An Zhang Professor, E-mail: zta2000@163.net
Shenyang, Liaoning 110004, China
Keywords: Particle Temperature, Plasma Spraying, Residual Stresses, Impact
Abstract
Residual thermal stress is caused by particle deposition of thermally sprayed coating
materials. The calculation of thermal stress is based on the estimate of particle’s temperature
during deposition of the coating and the analysis of subsequent temperature equalization
processes. Due to the wide variety of material and process parameters determining particle’s
temperature in the hot plasma flowing, systematic experimental tests are extremely difficult. In
order to estimate this temperature, a mathematical model was developed to calculate the yield
stress. One of features of current model is the introduction of the layer thickness. Calculated
results of the strain for different material combinations show that predicted values agree well
with the experiment data.
Introduction
For many years, many surface treatment methods have been developed to improve the
properties of materials which have been invented. in this paper the plasma spraying,the
technique of forming special coating , is mainly studied.
Residual internal stresses are caused by the different thermo-physical properties of the
substrate during the process of deposition of particle and residual internal stresses were
influenced by the spray painting technique. The effects of wide variety and distribution of
residual stresses between coating and matrix on the functional performance is the key.
The thermal exchange between Particle and plasma flow are very complicated and exist
lots of boundary condition on unsteady state. The calculation of thermal exchange process
through systematic analysis and measure of the partial temperature in the plasma flow are very
difficult.
Theory
In this article we try to obtain an analytical model to calculate the mechanics property of
partials including elastic limit and surface σk, as a function of time. As a molten particle strikes
the surface of a solid, it spreads out and forms a flat splat. The scheme of the process, we shall
refer to, is:
97
Fig.1 Schematic depiction of impact spreading of a single particle
The initial partial is a cylinder with both bottom diameter and height are equal to d0.
Particle, at the moment of impact, is also a cylinder, but now the height is equal to δmin and the
bottom diameter is equal to dmax.
particle height will be assumed to be continuous in [d0, δmin], in this model, the change of δ
instead of the change of time is considered.
The signal tungsten particle coated onto a 45 steel target was studied. (initial diameter 63-100
μm, initial injection velocity 60-80 m/s)
To evaluate mechanical stress, it has been recognized particle deformed in ideal
elastic-plastic range and stress-strain relation in the coating by
⎧ 0 εi = 0
σт = ⎨ , (1)
⎩σ 0 ε i > 0
The physical phenomenon can be explained by the law of conservation of energy, which
can be written in the following form:
E R = E P + E F , (2)

∫
where E = σ vdS is the power reaction to the forces of plastic deformation of particle;
R
k
Se
σ k -contact pressure on interface between substrate and particle. Se represents the surface on
which external forces are applied; v is velocity;

E P = ∫ σ 0ζ i dV is the power spent for plastic deforming; σ 0 :stress intensity; ζ i is deformation
V
velocity; V : particle’s volume;
E F = ∫ μ iσ 0 vT+ − vT− dS is the power spent for overcoming friction forces between contact
Sc
surface;
μ i is friction coefficient, which assumes the value of internal friction μ i = 1 3 ;
vT+ − vT− is the modulus of difference between velocities of 2 surfaces during contact; [1-7]
Moreover, in this equation we neglect the term dealing with elastic power, assuming that it
is negligible with respect to plastic one. This approximation seems to be correct if we think that,
at the moment of impact, particle is affected by a very large deformation. Of course, neglecting
98
this term will not permit us to observe some physical phenomena, such as elastic wave in
particle border.
The terms in equation (2) can be expressed as follows.
Supposing particle density is constant during the impact, we can write the volume
conservation law:
d 02 d2
π d0 = π δ, (3)
4 4
or, solving with respect to d:
d0
d = d0 . (4)
δ
With regard to velocity fields along X1 axis, we shall assume:
x1
v1 = −v1m , (5)
δ
Remembering again volume preserving law and taking into account the symmetry of
phenomenon, we can write:
∂v1 ∂v2 v2
+ + = 0, (6)
∂x1 ∂x2 x2
Substitute differential equation (5) into (6) and assuming v2= v2(x2):
dv2 v2 v1m
+ = , (7)
dx2 x2 δ
Considering the symmetry of partial deformation relating to the system, v2(0) must be equal to
0, so the whole velocity field is given by:
x v x
v1 = −v1m 1 , v2 = 1m 2 . (8)
δ 2 δ
where ζ ij indicates the deformation velocity tensor, it can be expressed as this kind:
1 ⎛ ∂v ∂v ⎞
ζ ij = ⎜⎜ i + j ⎟⎟
2 ⎝ ∂x j ∂xi ⎠
From equation (8) we can obtain deformation velocity field:
∂v1 v ∂v v
ζ 11 = = − 1m ; ζ 22 = 2 = 1m (9)
∂x1 δ ∂x 2 2δ
Remembering law of conservation of mass, ζ 11 + ζ 22 + ζ 33 = 0 , we obtain ζ 33 :
v1m
ζ 33 = −ζ 11 − ζ 22 = , (10)
2δ
99
and ζ ij = 0 , if i ≠ j .
From equations (9) and (10) we can obtain deformation velocity intensity, ζ i :
2
2 ⎛ v1m v1m ⎞ v
ζi = 2⎜ − − ⎟ = 1m (11)
3 ⎝ δ 2δ ⎠ δ
where ζ i =
2
(ζ 11 − ζ 22 )2 + (ζ 33 − ζ 22 )2 +
3
(
+ (ζ 11 − ζ 33 ) + 6 ζ 122 + ζ 132 + ζ 232
2
)
Regarding E P and E F , we obtain respectively:
v d3
E P = ∫ σ 0ζ i dV = σ 0 1m π 0 (12)
V δ 4
d
π d3
E F = ∫ 2 2πx2σ 0 v 2 μ i dx2 = v1m σ μ (13) Substituting (4) into (13):
0 24 δ 0 i
π d3 d3 2
E F = v1mσ 0 μ i 0 03 2 (14)
24 δ δ
According to the law of conservation of energy, the sum of equations (13) and (14) must be
equal to E R ,
π d3 ⎛ μ d32 ⎞
E R = σ 0 v1m 0 ⎜⎜1 + i 03 2 ⎟
⎟ (15)
4 δ ⎝ 6 δ ⎠
We can also calculate E E as:
πd 2
E R = σ k v1m . (16)
4
Substituting (4) into (16), we have:
π d3
E R = σ k v1m 0 , (17)
4 δ
So, from (15) and (17) we obtain the dependence of σk on δ:
⎛ μ i d 03 2 ⎞
σ k = σ 0 ⎜⎜1 + ⎟ (18)
⎝ 6 δ 3 2 ⎟⎠
and A represents lost energy for friction and deformation. For this purpose, we need to
calculate:
A(δ ) = ∫ (E P + E F )dt =
t
100
π t ⎛ μ i d 03 2 ⎞ v1m
= σ 0 d 03 ∫ ⎜⎜1 + ⎟ dt. (19)
4 0
⎝ 6 δ 3 2 ⎟⎠ δ
Noting that v1m dt = −dδ , we obtain:
π δ d
3
⎛ μ i d 03 2 ⎞ π ⎡ d μ ⎛ d 03 2 ⎞⎤
A(δ ) = − σ 0 ∫ 0 ⎜1 +
⎜ 32 ⎟
⎟dδ = = σ 0 d 03 ⎢ln 0 + i ⎜ 3 2 − 1⎟⎥ . (20)
⎜δ ⎟
4 d 0 δ ⎝ 6 δ ⎠ 4 ⎣⎢ δ 9 ⎝ ⎠⎥⎦
To determine σk, it is necessary to calculate σ0. We shall calculate σ0 by an energy balance,
observing that:
E K ( 0) − E K ( t ) = E P ( t ) + E F ( t ) ,
then, taking into account that our independent parameter is δ:
E K (d 0 ) − E K (δ ) = E P (δ ) + E F (δ ) = A(δ ) ,(21)
The kinetic energy is calculated by the following dependence:
πd 03 ρ v p
2
E K (d 0 ) = , (22)
4 2
From equations (20), (21) and (22), all of them calculated in δ=δmin, solving with respect to σ0:
ρv 2p
σ0 = 2 , (23)
d0 μ ⎛ d32 ⎞
ln + i ⎜⎜ 03 2 − 1⎟⎟
δ min 9 ⎝ δ min ⎠
where ρ is the density. δmin , vP is the layer thickness and initial moving velocity respectively.
Experimental procedure
Particle’s moving velocity was measured by self-recorder, as summarized in Fig 2.

Particle’s flying velocity can be calculated by vp=vtgβ, where v is the velocity of vertical
motion.
Fig . 2 The optically scanning of the plasma flowing with sprayed

particles by velocity recorder.
As regards δmin, we measured the layer thickness according to the micrograph. Taking into
account that amplification factor is 500. Then we calculated statistic parameters such as average
101
value δaver and standard deviation σ.
Fig. 3 Microstructure of coating and data for the layer thickness material W, d0=63μm,
vP =60 m/s, ρw=19300 Kg/m3.(×500)
Fig. 4 Microstructure of coating and data for the layer thickness material
W+1.5%La2O3, d0=63μm, vP =60. m/s, ρw=19300 Kg/m3 (we assume that the
percentage of La2O3 does not modify the density of W). (×500),
The unit of particle’s diameters is μm, and the unit of stresses is MPa. We consider velocity
equal to 60 m/s (left tables) and to 80 m/s (right tables), these evaluations by the formula(23)
are shown in the Tabs1 and tabs. 2 for the 1st and the 2nd experiment.
Tab.1 The 1st experimental evaluation of the elastic limit for vP =60 m/s (a) and 80 m/s (b)
d 0 , /μm σ 0 , MPa (vP =60 m/s) σ 0 , MPa (vP =80 m/s)
δ min = 9.901 δ min = 10 .514 δ min = 9.901 δ min = 10 .514
63 12.33 13.02 21.93 23.15
100 8 8.53 14.33 15.17
Tab.2 2nd experimental evaluation of the elastic limit for vP =60 m/s (a) and vP =80 m/s (b)
d 0 , /μm σ 0 , MPa (vP =60 m/s) σ 0 , MPa (vP =80 m/s)
δ min = 9.867 δ min = 9.867 δ min = 9.867 δ min = 9.867
63 12.3 12.3 21.86 22.6
100 8 8 14.3 14.79
With respect to the 1st experiment, minimum value of σ0 is 8MPa with an initial diameter
(d0=100μm) and initial velocity vp=60 m/s, while maximum value is 23.15 MPa with the
previous quantities ( d0=63μm, vP =80 m/s).
102
In the 2nd experiment, minimum value of σ0 is 8MPa with initial diameter equal to 100 μm
and initial velocity equal to 60 m/s, while maximum value is 22.6MPa for 63 μm and 80 m/s,
respectively.
In this paper, the effects of particle impacting on the temperature change were analyzed.
The dependence of yield stress on the temperature has been chosen to estimate particle
temperature changing. Fig5 gives the relation between the strength of materials and temperature.
According to curve 1A, the particle temperature under the experimental conditions can be
calculated.
yield stres, ×10 MPa
Fig .5 Relation between yield stress and heating temperature
Considering an interval of 8-23 MPa for σ0 in the 1st experiment, the temperature of
2776-3072 °C is obtained. As regards the 2nd experiment, considering an interval of 8-22.6 MPa
for σ0, a temperature interval of 2760-3072 °C is obtained.
In order to calculate yield stress σ0, it has been chosen to consider an average velocity of
70 m/s. From these meanings of σ0, then we obtain following data.
It is obvious that the heating temperature of the particle in the plasma flowing is
84.7%-89.3% of melting point of coating materials.
Tab.3 The particle’s temperature in the hot plasma flowing at the moment of impact on the
surface of the substrate
d0(μm) δ min (MPa) σ 0 (MPa) T( ) T/Tm
100 10.265 11.3 3027 0.893

63 10.265 17.26 2869 0.847
Where Tm is the melting point of the coating material W.
Covering the theory and laboratory experiments, the approximate method were conducted
to evaluate particle’s temperature with taking into the difference between temperature and
deformation in possessor layers. It avoids to investigate the thermal exchange process between
partial and plasma flow, and the unsteady boundary conditions.
Utilizing aforementioned results about particle size and temperature, stress analysis has
103
been performed by a model of the formation of residual stresses in the substrate-coating system
in plasma spraying processes. Main idea for this estimation consists of transforming analysis
from thermo-mechanical into mechanical only. The calculated and experimental results for W
and Al2O3 on steel are shown schematically in Fig. 6. The experimental data agree with the
calculated curve very well.
Calculation of the strains distributions was based on the following physical parameters for
coating and substrate materials and spraying technology: Young’s modulus E(×1011N/m2):
1.922, 4 and 3.8; Thermal expansion coefficient(×10-6 K-1):11.9, 5.11 and 8 ; Density
(×103kg/m3): 7.57, 15.62 and 5.56 for Steel, tungsten and alumina respectively, coating
thickness 1.79mm, 2.05mm, amount of sublayers: 12, 14 for W and Al2O3, respectively; current
350A; pressure 40V; mass flux of gasses: 1.1g/s for argon and 0.1 g/s for azotes; spraying
distance :100mm.
A comparison between the measured and calculated results show rationality of the
calculated model of particle’s temperature for metal coating and ceramic coating.
δ = 1.79mm
(a)
δ = 2.05mm
(b)
σ-The average measuring stress; δ-the average calculated stress.
(a) W on steel and for (b) Al2O3 on steel:
Fig 6. Comparison between calculated residual stresses curves and the measured values in the
coating
Thus, the numerical examination of the formation of residual stresses in the

substrate-coating system has made it possible to optimize and improve spraying technology. In
principle, varying the technological parameters, this model can be used to control the residual
stresses. Technology to spray high performance coating is based on evaluating of stress level.
Microstructure of substrate -coating are shown in Fig 7.
104
(a) (b)
(a) W and (b) Al2O3 on steel, respectively) (X125),

Fig7. Microstructure of substrate coatings in plasma spraying
Conclusions
1. Particle’s temperature increased to 84.7-89.3 percent of melting point of coating materials.
The advantage of current model is taking into account unsymmetrical temperature of the
particle in spraying layers.
2. The stress state of coating composite has been investigated by mathematical model of
spraying particle’s temperature. The mean stress showed good agreement with experimental
date. The model is feasible on calculating particle’s temperature of metal coating and
ceramics.
References
1. Tarasov V.A. Methods of analysis in mechanical engineering. Publ. N.E. Bauman Moscow
State Technical University. Moscow, 1996.
2. Zаrubin V.С., Оvchinnikov А.G. Quality of plasticity deformation. pub 1. N.E. Bauman
Moscow State Technical University. Moscow. 1990..
3. К.V. Frolov, et. Mechanical engineering. Encyclopedia. Publ. Mechanical engineering.
Moscow. 2001, 1-3(2):1. 1994. – 534.
4. Polukhin P.I., Gun G.Y., Galkin A.M. Intensity and elastic deformation of metals and alloys.
// lurgic publishing, Russian, 1976.
5. L. Vergani. // Mechanics of materials. Mac Graw Hill, Milan. Italey. 2001.
6. Bobylev А.В. Mechanical and mechanic property of metals. Publ. metallurgy. Moscow,
1987.
7. ljasnikov V.N, Ryazhenko B.F. mathematical model of plasma-spraying for powder sprayed
material. Electrical technique. 1979. 5:64-70.
8. Liping Niu, 2005;Study of part performance’s conformation by controlling residual stress in
plasma-sprayed coatings. Doctor’s dissertation, N.E. Bauman Moscow State Technical
University. Moscow, 2005.
105
OPTIMIZATION OF GAS CARBURIZING PROCESS IN BATCH

FURNACES WITH ENDOTHERMIC CARBURIZING ATMOSPHERE
WPI1, Olga Karabelchtchikova1 and Richard D. Sisson, Jr.1

1
WPI (Worcester Polytechnic Institute);
Center for Heat Treating Excellence
Department of Mechanical Engineering,
100 Institute Rd, Worcester, MA 01609, USA
Keywords: Optimization, Gas Carburizing, Model, Cost, Energy Consumption, Efficiency
Abstract
The paper addresses the current industrial issues with the gas carburizing process control and
carburizing time/cost optimization. The optimization strategy is based on 1) understanding the
effect of process parameters (carbon potential, temperature and time) on the mass transfer
coefficient and carbon diffusivity in austenite; 2) functional correlation of the observed
variations in the process parameters on the kinetics of carburizing; and 3) optimization of the
process parameters that would allow achieving the desired case depth with minimum cost and
processing time. The index of performance for the process optimization involves both the
surface carbon concentration and the case depth. While the first parameter depends on accurate
control of the atmosphere and the carbon potential in the furnace, the case depth is primarily
influenced by the furnace temperature and the duration of the carburizing process. Application
of this optimization technique should result in significant energy reduction by shortening cycle
time and thereby enhanced furnace capacity.
Introduction
Gas carburizing is an important heat treatment used for steel surface hardening. Although the
process has been successfully used in industry for over 50 years, the carburizing cycles are
generally designed through plant trials and empirical methods, and therefore, they are rarely
optimized [1]. From a customer’s perspective, the quality requirements for the carburized parts
include achieving a sufficient carbon concentration at the steel surface and a desired case depth
along the carbon concentration profile. Meeting these quality requirements helps ensure adequate
performance of the carburized parts for a particular application and helps avoid premature failure
in service. Carburized parts with insufficient case depths are subject to rejections [2] or
additional rework [1], which significantly increase the total processing cost and total processing
time. From a manufacturer’s perspective, the carburizing cycles should be time- and cost-
efficient. Anticipated shortages in natural gas supply and energy resources demand industry to
search for optimized process conditions and efficient energy utilization [3]. In the competitive
market this would require finding global optimal solutions to meet the specified quality
requirements while shortening cycle time and reducing energy consumption.
Optimization of the industrial carburizing parameters is typically pursued by trial and error
methods. In addition to being time consuming and expensive this approach yields suboptimal
result at the best [1]. Palaniradja et.al [2] reported their optimization work based on experimental
investigations and a Taguchi statistical approach. The authors considered three levels of the
carburizing temperature, carbon potential and time and evaluated their effect on the surface
107
hardness and case depth. While statistical analysis of the experimental data determined ‘the best’
combination of factors within the selected process parameters, and not the global optimum itself.
Another common optimization approach is to approximate the experimental data with a second-
order regression model [4] and search for an optimal solution using a response surface technique.
Application of the regression models may yield an adequate solution, although it ignores the
functional relationship between the process variable and the carburizing performance
measurements and, therefore, cannot be used unless extensive experimental data are available.
Sahay and Mitra [1] built their optimization model using numerical and analytical approach. The
carburizing process parameters were correlated to the plant performance metric and to the overall
cycle cost. Using extensive search method, the authors optimized the boost stage temperature
and time based on the minimum carburizing cycle cost as the optimization criterion.
Optimization of the carburizing parameters in this paper is the conclusive chapter in a series of
experimental and theoretical work on gas carburizing process control and optimization. A
carburizing model was developed and validated in the authors’ previous publications [5] and was
extensively used in this work to simulate the carbon concentration profiles and the corresponding
case depth. A method of direct flux integration was developed which allowed calculation of the
mass transfer coefficient and carbon diffusivity from the experimental data [6,7]. These kinetic
parameters were used to model the relationship between the controllable input parameters (carbon
potential, temperature and time) and the carburizing performance (surface carbon concentration
and case depth). The optimization strategy is based on 1) understanding the effect of the process
parameters on the mass transfer coefficient and carbon diffusivity in austenite; 2) functional
correlation of the observed variations in the process parameters on the kinetics of carburizing;
and 3) optimization of the process parameters that would allow achieving the desired case depth
with minimum cost and processing time. The results of this work will help meeting the
carburizing quality requirements and achieving significant energy reduction, shortening cycle
time and thereby enhancing furnace capacity.
Model Formulation and Optimization Framework
The mass transfer mechanism during gas carburizing consists of three stages: 1) carbon transport
from the atmosphere to the steel surface through a boundary layer, 2) chemical reaction at the
steel surface and 3) carbon diffusion in steel. The two control parameters determining the final
carbon concentration profile are: the mass transfer coefficient (β) defining the flux of carbon
atoms from the atmosphere to the steel surface and the coefficient of carbon diffusion in steel (D)
at austenizing temperature. The mass transfer coefficient is a complex function of the atmosphere
gas composition, carburizing potential and temperature [7,8], while carbon diffusivity depends on the
carburizing temperature, carbon concentration and steel alloy composition [7,9].
Carbon concentration profiles and the effective case depth were modeled numerically using a CP-
and temperature-dependent mass transfer coefficient and the concentration-dependent carbon
diffusivity in austenite [5,7]. The model is based on the finite difference approximation of the
parabolic PDE governing carbon diffusion in steel and a flux balance boundary condition
accounting for the mass transfer coefficient in the atmosphere:
∂C ∂ ⎛ ∂C ⎞
= ⎜D ⎟, (1)
∂t ∂x ⎝ ∂x ⎠
∂C
β ( C P − CS ) = − D (2)
∂x
108
where C is the carbon concentration in steel at any location x below the surface, D is the carbon
diffusivity in austenite, β is the mass transfer coefficient, CP is the carburizing potential in the
atmosphere, CS is the carbon concentration at the steel surface.
The index of performance for optimization was to find a combination of process parameters that
would allow achieving the target case depth of 0.6 mm with minimum time and total cycle cost. The
effective case depth was defined as the depth to 0.4 wt.% C. This criteria corresponds to Rc 50 or
greater and is generally accepted for carburizing process evaluation in industrial settings. The
primary controllable process parameters include the carburizing temperature (T), carbon potential in
the gas atmosphere (CP) and the process time. Increasing carburizing temperature enhances the mass
transfer coefficient in the atmosphere (β) and carbon diffusivity in austenite (D), and thus it shortens
time necessary to achieve the desired case depth [7]. Such a solution, however, may decrease
furnace life and promote excessive austenite grain growth. While increasing CP enables a greater
rate of carbon transfer from the atmosphere to the steel surface, it also increases tendency of such
atmosphere to form soot. In the occurrence of sooting, the carburized parts’ quality degrades due
to non-uniform case depth, while the overall process cost increases by the furnace downtime
during the burn-out cycle. Both of these constraints on high levels of T and CP were imposed on
the overall cycle cost by means of penalty functions as will be discussed later in the paper.
Results and Analysis
Figure 1 shows evolution of the case depth (at 0.6 mm below steel surface) at various carburizing
temperatures. The elevated temperatures increase both the rate of carbon transfer from the
atmosphere to the steel surface and the rate of carbon diffusion in austenite. Therefore, at the first
approximation – ignoring the cost penalties for excessive austenite grain growth and furnace
deterioration, increasing the carburizing temperature from 875 °C to 975 °C would shorten the
cycle time by a factor of 2.
0.8
T = 875 deg. C
Case depth evolution (at 0.6 mm), wt.% C
T = 900 deg. C
0.7 T = 925 deg. C
T = 950 deg. C
T = 975 deg. C
0.6
0.5
0.4
Effective case
depth criterion
0.3
0.2
0.0 0.5 1.0 1.5 2.0 2.5
Carburizing time, hr
Figure 1. Case depth evolution at various carburizing temperatures and Cp of 1.1 wt.% C.
Figure 2 is based on the results of the carburizing model simulation and shows the cycle time
necessary to achieve the target case depth under various combinations of the carburizing
temperature (T) and the atmosphere carbon potential (CP). Since elevated CP and T increase the
driving force for carbon transfer from the atmosphere to the steel surface and enhance the rate of
carbon diffusion in steel, respectively, high level combinations of these two factors require
109
~ 1.5-2 hrs to achieve the target case depth. Low level combinations of T and CP significantly
reduce the kinetics of carburizing and require up to ~ 5 hrs to achieve the same target case depth.
Time to achieve case depth (0.6 mm), hrs

5.5
4.5
3.5
2.5
1.5
1
900 1.2 1.3
950 1.1
1
1000
0.9
Temperature, deg.C Carbon potential, wt.%
Figure 2. Carburizing time required to achieve the target case depth of 0.6 mm for the cycles
with various combinations of carburizing temperature and carbon potential.
Austenite grain growth is another factor that should be considered in the carburizing quality
requirements. Prolong hold at the elevated temperatures may cause excessive austenite grain
growth and may result in poor mechanical properties and premature failure. The grain growth
kinetics for a particular combination of the carburizing process parameters was simulated using a
Beck type model [1] assuming an initial grain diameter of 40 µm:
⎛ Q ⎞
d n − d 0n = k0 ⋅ exp ⎜ − ⎟⋅t , (3)
⎝ RT ⎠
where d is the mean grain diameter at the end of isothermal hold at temperature T, d0 is the initial
grain diameter, k0 is the pre-exponential rate constant, R is the gas constant, Q is the overall
activation energy for grain growth, t is the holding time and n is the grain growth exponent. The
coefficients k0, Q and n were obtained by fitting the model to the experimental data according to
the work of Sahay et.al. [1]. Additional rework charges are required if the austenite grain size
exceeds 55 µm. These charges comprised of the furnace operating time and energy consumption
during the rehardening operation, which included heating to 850 °C and holding the parts at
constant temperature for 1 hr.
While Figure 2 suggests that shortening the processing time can be achieved by carburizing parts
at higher T and CP, finding an optimal combination of these process parameters can only be
feasible if the corresponding cost factors are also accounted in the model. The overall cycle cost
in this work was calculated from several cost constituents, which included labors and furnace
operating cost, gas and energy consumption, furnace maintenance and cost penalty associated
with additional rework in case of excessive austenite grain growth:
Cost total = Cost furnace + Cost gas + Cost energy + Cost penalty (4)
operating consumption consumption high T, Cp
⎛ $ furnace $ operator ⎞
Cost furnace = ⎜ + ⎟ ⋅ tCarb , (5)
operating ⎝ hr hr ⎠
110
ft 3 $
Cost gas = ⋅ ⋅ tCarb , (6)
consumption hr ft 3
⎛ ⎞ $
Cost energy = ⎜ Energyheatup + Energyhold ⋅ tCarb ⎟ ⋅ , (7)
consumption ⎝ to T at T ⎠ kWt
where tCarb is the carburizing cycle time at constant carbon potential and temperature.
The estimated prices for energy, natural gas, furnace operating time and annual maintenance cost
were obtained from the public resources of the Department of Energy [10] and from the
industrial heat treating partners. Although it is understood that the actual cost numbers will differ
from one manufacturer to another, application of the cost-model approach provides a framework
for optimizing the carburizing process parameters based on the steepest gradient descent of the
cost function rather than the actual cost numbers. The overall cost model accounts for the major
contributing cost factors and it can easily be adjusted to a particular manufacturer if the data are
available. Gas consumption for electrically fired batch furnace with endothermic atmosphere and
the carburizing chamber of 3 m3 was calculated from Equation (6) based on the previous
experimental data [11]. Energy consumption was simulated using CHT-bf software [12] for the
same batch furnace during heating and isothermal hold at the carburizing temperature.
The overall cost for the carburizing cycles with various combinations of the process temperature,
the atmosphere carbon potential and time [to achieve the target case depth, Figure 2] were
calculated from Equation (4) and plotted in Figure 3. The values were normalized to search the
optimal solutions based on the gradient of the total cycle cost rather than the absolute values. 0.732
3
0.975 7 756
0.9
26 7
0.7 95
5
14
05
00.9
0.8 44 6
0.88
0.7595
29
1
0.
3 62
0. 840.802.870 19
.913953
88
0019
0.99
0. 7
0.
73
14 3 71
863429
78
0.
6
0.8
1.25 9 0.6771
1 57
0 151 57
0.
43 .77.7 0. 6
1
3
0.95638
0.7
676007504. 7
1
07 0 0 0.63986 58 0.919 15
0. 8 1 48
0.90053
.6 95 7 1 24 0.88191
1 1.2 0 2 0.86329
0.
3
4 3 77 158 48 0.6
388
0.84467
60
0.5
Normalized total cycle cost
1 0.8260 5
Carbon potential, wt.% C
0.7 0.6 0.6 38 3

206.5
46
624 0.565
81
0.807488
2 8 14 7 0.7 81
2 84
0 8 0. 5209 52 6
0.9 0. 6 0.5 9
0.62124
1.15 0.5 0.7701 0. 751 57

0.4909
5
0.6398
0. 7329
0.56538
95
77 1
0.62
3233
0.8
0.56
0.5 46 76
71
0.7 157
0.6 0.7
0.714
0.6
9
4886
0.795
28 1
0.60.6
1 24
70 1
0.5
5 38
1.1
6 0.6.677
0.75
95 7 14 3
02 6
5839
4
0.7
0.60.6
1 3
84 6 8 14
0
58 1
2
46 7 0.52
0. 5095
48
1.05
2
0.6
6026
0.
78
0.
88
0.
77
6 621 240.50.
1
58
0.5
43
01
4
0.5
9
05 07
1
0.8 88 81
0.7 0.8 00. .8463 2
0.6
0.5
26 0.8
0. 86 0. . 67
65 3
70 078264 6 9
0. 719 0.743 057
39
8
62
0.71 57 8 81
0. 4
0.7
2935
0.6 0.
5
12
60
71
0.4
57
39 8 0.
67
32
0.8
0.844
43
5 71
0119
95 71
26
0.95 07
0.67
7573
95
0.8
0.0.71
71 4 3
1.3 43
8
29
0.69
0.0.77
0.8
0
63
65 7 1
900 0.8 26
0.6
1.2
84
3
05
8
950 1.1 0.9

1 880 900 920 940 960 980 1000
Temperature, deg.C 1000
0.9 Carbon potential, wt.% C Temperature, deg.C
a) b)
Figure 3. Normalized total process cost for various carburizing cycles producing the target case
depth of 0.6 mm: a) 3D surface representation, b) contour representation.
As follows from Figure 3 there is a distinct range of controllable process parameters (T and CP),
where the target case depth can be achieved with minimum cycle time and minimum overall
cost. The optimal range of T and CP centers around 926-938 °C and 1.08-1.15 wt.% C,
respectively, within which the target case depth is achieved in 2.4 hrs with cost < 50% of all
explored combinations. Depending on the acceptable cost range, the optimal combinations of T
and CP can be adjusted for tighter tolerances. Increasing the carburizing temperature beyond 940
°C sharply increases the total process cost due to rework required for large austenite grain size.
Exceeding carbon potential beyond 1.15 wt.% C also increases the total cycle cost as it increases
the atmosphere tendency to form soot and will require more frequent burnout cycles. While the
cycles with low level combinations of T and CP [below 920 °C and 1.05 wt.% C, respectively]
111
require lower hourly gas- and energy- consumption, the kinetics of carburizing is so low that it
requires significantly longer carburizing time to achieve the desired case depth. As a result, cost
of the furnace operating time overpowers the hourly savings in the gas and energy resources and
results in higher overall cycle cost.
Conclusions
Optimization of gas carburizing process in this work was accomplished by simultaneously
shortening the carburizing cycle time to achieve the desired case depth and minimizing the
overall cycle cost. The cost function used for optimization included the cost of gas and energy
resources, furnace operating time and cost penalties due to rework of large austenite grain size and
furnace maintenance at high temperature and carbon potential. The optimal combinations of the
carburizing temperature and the atmosphere carbon potential were found to be within 926-938 °C
and 1.08-1.15 wt.% C range depending on the acceptable cost constraints. Overall, application of
this optimization technique will help meeting the carburizing quality requirements and achieving
significant energy reduction, shortening cycle time and thereby enhancing furnace capacity.
Acknowledgements
The support of the Center for Heat Treating Excellence (CHTE) at Worcester Polytechnic Institute
(WPI) is gratefully acknowledged. The authors are also grateful to Md. Maniruzzaman from WPI
and Scott Johnston from Caterpillar Inc. for their input and valuable discussions.
References
1. S.S. Sahay and K. Mitra “Cost Model Based Optimization of Carburizing Operation,”
Surface Engineering, 20 (5) (2004), 379-384.
2. K. Palaniradja, N. Alagumurthi and V. Soundararajan “Optimization of Process Variables in
Gas Carburizing Process: A Taguchi Study with Experimental Investigation on SAE 8620
and AISI 3310 Steels,” Turkish Journal of Engineering and Environmental Sciences, 29
(2005), 279-284.
3. F. Kuhn “Energy Situation in Europe and Conservation in Some Industrial Furnace
Uses,”Industrial Heating, 50 (11) (1983), 25-30.
4. B.M. Khusid, E.M. Khusid and B.B Khina “Optimization of Properties of Carburized High-
Chromium Steels,” Journal of Materials Science, 30 (1995), 2989-2998.
5. O. Karabelchtchikova, M. Maniruzzaman, R.D. Sisson, Jr. “Carburization Process Modeling
and Sensitivity Analysis using Numerical Simulation.” Proc. MS&T, Cincinnati, OH, Sept.
25-28, (2006), 375-386.
6. O. Karabelchtchikova and R.D. Sisson, Jr., “Carbon Diffusion in Steels – a Numerical Analysis based
on Direct Integration of the Flux”, Journal of Phase Equilibria and Diffusion, 26 (6) (2006), 598-604.
7. O. Karabelchtchikova and R.D. Sisson, Jr., “Calculation of Gas Carburizing Kinetic
Parameters from Carbon Concentration Profiles based on Direct Integration of the Flux”,
Defect and Diffusion Forum, 266 (2007), 171-180.
8. P. Stolar and B. Prenosil, “Kinetics of Transfer of Carbon from Carburizing and
Carbonitriding Atmospheres,” Metallic Materials, 22 (5) (1984), 348-353.
112
9. J. Agren, “Revised Expression for the Diffusivity of Carbon in Binary Fe-C Austenite,”
Scripta Metallurgica, 20 (11) (1986), 1507-1510.
10. Department of energy, Energy Information Administration: www.eia.doe.gov
11. O. Karabelchtchikova, S.A. Johnston and R.D. Sisson, Jr, “Gas Carburizing Atmosphere
Development. Part I: Thermodynamics of Carburizing Endothermic Atmospheres with
Various Enriching Hydrocarbon gases”, submitted to Metallurgical Transactions B.
12. J. Kang, Y. Rong and W. Wang, “Numerical simulation of heat transfer in loaded heat
treatment furnaces,” Journal of Physics, 4 (120) (2004), 545-553.
113
EXPERIMENTAL AND NUMERICAL STUDY OF FLAME LOAD HEAT

TRANSFER IN AN EXPERIMENTAL FURNACE
Ashwini Kumar1, Raj Venuturumilli1, László I. Kiss2, Géza Walter3

1
ANSYS, Inc., 1007 Church Street, Evanston, IL 60201 2Centre universitaire de recherche sur
aluminium (CURAL), Université du Québec à Chicoutimi, 555 boul. de l’Université
Chicoutimi, Québec, G7H 2B1 3EGI Contracting Engineering Co. Ltd. 4-20 Irinyi str., Science
Park, Bld. B, Budapest, H-1117 Hungary
Keywords: Experimental Furnace, Furnace Modeling, Flame Interaction, Recycling, CFD
Abstract
Flame impingement on solid objects is a routinely encountered phenomenon in metallurgical

operations. This was studied in an experimental furnace in order to obtain heat transfer. In this
paper, the same is simulated using a Computational Fluid Dynamics (CFD) approach and the
resulting temperature, velocity and chemical composition distributions were compared to the
experimental data. This comparative analysis demonstrates the potential of mathematical
modeling not only in complementing the experiments but also in providing a cost-effective
framework for obtaining the data after proper validation with the experimental data.
Introduction
Aluminum furnace operators constantly strive to achieve higher furnace efficiencies in order to
reduce the costs and increase the throughput. Central to furnace operation is the combustion
system that will not only produce a stable flame but also result in efficient heat transfer to the
load. To address the industry need to understand the flame-load interaction better and quantify
the heat transfer rates, Walter et al [1] and Kiss et al. [2,3] have successfully devised and
conducted an experimental procedure with a reverbatory type semi-industrial, laboratory furnace.
They studied four different flame types, produced by two burners, for three geometrical
configurations. Conventional as well as low NOx burners were studied. The research was
focused on the separate determination of the radiative and convective components of the local
heat fluxes. Special attention was given to the measurements of heat fluxes in the direct flame
impingement point created in the third experimental phase. Additionally, flame temperatures,
velocity profiles, refractory temperatures, and flue gas compositions were also measured. The
measured convective heat fluxes were compared with computed results, obtained using
numerous empirical heat transfer correlations, published in the literature. For instance, the high
speed jet flame transfers 54% of the total heat exchange by convection in the impingement
arrangement. This behavior is very different from that in parallel firing when only about 20% of
the total heat flux has been transferred by convection. Details of the experimental furnace as well
as the operation procedure are described in [3]. In this study, it is intended to reproduce some of
this extensive experimental work, within the framework of Computational Fluid Dynamics
(CFD). Due to space limitation, only one case is presented.
In many industries, CFD modeling has played an increasingly important role as a cost effective
tool in evaluating/improving industrial processes. Over the past decades, the aluminum industry
has begun to use this tool to analyze and then improve their processes [4-6]. Indeed, as part of a
larger program involving modeling and in-furnace measurements, Aleris, a major aluminum
115
company, was able to show significant financial gains [4]. Although this previous work has
established that CFD can be used to improve the performance of many aluminum industry
processes, there is still a question on the accuracy of the results produced from such models. This
paper addresses that question by presenting a validated CFD model. Furthermore, it will be
shown that through a validated model, one can acquire the data beyond that seen in
measurements. Thereby, demonstrating the complementary nature of CFD to physical
measurements.
Problem Description
The experimental furnace considered for this work is essentially a rectangular box with a raised
step towards the middle of the furnace. This arrangement was chosen in the third phase of the
experimental work [1], in order to simulate the effect of flame impingement on the corner of a
solid charge. Figure 1 shows a photograph of the experimental furnace and a schematic
illustrating the combustion zone, burner, and calorimetric plates, representing the load and the
cooling water tubes. In order to provide more detailed information on the heat transfer between
flame and charge, an array of heat flux sensor sockets were drilled into the calorimetric plates.
Two mobile heat-flux sensors, an absorptive (black-painted) and a reflective (gold-plated) one,
have been used to provide input values for the calculation of local convective and radiative heat
fluxes. These water-cooled sensors were inserted into the sockets during the heat-flux data
acquisitions. The sensors were recurrently calibrated, the surface emissivities checked and in
case of need, recovered. The emissivities of absorptive and reflective sensors were kept at about
0,96 and 0,1 respectively.
(a) (b)
Figure 1 (a) Experimental furnace setup (b) Schematic of the experimental setup
For the CFD model (Figure 2), the geometric features of the physical furnace are simplified, as
these features, while do not influence the accuracy of the results, add to the computational cost.
Examples of the simplifications include replacing the furnace outer walls with equivalent thermal
resistances and excluding the detailed burner modeling. Taking advantage of symmetry, only
half of the furnace has been modeled. Similarly, the calorimetric plates are represented by a thin
shell (approx. 30 mm) with high heat transfer coefficient to represent water-cooling. These
water-cooled plates are covered by 1/4” of Fiberfrax insulation on the top. Thus, only the
sensors, which are also water-cooled, are directly exposed to the flame, but not the plates.
The experimental work involved the analysis of several different kinds of flames, such as, low
speed short and long flames as well as high-speed LNI and envelope flames. Three different
geometrical arrangements that represent realistic flame-charge interactions were used (flat bath,
116
parallel firing; flat bath, inclined burners; flame impingement on the corner of a solid charge).
The scope of this paper is restricted to the case of the high-speed LNI burner flame. It is a
premixed burner where fuel (natural gas: 95.2% CH4, 0.4% CO2 and 4.2%N2) and air (10%
excess by mass) come in as separate streams, at the inlet to the burner, and mix with each other,
towards the downstream end, before coming out of the nozzle, as nearly a homogeneous mixture.
Even though the burner configurations and flow rates affect the mixing patterns at the burner
outlet, a detailed analysis of these dependencies falls beyond the scope of this work.
Figure 2: Computational geometry and mesh
Computational Approach
The computational approach follows closely the experimental setup, with a few exceptions, as
indicated in the previous sections. A general-purpose finite volume commercial CFD code,
FLUENT 6.3 (ANSYS, Inc. Canonsburg, PA) has been used in this study [7]. The code solves
for the mass, momentum, species and energy conservation equations at each computational cell
volume, with appropriate sub-models for simulating the underlying complex physics, as
described below.
Turbulence is modeled using the Reynolds Averaged Navier-Stokes (RANS) based standard k-ε
model. The premixed flame is simulated using the multi-species transport model with volumetric
reaction rate, based either on the finite rate kinetics or on the turbulent mixing rate (eddy
dissipation rate [7]). This model predicts the concentrations of the major combustion products, as
prescribed by the reaction mechanism, used along with the fuel and oxidizer (in this case CH4,
O2, N2, CO2 and H2O). This model is based on the assumption that the rate of combustion, at any
local point, is governed by the limiting value of the two rates, i.e., kinetic and turbulent mixing
rates. A major advantage of the eddy-dissipation model is that it is equally applicable to non-
premixed flames, as well as, premixed flames. Thereby, allowing one to perform a parametric
study on the effects of partial premixing.
It is necessary to model the radiation heat transport in furnaces in order to calculate the thermal
fields accurately. Radiation transport, apart from being spatially varying, is also direction
dependent. Besides, combustion produces greenhouse gases, such as CO2 and H2O, that
participate, absorb, and emit radiation. These complexities make the radiation modeling non-
trivial. A Discrete Ordinate (DO) model, that is used in this work, provides a detailed framework
for a radiation transfer equation (RTE) solution, taking all the aforementioned aspects into
account. However, for a successful radiation transport simulation, one needs to provide an
117
appropriate sub-model for calculating the gas absorption coefficient. The absorption coefficient,
in this case, must be a function of local temperature and gas composition. Thus, a “weighted-
sum-gray-gas-model” (WSGGM) [8] is used to estimate the absorption coefficient of the gas
mixture at every computational cell.
This section presents computational results, obtained from the simulation of high velocity flame
interaction, with raised step in the experimental furnace. We will first discuss the physics of the
problem from the computational model results perspective and then proceed to validate the
model against the experimental data. One of the prime advantages of a computational model is
that it provides information on every single point in the furnace. For example, the reactive jet
dynamics, due to the presence of the raised step, can be understood from the velocity contours on
the furnace center plane (referred to as symmetry plane from henceforth) as shown in Figure 3a.
The peak jet velocity accomplished for the assumed burner gas flow rate is 85 m/s, which is in
good agreement with the reported value of 90 m/s for the high velocity flame burner. This high
velocity fluid decelerates as it approaches the vertical part of the step, forming a stagnation point
at the impingement location. This, of course, results in the bifurcation of the jet into two separate
streams. This is more clearly seen from the burner jet path lines, presented in Figure 3b, which
also shows the resultant recirculation patterns above and below the jet. The relative strength of
the recirculation cells can be seen from the computed vorticity levels. Vorticity is a measure of
the local angular rate of rotation of fluid and is defined as the curl of velocity. Presence of the
raised step creates a relatively strong recirculation cell below the jet and a relatively weak
recirculation cell above the jet. Similarly, the flame shape is clearly seen from the temperature
contours on the symmetry plane, as shown in Figure 4. A peak flame temperature of about 1800
C, observed upstream of the impingement point and the hot combustion gas stream, proceeding
downstream from the flame, is cooled by convective, as well as, radiative heat transfer to the
load and furnace walls.
(a) (b)
Figure 3: Velocity contours (m/s) on the symmetry plane of the furnace (left) and gas path lines
colored by vorticity (right).
The LNI burner is supposed to create favorable conditions for the high velocity flame to be
anchored at the burner exit. Since we have not included the burner itself in the model, the flame
stabilizes at the location governed by fluid dynamics, i.e., at a location where flame propagation
speed is balanced by the local fluid velocity. This has resulted in the modeled flame to be
downstream of that of the experimental flame, which in turn, should explain the observed
differences in the experimental and model results
118
Figure 4: Temperature contours (ºC) on the symmetry plane
(a) (b)
Figure 5:(a) Comparison of the measured and calculated furnace crown temperature ((ºC) along
the crown centerline (b) Heat flux along the centerline of the burner
Figure 5a compares the furnace crown temperature, as calculated by the simulation model, to the
experimental data. The results are in good agreement qualitatively. The model predicts relatively
flatter profile along the length of the furnace, as also seen with the measured data, but over
predicts the crown temperature by about 10-12%. This difference between the two is attributed to
the use of effective heat transfer coefficient to model the wall heat transfer external to the
furnace. This effective heat transfer coefficient assumes a uniform refractory thickness and
accounts for the heat transfer to the ambient but does not account for the presence of viewing
ports and other inclusions in the walls of the experimental furnace. It must be noted that the
computational costs involved in including all the details of furnace geometry far exceed the
minor loss in the accuracy by ignoring them.
However, the differences in the predicted flame shape and the wall heat loss seem to have a
minimal affect on the predicted heat fluxes to the load, as can be seen from Figure 5b. Ten
numerical heat flux sensors are placed along the length of the load on the centerline analogous to
the experimental set up. The heat flux calculated at these sensor locations is plotted and
compared against the measured data. Note that the break in the curve demarcates the
impingement point of the load, with the left branch, representing the lower calorimetric plates
and the right branch representing the raise calorimetric plates. Simulation results are in
qualitative agreement for both the branches while the right branch is also in good quantitative
119
agreement. Predicted peak heat flux value of 224 kW/m2 also agrees very well with the measured
value of 226 kW/m2. Since the most important quantity to be calculated is the heat fluxes, one is
justified in making the model assumptions based on sound engineering judgment.
Conclusions
An experimental furnace that used to quantify the convective and radiative heat fluxes for
aluminum furnaces is simulated using a computational fluid dynamics model. Ignoring the
burner details, a homogenized mixture of fuel and oxygen was assumed to enter the domain and
combust to form a premixed flame. The simulation resolved the flow, thermal, and chemical
composition fields, indicating the flame behavior as well as its heat transfer characteristics.
Model predictions are then compared to the measured data and found to be in good qualitative
agreement. Observed differences are potentially due to the model assumptions on burner, furnace
wall heat transfer characteristics, and other differences in the experimental and numerical setups.
Due to the time and space constraints only the high velocity flame case is presented in this paper.
However, the authors plan to present the results of the expanded work scope including other
flame types at the conference.
Acknowledgements
The authors would also like to acknowledge the contributions of Alcan International and North
American Mfg. by supporting the experimental work. The fourth author gratefully acknowledges
the support of the Ministère de l’Éducation du Québec in the form of a post-graduate scholarship.
References
[1] G. Walter, L.I. Kiss, A. Charette, and V. Goutiere, “Flame-object Heat Transfer using
Different Burner Types and Orientations.”, Light Metals 2006, The Minerals, Metals & Materials
Society.
[2] L.I. Kiss, A. Charette, R.T. Bui, “Determination of Thermal Boundary Conditions on
Furnace Walls”,. Intl. Conf. Num. Exp. Meth. In Heat Transfer, ed.. P. Brebbia. (1991), 256-267.
[3] L.I. Kiss, G. Walter, V. Goutiere, A. Charette, and W. Stevens. “Heating Patterns Produced
by Different Industrial Flame Types.” Light Metals 2002, 731-738.
[4] C.K. Belt, B.M. Golchert, P.E. King, R.D. Peterson, and J.L. Tessandori, “Industrial
Applications of DOE Energy Savings Technology to Aluminum Melting,” Light Metals 2006,
[5] B.M. Golchert, C.Q. Zhou, A. Quenette, Q. Han, and P.E. King, “Combustion Space
Modeling of an Aluminum Furnace,” Light Metals 2005.
[6] B. Golchert, A. Kumar, R. Venuturumilli, A. Adhiya, C. Belt, and J. Tessandori. How
Flames/Loads Interaction Affects Furnace Efficiency in Round Top Furnace Operation. Light
Metals 2007.
[7] Anonymous 2007.Fluent 6.3 Users Manual
[8] B. F. Magnussen and B. H. Hjertager., “On Mathematical Models of Turbulent Combustion
with Special Emphasis on Soot Formation and Combustion” In 16th Symp. (Int'l.) on
Combustion. The Combustion Institute, 1976.
120
Influence of the process parameters on the multi-directional forging operation

of a two cylinder crankshaft
Sven Mueller, Philipp Lau, Rouven Nickel
Institut fuer Integrierte Produktion Hannover gGmbH,

Hollerithallee 6, 30419 Hannover, Germany
Keywords: Bi-Directional Forging, Precision Forging, Flash, Flat Long Pieces
Abstract
Precision forging is defined as a flashless near net shape forging technique. Its deployment
permits the procurance of quality grades in the tolerance class between IT 8 and IT 10. By use of
the forging heat, the flashless precision forging provides an integrated heat treatment. This is
possible, because an additional process step, the clipping, can be entirely omitted. Subsequent to
forging and heat treatment, there is only a final fine machining of the functional surface with
very little chip volume required.
In the collaborative research project SFB 489 a two-cylinder-crankshaft was selected as an
example for complex flat long pieces with a characteristic mass distribution along the
longitudinal axis. The continuative development contemplates the thermal and mechanical tool
tensions, which are just as complex as the crankshaft itself. Furthermore, a parameter study on a
multi-directional forging tool is made.
Introduction
Bulk forming is still a relatively novel production technology. Its main advantages are high
productivity and the excellent mechanical properties of the forged parts, namely the continuous
and stress related fibre orientation. Despite these indubitable advantages, it is in constant
competition with other technologies, e. g. casting or sintering. There is also an increasing trend
of substituting bulk formed steel products with parts made from non-ferrous metals, like
aluminium or magnesium. Moreover, producers of drop forged parts have to deal with increasing
international competition and a growing product variety [1]. Therefore, in addition to
organizational optimizations of production processes, it is necessary to strengthen the
competitiveness of bulk forming technologies.
One way to enhance the engineering potentials is to establish the flashless precision forging
technology. Today, the flash of an industrially forged crankshaft amounts to 30 % of the used
raw mass. The raw part is formed in several stages in closed dies. In the following process step
the flash is removed. Subsequently, the crank pin angles for three or five cylinder crankshafts are
bent. Cost analysis for forged crankshafts show that the share of material costs in the total costs
can rise to 45 %. By approximating the drop forged part geometry to the final component
geometry, not only less material is used but time- and cost-intensive cutting processes can be
reduced or left out as well [2, 3]. Thus, the production efficiency of bulk formed crankshafts
increases [4].
121
In the context of a Collaborative Research Project (SFB 489) supported by the German Research
Foundation, sample process chains for flashless precision forging of rotation-symmetric parts,
represented by gear wheel and gear shaft, and flat long pieces, represented by a crankshaft, are
developed [5, 6, 7, 8, 9, 10, 11].
Forging sequence of flashless precision forged two cylinder crankshaft
In this research project the forging sequence of two cylinder crankshaft consists of four stages.
During the first two stages, the mass for the crank web is allocated by lateral extrusion. The next
stage is a bi-directional forging operation. In this phase the crank web is formed and the crank
pin is displaced radially while an upsetting of the part takes place. Finally, the last forging
creates the near-net-shape end geometry without a flash. The forging sequence developed in this
research project, is displayed in figure 1.
Figure 1: Forging sequence for a neat net-shape crankshaft without flash
The greatest challenge of this forging sequence is the development of a tool for the multi-
directional forging process. Since the multi-directional tool will be used in a hydraulic press
which acts only in one direction, the movement of the press has to be diverted in a horizontal
direction to displace the crank pins. For this direction change a wedge gear is implemented into
the tool. For the development of a wedge drive, it is necessary to consider, that the wedge angle
has to be designed in a range between 35° to 45°. Otherwise there is a danger of self-locking and
the required forging force rises sharply. The movement of every part of the tool has to be
predetermined. For the optimization of the tool kinematics and the forging process, which is
tested using FE-simulations, an iterative proceeding is adopted.
For this iterative proceeding it is assumed, that the end geometry is given and all pre-forms for
the forging sequence are already completed. The tools are to be preferably simple and durable.
The die for the main bearing in the middle of this crankshaft is mounted stationary. All other
parts are moveable. The outer dies which form the main bearings move along the axial direction
of the crankshaft and the dies for the crank pins move along a diagonal axis. In order to achieve
this movement, an additional wedge drive is implemented in the tool [10].
Figure 8 shows the bi-directional forging tool:
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Figure 2: Tool concept for the multidirectional forging operation
The multi –directional forging operation

The procedure of the multi-directional forging operation can be described as follows: During the
vertical punch movement of the press the upper die moves down. The axial and radial operating
tool components, which are responsible for shape forming for the main bearing and the crank
pin, enclose the pre-form at the bearings and fix it in its position. The crank webs are located
between shape forming tool components and move bulk in the axial direction during the forging
operation.
On account of the symmetrical constructed wedge gear, the tool for the main bearings in the
lower die moves along the axis of the crankshaft and affects a bulk forming operation of the pre-
form. Simultaneously a radial operating wedge gear in the upper die generates the offset of the
crank pin with the tool for the crank pin. During the forging operation, the upper and lower dies
have to be pressed together against opening. The closing forces are realized during the
compression of spring packets. For this tool six spring packets are required in the upper and
lower die respectively. Every packet consists of 12 alternating disk springs.
Due to the crank pin being offset by 14.5 mm during the third forging operation, the deformation
degree of the moved crank pins is the largest. In addition, there is a high degree of deformation at
the main bearings, because the material of the crank webs is pressed into the bearings.
Not till then a synchronization of the described forming movement, the multi-directional forging
operation produces the desired intermediate geometry. If the movements are executed
consecutively, forging fault or unusable intermediate geometries will be generated due to the
resulting flow of material.
By virtue of the tools’ special construction, bulk forming operations across the press movement
can be achieved on an ordinary operating press.
The diverting of the tool proceeds horizontally and allows a direct deduction of the closing
movement from the movement of the press. After the multi-directional forging operation,
previous deformation degrees taken into account, the deformation degree amounts to φ = 3.5.
The influence of the process parameters on the multi-directional forging operation
Due to the tool’s intricacy and the number of its moving parts, the multi-direction forging
process is very complex and therefore susceptible to discrepancies and failures. For this reason
this paper deals with analyses of the single process parameters, e. g. the coefficient of friction
123
between the blank and the tool or the forging speed of the press. For the analyses of the
influencing parameters a simulation model was built up. Within this simulation model the
influencing parameters vary. In addition of all possible combinations of the influencing
parameters a matrix with 90 single simulations results. By using the statistic design of
experiments the amount of simulations can be reduced. Figure 2 describes the connections
between the process’ influencing variables and the target variables.
Figure 3: Influencing and target variables on the multi-directional forging process
A range of temperatures is defined for the influencing variables. For the temperature of the blank
minimum temperature is fixed at 1100 degree Celsius and the maximum temperature at 1300
degree Celsius. The minimum temperature is defined by the sufficient deformability of the
material and the maximum temperature is fixed by the nethermost melting phase. In the
numerical analyses, the temperature within the defined scope is raised by 50 centigrade steps.
The friction between the tool and the work piece is specified with the numerical simulation
software Forge3 as a combination of the friction factor principle (m) and the coulomb friction
(µ). During this development the friction is successive defined with the variables (µ=0.1, 0.2,
0.3; m=0.2, 0.4, 0.6). Since the multi-directional tool will be used in a hydraulic press, the press
speed is defined with 10, 15, 20, 25, 30 and 50 mm/s.
Figure 4: Influence of the temperature on the press force
The main focus of this project is the maximum press force. As a first step, the initial temperature
of the blank is determined. During the forging process, the speed of the press is maintained at
25 mm/s, while the temperature of the blank is gradually raised from 1100 °C to 1300°C. In
addition, the coefficient of friction between blank and tool is modified. Thus, it is possible to
124
determine the two parameters’ individual effects on the process. Figure 4 displays the correlation
between blank temperature and press force.
The trajectory depicting the force, in dependency of the temperature, shows concave
characteristics and decreases with higher temperature. The coefficient friction between the blank
and the tool influences this curve inasmuch as a higher coefficient of friction increases the force.
With temperatures above 1250°C differences are no longer discernible.
The influence of friction between the individual parts of the wedge gears
In the last chapter different process parameters like the temperatures of blank and tool were
discussed. This section deals with the friction coefficient between different parts of the wedge
gears. In order to determine the friction parameters a sliding element between the respective
components of the moving parts is required. Usually, a hard / soft matching is used for this
purpose. The soft element consists of a bronze alloy with emergency operating features. For the
emergency scenario, when the lubrication coating stalls, the coefficient of friction is set at
µ = 0.2 while under normal working conditions and with a working lubrication coating, the
coefficient of friction is approximately µ = 0.15. If these circumstances are taken into
consideration, the forces, which have to be implemented by the press, differ notably from
previous results.
Figure 5 shows the amount of energy required as well as its distribution.
Picture 5: Influence of the friction on the total forging energy and its distribution
On account of the various friction partners the friction energy makes up a large share of the
process energy required. In the emergency scenario, 50 percent of the total energy consumed
originates in friction. In the standard working scenario with lubrication the friction causes about
30 percent of the total energy consumption. For the evaluation of a hydraulic press it is inevitable
to know its maximum force in order to verify if the press is capable to produce the required
force. With the numerical simulations of the forging process and in consideration of the different
friction coefficients between the various wedge gears, the diagrams of the total press force,
dependent on the forging stroke rate, are created.
In figure 6 the total press force is displayed. In the emergency scenario the maximum force
reaches about 12 MN, this value is situated at the top end of the maximum press force scale. For
125
a standard forging operation it is expected, that the trend of the force curve increases
exponentially. Due to the numerous friction partners, the multi-directional forging operation
deviates from this pattern. Thus, the trend of the trajectory depicting the press force increases
nearly unidimensional. Within the standard forging parameters the maximum press force is close
to 8 MN. For this reason the lubrication of the wedge gears is an important prerequisite to the
multi-directional forging process. Bearing that condition in mind, the forging process can be
safely conducted on an existing press.
Figure 6: Influence of the friction on the total press force
Summary and future prospects
The flashless precision forging provides an opportunity to curtail the process chain. The clipping
process is no longer necessary and the forging heat can be used for an integrated heat treatment.
Solely a final machining of the functional surface with low chip volume is needed. Within the
development of the forging sequence it is necessary to integrate a multi-directional forging
process for precise mass distribution and for an exact profile pre-forming prior to the final
precision forging step. The application of multi-direction tools in forging processes increases the
range of forged components. Two single step processes of a standard forging operation can be
condensed into one multi-directional process. Compared to alternative manufacturing
technologies like casting or sintering, multi-directional forging can increase the competitive
position. The development of such innovative forging methods is still in progress. In future the
sensitivity of the multi-directional forging process to different process parameters is to be shown.
The main influencing parameters are the friction and the temperature. The control of the
temperature is possible by adjusting the handling times, but the coefficient of friction can’t be
controlled by external intervention. Bearing the impact of the influences in mind the process
frame can be defined. Currently the preparation for the testing and verification of the forging
sequence is in progress. The optimization of process chain and part quality constitutes a worthy
objective for further research.
References
[1] VDI-Z Integrierte Produktion: Schmiedeteile aus Aluminium. Steigende Nachfrage sorgt fuer
kontinuierliches Wachstum, Vol. 143, Issue 6, (2001), pp. 72-73.
[2] Balendra R.: Net-shape forming: state of the art. Journal of Materials Processing Technology,
Vol. 115, Issue 2, (2001), pp. 172-179.
126
[3] Doege, E.; Behrens, B.-A.; Wiarda, M.: Verkuerzte Prozessketten durch das
Praezisionsschmieden von Zahnraedern – Auswirkungen auf die konventionelle
Schmiedetechnik, HFF-Bericht Nr. 13, (1996). pp. 257-260.
[4] Bar and Rod Market Development Group of American Iron and Steel Institute: Steel’s
Institute and Economic Progress in the Production of Lighter and Smaller Engine Components,
(2001), p. 20.
[5] Broß, G.; Muessig, B.: Gratloses Präzisionsschmieden von Langteilen im Halbwarmbereich,
Schmiede-Journal September (1999), pp. 24-25.
[6] Bach, Fr.-W., et al: Reducing the process chain for the production of gear wheels by
precision forging - Integration of Heat Treatment and necessary changes for the process
management, Steel Grips, September 2004, GRIPS Media GmbH, (2004).
[7] Doege, E., et. al, Precision Forging of Crankshafts, Production Engineering, X/2 Volume X
Issue 2, (2003), pp. 29-34.
[8] Behrens, B.-A., et al: Further development in the precision forging technology for high duty
automotive parts, Pro-ceedings of the Sixth Global Innovations Symposium, 2005 TMS Annual
Meeting and Exhibition, 13.-17. February 2005, San Francisco
[9] Förster, H.; Reinsch, S.; Schott, A.; Specker, A.: Flashless Precision Forging of Flat Long
Pieces, Proceedings of the 4th International Seminar on Precision Forging (ISPF), Japan (2006),
pp. 117-122
[10] Müller, S.; Reinsch, S.; Specker, A.; Telkamp, K.: Bi-directional Forging of Long Flashless
Pieces TMS (The Minerals, Metals Materials Society) 2007, 136th Annual Meeting &
Exhibition, 26. February 2007, Orlando, Florida, USA
[11] Behrens, B.-A.; Doege, E.; Reinsch, S.; Telkamp, K.; Dähndel, H.; Specker, A.: Precision
forging processes for high-duty automotive components, Journal of Materials Processing
Technology, 185, (2007), pp. 139-146
127
CONTROLLED SHEET METAL STRAIGHTENING
B. - A. Behrens, R. Krimm
Institute of Metal Forming and Metal-Forming Machines

Leibniz Universitaet Hannover
An der Universitaet 2, D-30823 Garbsen, Germany
Keywords: Metal Forming, Measurement and Control Technology, Automation, Straightening
Abstract
Straightening the sheet-metal in advance of forming operations needs to be improved. Today the
straightening rolls are positioned manually or by means of an adjustment unit by the machines
operator using his expert knowledge. A controlled adaptation of the rollers positions to the
depending on the coil-radius variable curvature and properties of the sheet-metal is not realized
yet. For this reason the flatness of the straightened sheet metal is limited and modifies while
unreeling the coil. The paper shows a way to control the roller positions depending on the
residual bending of the straightened sheet metal. The controlling system of a testing straightener
was amended to vary the roller positions in dependence of the sheet metals residual bending.
Using adequate controller settings it was possible to stabilize the straightening process to a
certain extend and to obtain good straightening results from coiled sheet metal.
Introduction
Around 700 Enterprises produce sheet metal products in Germany with a sales volume of
8 billion € [1]. Thus the industrial sector is of importance for the economy of the whole country.
In the long term the branch will only survive in the global market producing high quality-parts
with innovative features. With this purpose demands on coil ware used as primary material are
high. The sheet metal needs to be almost free of imperfections that means variations in thickness,
lacks of flatness as well as residual stresses and anisotropy [2]. Lacks of flatness can be
subdivided in windable and unwindable imperfections. Windable imperfections can be
eliminated by bending around one axis. This kind of imperfections (figure 1, left side) [3] is
generated reeling the sheet metal to coils and therefore always existing in advance of processing.
Sheet metal with unwindable imperfections is additionally bended around another axis (figure 1,
right side).
a) Bending c) Waves at the Edges
b) Waves d) Waves in the Middle
Windable imperfections Unwindable Imperfections

Figure 1. windable and unwindable imperfections
Flat sheet metal strips containing residual stresses become uneven cutting blanks [4, 5].
Windable imperfections can partially be seen in advance of processing.
129
Imperfections as well as residual stresses can be reduced by multiple plastic deformation of the
sheet metal in a roller straightener. Residual stresses and their distribution along the sheet metals
profile can’t be measured in industrial praxis. Reducing the imperfections by straightening,
residual stresses are reduced too [8]. The elimination of unwindable imperfections by roller
straighteners is impossible today. Beside approaches with flexible rolls [6] this can be realized
only by stretch forming the material in addition to alternating bending. This however leads to a
variation of the sheet metals thickness and is unimaginable in metal forming industry today. This
paper regards the straightening of windable imperfections.
Figure 2 shows the design of an automatic facility to process coil material. The sheet metal is
unreeled by a decoiler and lead through a roller straightener and the loop to the feeder of the
press before being processed.
By the alternating arrangement of the rolls an alternating bending is forced on the sheet metal.
To obtain positive straightening results it is necessary to take the properties of the sheet metal
into account. To adjust the deformation which is forced upon the sheet metal by the machine, the
upper rolls are mounted in a so called roller frame. This frame can be moved up and down and
tilted in a controlled manner. The bearing points of the rolls are positioned on a straight line
(linear adjustment). In this operating mode there are only two parameters to be varied to set the
positions of the rolls [7].
move in Rolls Roller Frame move out Rolls Feeder
Coil Upper Rolls Loop
Lower Rolls
Decoiler Roller straightener Press

loop cavity
Figure 2. Automatic facility to process coil material
In contrast to this linear adjustment, the individual adjustment of the rolls is realized only in few
machines equipped with less than 10 rolls. With an increasing number of rolls the strain
hardening of the sheet metal grows and the ductility for the following processes decreases. In [8]
the trend of residual stresses in the sheet metal after straightening is given as a reason for an
individual adjustment of the rolls. The interval for suitable roller positions is smaller in machines
with few rolls than in straighteners with a higher number of rolls [9]. For this reason machines
with few rolls provide a small number of adjustment data sets which can be qualified as initial
value for a controlling system. Roller straighteners have no controlling systems today to adjust
the roller positions in dependence of the residual bending after straightening. The roller positions
are set at the beginning of production manually or by means of servo systems and remain
unchanged while unreeling the coil. The machines settings are determined according to the
operators expert knowledge and individual trials. This modus operandi does not guarantee a high
quality of straightening because the bending of the sheet metal in advance of the straightening
process varies with the unreeled strip length of a coil [10].
Road Map to a Controlled Roller Straightener
The objective of the investigations described in this paper was the stabilization of the
straightening process for the whole strip length on a coil using a control system which employs
130
the residual bending of the sheet after straightening as command variable. Trials were carried out
on a testing roller straightener present at the Institute for Metal Forming and Metal Forming
Machines (IFUM), Leibniz Universität Hannover, Germany. This straightener provides seven
rollers and hydraulic facilities to adjust the vertical positions of the four upper rollers
individually (figure 3).
Setting Mechanism
Frame
1 2 3 4
Vertical Adjustable Rollers

Fix Rollers
Underlay Rollers
Figure 3. Testing roller straightener
Measuring a control variable

Various approaches were described in the past to measure the residual bending of sheet metal
between straightener and forming press [11, 12, 13]. An unsolved problem within all these
methods is the overlaid tensile and bending stress which occurs between straightener and press as
a result of the constraint strain situation in the sheet metal. On one hand the reactive forces are
induced by the move out rolls acting as a clamp in this case and obstructing free bending of the
sheet metal strip. On the other hand the sheet metal in the loop entails tractive forces and tensile
strain in the sheet by its own dead weight. Both effects have an impact on the sheet’s bending in
the measuring device. All geometric measuring methods face this problem. The measurement of
non-geometric quantities and a following calculation of the residual bending will not succeed
because a material model would be needed. The material properties of the sheet metal are not
well enough known to calibrate such a model (see chapter 3). The deviation of calculating results
from reality produced by means of this model would lead to failures. On the other hand the
removal of these failures is the motivation to develop the here described control system. While
sufficient measuring devices are unknown yet, we used a not tactile working three-point sensor.
opt. position encoder
move out rolls
moving direction Outlet
s1 s2 s3
Borders of measurement range

sheet metal
s: vertikale sheet position s

x: horizontal position of position encoders s3
2 h
}
s −s
h = s 2 − ( 3 1 ⋅ ( x 2 − x1 ) + s1 ) s
x3 − x1
1
x x
x1 2 3
Figure 4. Roller straightener and measuring device
131
An impact of these sensors on the sheet metals bending can be excluded. Propounding a linear
equation with the first and the last dataset it is possible to calculate the deviation of the sheet
strip from a straight line in the middle (so called h, figure 4).
The variable h is not suitable to calculate an exact bending line. However h is fit to be used as a
command variable because its sign has the correct direction.
Control circle
Elements of the control system are the control path (straightener and sheet metal), PI-controller
and the hydraulic actuators to vary the vertical roller positions. Either the position of a roller can
be controlled or the force occurring at one of the upper rollers. Force or position can be chosen at
the control panel. Figure 5 shows the schematic assembly.
Bending-Dependent Target Value
Factual / Pactual
for one Roller
Controlled System: Straightener and

sheet metal
hTarget =0
ΔF / ΔP
PI-Controller
Factual / Pactual hactual hactual
Fix Target Values

for the other Rollers
t
ΔF / ΔP = KP (hactual(t ) − hTarget ) + KI ⋅ ∫ (hactual (t) − hTarget )dt
t0
Figure 5. Control circle
The value of h is transferred to a PI-Controller which calculates a correction value depending on

the preset parameters. By means of this value the position or the force (depending on the chosen
operating mode) of one of the upper rollers will be adjusted. Furthermore a linear adjustment of
the rollers as usual in straighteners today is implemented. Roller forces as well as roller positions
are imaginable as command variable to obtain straight sheet strips. Both operation modes were
tested to verify the control system. Using the force control a strong interaction between the
individual rollers occurred. Increasing the force at one roller by moving it downwards for
example causes counter-forces of similar scale at near by rollers. On figure 6 this is explained for
a variation of the target value of roller three.
Roller forces interact in force control modus,

Variation of the Force at Roller 3 in Simulation,
the sheet metal appears as a lever,
Positions of Rollers 1,2,4 fix feeder generates variing vertikal forces
-4
*10 Residual bending 1/r [1/mm]
2 ΔF3
0
-2
Roller 4 Roller 3
-4
-6
ΔF2 ΔF4
-8
Roller 1
-10
-12
Roller 2
-14 The control system tries to clear
-16 this, in consequence the rollers move
1000 2000 3000 4000 5000 6000 7000 8000 9000
permanent, instability,
Force [N] value deviation
Figure 6. Changing of roller forces varying force at roller three
The positions of rollers one, two and four are unmodified. Varying the force of roller three both
132
the residual bending of the sheet metal and the force at rollers one, two and four changes. This
graph was created by a simulation according to [8]. Moreover the changing of the contact angle
between the sheet metal and the following roller impacts a variation of the vertical roller force in
dependence of the sheet metal strips velocity. In force-controlled operation mode the control
system tries to eliminate all these disturbances. This control activity has a retroactive impact on
the force of roller three and so on. The system contains instabilities.
An interaction between the rollers can be observed in the position-controlled operation mode too.
Here it is much smaller than in the force-controlled mode because it occurs only when the roller
straightening machine is deformed. The stiffness of the machine is much higher than the stiffness
of the sheet metal. For this reason the adjustment of a roller position has a big impact on the
deformation of the sheet metal and nearly no effect on the deformation of the machine. The
demand of control activity is small in this case because the system does not tend to vibrate.
Roller straighteners are always more stiff than the processed sheet metal, so this can be stated for
all machines of this kind.
Initial setup
Before starting the control system, initial values for the roller positions need to be set up.
Suitable initial values provide little residual bending after straightening even without activated
control system. To obtain such values we started a great number of simulations according to [8]
varying input data as material properties, pre-bending and the positions of the straightening
rollers. The program described in [8] calculates the roller forces and the residual bending after
straightening.
Testing the Control System
The roller whose position shall be controlled can be selected at the operating screen. The control
system can be started after positioning all rollers at the initial positions. Figure 7 shows the
dependence between the residual bending and the roller position for roller 4 and roller 3.
Furthermore the straightening results can be seen in the upper part of the figure. The straightened
sheet metal strips stand vertical below another strip used as a ruler. Both curves take a
monotonous course in the area of no residual bending. That means both rollers are proper to be
adjusted by a PI-controller using constant parameters to achieve satisfying straightening results.
The Photos of the sheet metal strips verify this assumption.
ΔP4 ΔP3
Ruler
Straightening Result
Sollwertvariation von Rollenposition 4 Sollwertvariation von Rollenposition 3
Rolle 1,2,3 fest Rolle 1,2,4 fest
-4 -4
*10 Residual Bending 1/r [1/mm] *10 Residual Bending 1/r [1/mm]
5 2
Roller 1 0
Roller 4 Roller 4
--2
Roller 2 -4
-6 Roller 2
0 Roller 3
-8 Roller 1
-10
Roller 3
-12
-14
-5 -16
-1 -0,5 0 0,5 1 1,5 2 2,5 3 -1 -0,5 0 0,5 1 1,5 2 2,5 3
Rollerposition [mm] Rollerposition [mm]
Figure 7. Residual bending controlling the position of roller 3 and 4
133
In contrast to this rollers 1 and 2 were not suitable to be adjusted by the control system (figure 8).
Residual bending remained in all trials in the sheet metal. This result meets the expectations for
roller 1 (figure 8, right) because the curve shows local extrema which lead to instability of the
system. Controlling roller 2, a straightened sheet metal without residual bending seems to be
achievable in simulation. On the other hand roller 2 is not always in operation around a residual
bending of zero. Deviations between simulation and reality as a result of (not exact enough
known) material properties that are varying pre-bending of the sheet metal strip explains the
failure of the system in this case.
ΔP2 ΔP1
Ruler
Straightening Result
Sollwertvariation von Rollenposition 2 Sollwertvariation von Rollenposition 1

Rolle 1,3,4 fest Rolle 2,3,4 fest Geht nicht
-4 -4
*10 Residual Bending 1/r [1/mm] *10 Residual Bending 1/r [1/mm]
2 0,5
1 Roller 1 0
Roller 4
0 -0,5
Roller 4 Roller 1 Roller 2
-1 -1
Roller 2
-2 -1,5
Rolle 4
-3 -2
Roller 3
-4 Roller 3 -2,5
-5 -3
-1 -0,5 0 0,5 1 1,5 2 2,5 3 -1 -0,5 0 0,5 1 1,5 2 2,5 3
Rollerposition [mm] Rollerposition [mm]
Figure 8. Residual bending controlling the position of roller 1 and 2
Controlling the wound up and the unwinded Coil
According to common standards the material properties of cold rolled steel vary up to 12 %.
Fabricators do not know how often the coil was decoiled, wound up, chopped, split or pre-
straightened using it to manufacture his products. As a consequence forming history and material
properties are unknown. The same can be said for the not measurable pre-bending while the
sheet metal is in a constrained situation. For this reason every calculation model for roller
straightening is of limited accuracy.
To verify the control systems performance we made straightening trials using a new sheet metal
coil as well as a nearly decoiled one (figure 9). In both cases satisfying straightening results were
realized. The roller positions adjusted by the control system vary around 0.2 mm.
134
Coil, Unwinded [d=520mm] ΔP3
good Results
Residual Bending Position Roller 3 on Coil
1/r [1/mm] Unwinded Wound up
-4
*10
2
{
Coil, wound up [d=940mm] Roller 4
{
--2
-4
-6 Roller 2
-8 Roller 1
-10
Roller 3
-12
Good Results -14
-16
-1 -0,5 0 0,5 1 1,5 2 2,5 3
Rollerposition [mm]
Figure 9. Residual bending controlling at the inside and outside radius of the coil
Conclusions
Applying capable initial values it is possible to stabilize the roller straightening process by means
of a control system which uses the residual bending of the sheet metal as target variable. The
positioning of the not controlled rollers is essential for the straightening processes sensitivity, if
the straightening machine has few rollers (less than approximately 10). Amending the research
activities presented in the text (controlling the positions of individual adjustable rollers)
additional control strategies were investigated which did not succeed in combination with the
testing roller straightener. The development of a reliable sensor to measure the residual bending
of the sheet after straightening is an objective for future research. Reasons are overlaid tensile
and bending stresses impacting the measurement results. Calculation models for roller
straightening based on given material properties are limited in accuracy because of the unknown
forming history.
References
1 Homepage of Industrieverband Blechumformung (IBU),

www.industrieverband-blechumformung.de, Jan. 2006
2 Henrich, L.-S., Theoretische und experimentelle Untersuchungen zum Richtwalzen von

Blechen, Dissertation Universität - Gesamthochschule Siegen, 1994.
3 Buchholz, O.-W., Beitrag zur Frage der Eigenspannungen und der Planheit von
kaltgewalztem Feinblech, Dissertation Technische Universität Hannover, 1973.
4 Theis, H., “Stripe Shape Variability”. Metal Forming, April 1991, p 23-25.
5 Madea, Y., Hattori, S., “Simulation of Strip Shape in Rolling and Levelling Processes.”
Kobelco Technology Review, No.13 April 1992, p .31-35.
6 Homepage of ARKU,
www.arku.de/ARKU/Pressearbeit/InfoMax/ARKU_InfoMAX_19D.pdf
7 Doege, E. (editor), Praxisnahe Entwicklungen am IFUM - mittelfristig umsetzbar.
135
17. Umformtechnisches Kolloquium Hannover 2002, p. 71-75.
8 Menz, R., Entwicklung eines analytischen Simulations- modells als Grundlage einer
geregelten Richtmaschine, Dissertation, IFUM, Leibniz Universität Hannover, 2002
9 Doege, E., Menz, R., Sensorgröße Kraft zur Online-Regelung von Blechrichtmaschinen,
Research report AiF 10828 N. Verein Deutscher Werkzeugmaschinenfabriken e.V.,
Frankfurt/M., 1998.
10 Schroeder, L., „Richten von Blechen und Bändern“ 7. Fachtagung FORUM BLECH,
Schweizerische Vereinigung für Blechverarbeitung und Metallbau, 28. March 1996 in
Dietikon.
11 Finckenstein, E., Kleiner, M., Chatti, S., „Krümmungssensoren zur Konturerfassung

walzgebogener Teile“, Sensor Magazin, 3/98 p. 18-20.
12 Straßmann, T., Prozessführung für das Walzrunden auf der Basis Neuronaler Netze,
Dissertation, Universität Dortmund, 1995
13 Averhage, M., Liewald, M., Straßmann, T., Konstruktion eines Krümmungssensors für den
Einsatz an einer Walzrundmaschine, Lehrstuhl für Umformende Fertigungsverfahren,
Universität Dortmund, 1995
136
DRILLING AND MILLING OF INTERMETALLIC γ-TiAl
Prof. Dr.-Ing. Dirk Biermann, Dipl.-Ing. Stefan Bergmann

Department of Machining Technology, University of Dortmund,
Baroper Str. 301, 44227 Dortmund, Germany
Keywords: γ-Titanium-aluminides, Machining investigations, Drilling, Milling,

Intermetallic compound, Production process
Abstract
γ-Titanium-aluminide (γ-TiAl) is an intermetallic compound. It offers a very good hot

strength, a high Young´s Modulus and tensile strength as well as a low density
(3.9 g/cm3). The main fields of its application are connecting rods, engine valves, turbo-
chargers for internal combustion engines and turbine blades. The key advantage of
deploying γ-TiAl results in a reduction of moving masses together with a minimization in
engine vibrations. Contrary to the outstanding lightweight material properties, problems
occur when machining is carried out. The bad machining behavior results from the high
hardness and brittleness in combination with the low thermal conductivity. These
properties lead to high cutting forces, cutting temperatures and rapid tool wear. The
article comprises investigations on the machining of a γ-TiAl alloy. Studies on drilling
and milling were conducted focusing on appropriate conditions for a high-quality
machining process. This paper presents results from selected machining tests, e. g.
cutting forces, tool wear, surface integrity as well as tool and process design.
Introduction
The optimization of car engines and aviation turbines is of enormous significance
because of the limited availability of sources and the need to minimize environmental
impact. The employment of materials with high weight-specific properties basically
offers potential for reducing the weight of an engine. Particularly with regard to moving
parts, the usage of lighter materials enables the whole design of an engine to be
optimized in terms of its weight. Reduction in the weight of subassemblies, e. g. turbine
blades, blisks, valves, connecting rods is mainly achieved by the application of light
weight materials. Besides the low density, sufficient heat strength, creep resistance as
well as corrosion resistance is necessary concerning the demands on the specific
material properties. Among other state-of-the-art lightweight materials, intermetallic
compounds belong to the most promising approaches for engine applications. [1, 2]
In this connection, research has been carried out to implement a γ-Titanium-aluminide
alloy as a material for connecting rods for combustion engines. These investigations are
carried out within a joint project of five partners (industrial companies and university-
institutes) and it is financed by the BMBF (German Federal Ministry of Education and
Research). Other applications are the use of γ-TiAl-alloys in outlet valves or turbo
charger wheels (Figure 1). [3]
137
Figure 1: Fields of application of γ-TiAl alloys
In most cases, engine parts have to be machined at the last stage of the process chain.
The operations are for example milling, drilling or threading operations. Due to their
outstanding material properties, machining is accompanied by several problems. These
problems emerge from high cutting forces or abrasive conditions. It is necessary to use
low cutting parameters to reduce tool wear. Due to this, manufacturing costs rise as a
result of the high tool costs, so process and tool optimizations are necessary to
minimize production time and tool wear. [4]
Material
The investigated γ-TiAl alloys have been vacuum arc melted and extruded by the GfE
company in Nuremberg, one of the partners within this joint project. The Chair of
Physical Metallurgy and Materials Technology of the BTU Cottbus, another partner,
accomplished the material characterization. At first, the γ-TiAl-alloy containing 46 %
aluminum (by weight) was tested, but poor forging behavior, problems during the crack-
tests of the partner BMW and material chip-outs during machining led to an optimization
of this material.
Ti-46Al-0.5Mo-0.8Cu-0.2Si Ti-44.5Al-0.5Mo-1.0Cu-0.2Si
Condition forged forged
Density ρ = 3.9 g/cm3 ρ = 3.9 g/cm3
Youngs modulus E = 159 – 173 GPa E = 162 – 170 GPa
Yield strength σ0.2 = 750 – 760 MPa σ0.2 = 760 – 790 MPa
Tensile strength UTS = 750 – 812 MPa UTS = 780 – 904 MPa
Fracture elongation El = 2.6 % El = 4.2 %
Micro Hardness 355 HV0.1 344 HV0.1
Fatigue strength (R = -1) σa (107) = 675 MPa σa (107) = 625 – 675 MPa
Type 1 Type 2
Fully recrystallized structure Partly recrystallized structure with
lamellar areas
Source: BTU Cottbus Source: BTU Cottbus
Ti-46Al-0.5Mo-0.8Cu-0.2Si Ti-44.5Al-0.5Mo-1.0Cu-0.2Si
extruded (14:1) + 4h 950 °C/ furnace extruded (14:1) + 4h 950 °C/ furnace
Figure 2: Material structure of the investigated γ-TiAl alloys
138
The new γ-TiAl-alloy contains 44.5 % aluminum (by weight) and due to that, it exhibits a
higher ductility (see Figure 2), which improves the machining behavior. Figure 2 also
displays the structure of both alloys after the extrusion and heat treatment.
The figure shows a mainly globular structure for alloy type 1 with 46% aluminium and a
structure with larger lamellar areas for alloy type 2 with 44.5% aluminium. The larger
lamellar areas are responsible for the improved ductility of alloy type 2. Through the
variation of alloying elements, a slight increase in tensile and yield strength was
achieved.
Drilling Investigations
Within the mentioned project, drilling investigations were performed at first on alloy
type 1. The results showed that the fine grained cemented carbide tools with stable
cutting edges are appropriate to machine γ-TiAl [5]. The best tested tool (tool 1) was
chosen for the subsequent tests with the improved alloy type 2. In the preliminary tests,
the uncoated tool 1 achieved slightly better results than the conventionally TiAlN coated
tool 1. For following tests, two different coating types were tested: a high aluminum
contending TiAlN-coating and an AlCr multilayer coating. These tools have been
compared to a HC twist drill (tool 2), that has a rounded tool tip and is designed for cast
irons and a HW drilling tool with brazed PCD inserts (tool 3). Figure 3 shows the tested
tools and their main characteristics, e. g. cutting angles and tool substrates. The rake
angle of all tools is neutral or slightly negative, which leads to a stable cutting edge.
Cutting material: HW (Tool 1)

HC (Tool 1 with
TiAlN or AlCr, Tool 2)
Tool 1, cemented carbide K20 F, uncoated
PCD (Tool 3)
Tool diameter: 8.1 mm

Spin angle: λ = 0° (Tool 1 and 3)
λ = 25° (Tool 2 )
Tool 1 with TiAlN
Rake angle: γ = 0° (Tool 1 and 3)
γ = 5° (Tool 2)
Tool 1 with AlCr multilayer Clearance angle: α = 9° (Tool 1)

α = 17° (Tool 2)
α = 18° (Tool 3)
K20F: ~ 93 % WC, 7 % Co
Tool 2, cemented carbide DK255 F, TiAlN multilay. Hardness ~ 1700 HV30
Grain Size ~ 1µm
DK255F: ~ 92 % WC, 8 % Co
Hardness ~ 1720 HV30
Tool 3, PCD brazed on cemented carbide Grain Size ~ 0.7µm
Figure 3: Drilling tools for machining tests

In the following Figure 4, the feed forces and drilling torques of tool 1 without coating,
tool 2 and tool 3 are displayed. Tool 1 generated the lowest feed forces because of a
small chisel edge of about l = 0.6 mm. At a cutting speed of vc = 100 m/min, the cutting
temperatures achieved a value that exceeded the warm strength of the cemented
carbide and the cutting edge of tool 1 was distorted. The TiAlN-coated tool 2 achieved
vc = 140 m/min when a chipping off of material at the rake face stopped the test. Up to a
139
cutting speed of vc = 100 m/min, the feed force and drilling torque values rose
moderately, at higher cutting speeds the slope of both courses (of tool 1 and tool 2)
increased and this indicates the upcoming end of the tool test. Tool 3 passed the test up
to vc = 150 m/min. For these cutting conditions, tool 3 did not show any wear or material
chipping out. A slightly higher feed rate of f = 0.06 mm/rev led to an immediate
destruction of the PCD inserts.
Workpiece Ti-44.5Al-0.5Mo-1.0Cu-0.2Si (forged) Spin angle: ε = 0° (tool 1, tool 3)

Cutting speed: vc = 30…150 m/min ε = 25° (tool 2)
Feed rate: f = 0.05 mm/rev Cutting material: HW (Tool 1)
Tool diameter: d = 8.1 mm HC TiAlN (Tool 2)
Lubrication: Oil, 50 bar PCD brazed on HW (Tool 3)
2500 7
Tool 1 Tool 1
Tool 2 Nm Tool 2
N
Tool 3 Drilling torque MB Tool 3
Feed force Fz
5
1500
4
1000 3
2
500
1
0 0
0 50 100 m/min 200 0 50 100 m/min 200
Cutting speed vc Cutting speed vc
Tool 1 after vc = 100 m/min Tool 2 after vc = 140 m/min Tool 3 after vc = 150 m/min
Figure 4: Cutting forces when drilling γ-TiAl with different tools
To find out if a coating may improve the tool performance, tool 1 was coated with a high
aluminum containing TiAlN-coating and an AlCr-coating. The results in Figure 5
illustrate that due to the coating, feed force and drilling torque are slightly lower. This
may be caused by lower friction and fewer material adhesions compared to the
uncoated tool. With the AlCr coating, tool 1 achieved a maximum cutting speed of
vc = 120 m/min, because of a higher hardness and lower thermal conductivity of the
coating compared to the substrate. The TiAlN coated tool 1 achieved a higher maximum
cutting speed of vc = 150 m/min until the tool was broken. The reasons are a very high
hardness of the coating in combination with a very good adhesion of the coating to the
substrate. Surprisingly, the drilling torque of this tool decreased with higher cutting
speeds. A possible reason could be a thermal induced reduction of the material strength
of the γ-TiAl at higher cutting speeds without the problem of material adhesion to the
tool.
140
Workpiece: Ti-44.5Al-0.5Mo-1.0Cu-0.2Si (forged) Spin angle: ε = 0°
Cutting speed: vc = 30…150 m/min
Feed rate: f = 0.05 mm/rev Cutting material: HW 1700 HV
Tool diameter: d = 8.1 mm HC TiAlN 3300 HV
Lubrication: Oil, 50 bar HC AlCr 3000 HV
Tool 1 uncoated Tool 1 TiAlN-coated, Tool 1 coated with

high Al-content AlCr multilayer
800 3
N
Drilling torque MB
Nm
600
Feed force Ff
500 2
400 1,5
300
uncoated 1
200
TiAlN
100 0,5
AlCr
0 0
0 20 40 60 80 100 120 m/min 160 0 20 40 60 80 100 120 m/min 160
Figure 5: Effect of coatings on the machining forces

A quality control of the drilled holes showed big differences concerning the diameter and
concentricity deviation of the three tool types. Tools 1 and 3 with sharp grounded cutting
edges led to small deviations of the mentioned values, but tool 2 with the rounded tool
tip did not center well within its holes and therefore produced a poor drill hole quality. To
improve the quality and keep the performance of the tool on the same level, two
variations of the serial tool type 2 were investigated. These variations are displayed in
Figure 6 in comparison to the serial tool 2.
Dimension of Diameter: Ø = 8,1 mm
chisel edge: Substrate: HC DK255 F
Coating: TiAlN/TiN
0.82 mm Multilayer
Tool 2, serial type
Rake angle:
Serial type: γ = 5°
0.42 mm Variation a: γ = 5°
Variation b: γ = 5°
Tool 2, variation a
Clearance angle:
Serial type: α = 17°

Variation a: α = 15°
0.46 mm Variation b: α = 15°
Tool 2, variation b
Figure 6: Variation of tool 2
Figure 7 presents the achieved optimizations of tool 2 compared to the hole
straightness and roundness results of tools 1 and 3. The diagram contains the best and
worst measurements of roundness and hole straightness in full range of the cutting
speed, i. e., between vc = 30 and 120 m/min. It can clearly be recognized that the
straight fluted tools 1 and 3 with sharp tool tips produced the best drill hole qualities. But
141
via the variation of tool tip and rake face, tool 2b achieves about 10 to 20 µm smaller
diameter deviation and about 130 µm lower hole straightness deviations. As it can be
seen in Figure 8, tool 2b generated significantly higher feed forces than tool 2a and 2c.
This high value of feed force is a reason for the low hole straightness deviation,
because the high feed force avoided big tool oscillations successfully.
Workpiece: Ti-44.5Al-0.5Mo-1.0Cu-0.2Si (forged) Feed rate: f = 0.05 mm/rev

Cutting speed: vc = 30…120 m/min Tool diameter: d = 8.1 mm
Lubrication: Oil, 50 bar Cutting material: HW (Tool 1)
HC TiAlN (Tool 2)
PCD brazed on HW (Tool 3)
120 250
µm
Hole straightness deviation

µm
Deviation of diameter
80
150
60
100
40
50
20
0 0
Tool 1 Tool 2 a Tool 2 b Tool 2 Tool 3 Tool 1 Tool 2 a Tool 2 b Tool 2 Tool 3
serial serial
Figure 7: Comparison of deviation of diameter and hole straightness deviation
But the general relationship of the drill hole quality can not be changed through the
geometrical variations of tool 2. Tool 1 generated the best drill hole qualities, followed
by the PCD-equipped tool 3 and then the optimized tool 2b. The serial tool 2 achieved a
lower deviation of diameter than tool 2a, but a worse hole straightness deviation.
As just mentioned, Figure 8 shows the feed forces of the three different types of tool 2.
The serial tool generated lowest feed forces due to the rounded tool tip.
Workpiece: Ti-44.5Al-0.5Mo-1.0Cu-0.2Si Cutting speed: vc = 30…140 m/min
(forged) Feed rate: f = 0.05 mm/rev
Lubrication: Oil, 50 bar Cutting material: HC TiAlN
Tool diameter: d = 8.1 mm Spin angle: ε = 25°
2400
N
2000
1800
Feed force Ff
Tool 2 a
1600
Tool 2 b
1400
Tool 2 serial
1200
1000
800
0
30 50 70 100 120 m/min 140
Cutting speed vc
Figure 8: Feed force of serial and optimized drilling tool no. 2 at different cutting speeds
142
Tool 2a with the reduction of cutting edge permitted highest cutting speeds at medium
forces, tool 2b with the planar grounded rake face and sharp tool tip generated the
highest forces and showed material chip-outs beginning at vc = 120 m/min, so the test
stopped there.
To get an impression which tool type allows the longest tool service life, tests with three
HC-tools (tool 1, 2a and 2 serial type) were performed, displayed in Figure 9. Because
of the limited number of test components, the tests had to be stopped before the tools
reached the service life end. During the tests, material adhesions complicated the
measurement of the width of wear land, because γ-TiAl can not be detached easily. So,
the feed force was measured to characterize the process development. Only tool 1
shows constantly growing feed forces, the other tools remained static at feed force
values of Ff = 1000 N and 1050 N, respectively. So the result of this test is that each
tool achieved at least 1.2 m of feed stroke at vc = 70 m/min.
Workpiece: Ti-44.5Al-0.5Mo-1.0Cu-0.2Si Diameter: d = 8.1 mm
(forged) Drillhole depth: t = 20 mm
Cutting material: HW (Tool 1) Cutting speed: vc = 70 m/min
HC + TiAlN (Tool 2 and 2a) Feed rate: f = 0.05 mm/rev
Spin angle: ε = 0° (Tool 1) Lubrication: Oil, 50 bar

ε = 25° (Tool 2 and 2a)
1200
Tool 2
800
Feed force F
600
Tool 1, HW
400 Tool 2 a
Tool 2, HC, serial
200 Tool 2, HC, var. a
0 20 40 60 80 100 120
Tool 1
Number of drillhole
Figure 9: Development of the feed force of three tool types
Milling Investigations
As it was written in the part “Material”, the γ-TiAl investigations started with an alloy
containing 46 % aluminum. That alloy was milled with triangle formed insert tips of
multilayer (Ti, Al)N-coated cemented carbide (Figure 10, left side).
143
Insert 1 Insert 2 Insert 3 Insert 4
Cutting material: HC F30M HC F30M HC F30M HC F100M
Rake angle: 10° 0° 0° 0°
Width of cutting
edge chamfer: 0.08 mm 0.08 mm 0.08 mm 0.08 mm
Grainsize: 0.8 – 1.0 µm 0.8 – 1.0 µm 0.8 – 1.0 µm 0.3 – 0.5 µm
Hardness: 1650 HV10 1650HV10 1650 HV10 1950HV10
Coating: - (Ti, Al)N – TiN-Coating -
Figure 10: Cutting inserts for milling investigations

The inserts were chosen based on the first drilling and tapping tests which showed that
stable cutting edges and hard substrate materials are well applicable.
They are made of fine grained HC and two geometries – a neutral and a slightly positive
one, have been selected. Important characteristics of the insert tips are displayed in
Figure 10, as well. Figure 11 shows the experimental setup in a Grob BZ 600 machine
tool. During the tests, the passive forces were measured and the forces in x- and y-
direction were calculated to determine the “Active force”.
Milling tool
Clamping device
FP
Passive force
γ-TiAl-workpiece
Force measurement device
Figure 11: Experimental setup for milling tests

Figure 12 shows these measured forces depending on the feed per tooth for different
cutting speeds. The growing stock removal volume is responsible for rising forces at
higher feeds. The measured forces of tip no. 1 at vc = 70 m/min, are extensively higher
than those of tip no. 2 and for that reason, the ordinate of this diagram was arranged
differently than that of all the other three diagrams. There is a significant difference
between the cutting force gradients at vc = 30 m/min and vc = 70 m/min, too. The insert
tip no. 1 with the positive rake angle broke at fz = 0.5 mm whereas tip no. 2 was able to
tolerate even feeds of fz = 0.8 mm. The reason is the larger wedge angle of insert tip 2,
the thermal load of the cutting process is spread into a larger cutting material volume
and so the hot temperature strength of the cutting material does not need to be that
high.
144
Workpiece: Ti-46Al-0.5Mo-0.8Cu-0.2Si Cutting speed: vc = 30…70 m/min
(forged) Cutting depth: ap = 0.1 mm
Feed per tooth: fz = 0.1 - 1 mm
Lubrication: Emulsion Cutting material: HC
Insert 1 Insert 2
1200 1200
Cutting Force F
Cutting Force F
vc = 30 m/min vc = 30 m/min
N N
800 800
600 600
400 400
Active force Active force
200 200
Passive force Passive force
0 0
0 0,2 0,4 0,6 0,8 mm 1,2 0 0,2 0,4 0,6 0,8 mm 1,2
Feed per tooth fz Feed per tooth fz
4000 1200
Cutting Force F
vc = 70 m/min vc = 70 m/min
Cutting Force F
N N
3000
800
2000 600
400
1000 Active force Active force
200
0 0
0 0,2 0,4 0,6 0,8 mm 1,2 0 0,2 0,4 0,6 0,8 mm 1,2
Feed per tooth fz Feed per tooth fz
Figure 12: Cutting forces when milling γ-TiAl with HC cutting inserts
At tip no. 1, the thermal impact is concentrated onto the positive cutting edge, that got
extremely hot at a cutting speed of vc = 70 m/min and than showed large material chip-
offs and tip destruction. At a lower cutting speed of vc = 30 m/min, tip no. 1 generated
slightly lower cutting forces than tip no. 2.
After different tests of the project partners, the γ-TiAl alloy had to be changed to a type
with 44.5 % aluminum. Based on a lot of further cutting tests (drilling, turning, boring,
tapping) and the first milling tests, round insert tips were chosen for the continuation of
the milling investigations (Figure 10, insert tips 3 and 4). Promising results shows insert
tip 4 that provides new extremely fine grained cemented carbide with a hardness of
1950HV10. The rake angle was neutral and the lubrication concept was changed from
emulsion to dry machining, which was not possible with insert tips 1 and 2. The
following Figure 13 depicts the good advantages of the new insert types. At a feed per
tooth of fz = 0.5 mm, the cutting speed could be set up to vc = 200 m/min (tip no. 4) and
the cutting forces were significantly lower than those of the tips no. 1 and 2. At the
highest cutting speed of vc = 200 m/min and without emulsion insert tip no. 4 started to
glow and that was the reason to stop the test at that point. Investigations at a lower feed
per tooth were performed as well, and there the combination of the new γ-TiAl alloy and
the round insert tips showed significantly lower forces and flank wear. The main reasons
for the outstanding optimization is surely the application of the new cutting material and
insert tip form, because for the other machining operations, the change of the TiAl-alloy
only led to smaller improvements.
145
Workpiece: Ti-44.5Al-0.5Mo-1.0Cu-0.2Si (insert 3 and 4) Cutting speed: vc = 30…200 m/min
Ti-46Al-0.5Mo-0.8Cu-0.2Si (insert 1 and 2) Cutting depth: ap = 0.1 mm
(forged) Feed per tooth: fz = 0.5 mm
Lubrication: Emulsion, dry Cutting material: HC
Insert 3, dry machining Insert 4, dry machining

700 700
N N
Cutting force F
Cutting force F
500 500
400 400
300 300
200 200
100 100
0 0
0 50 100 150 m/min 250 0 50 100 150 m/min 250
Insert 1, emulsion Insert 2, emulsion
3000 3000
N N
Cutting force F
Cutting force F
2000 2000
1500 1500
1000 1000
500 500
0 0
0 50 m/min 150 0 50 m/min 150
Figure 13: Milling with different tools and lubrication concepts
Summary
Machining of γ-TiAl is very challenging because of the outstanding material properties of

this material, especially the strength, low thermal conductivity and brittleness. The
Department of Machining Technology (ISF) accomplished drilling and milling tests for
two different types of TiAl-alloy and through that, cutting tools have been improved and
feasible machining methods were developed. Drilling is well practicable with straight
fluted TiAlN-coated HC-tools of the group K20F and with PCD-equipped tools at cutting
speeds up to vc = 150 m/min and feeds of f = 0.05 mm/rev. Due to the high cutting
forces and temperatures when machining γ-TiAl, drilling works best with oil lubrication.
Milling is possible without lubrication up to cutting speeds of about vc = 150 m/min with
round HC insert tips. Face milling operations showed better tool service lifes with
emulsion than dry machining, but they are not directly comparable because of different
rake angles and substrate materials. Extremely fine grained substrate material with a
grain size of 0.3 - 0.5 µm, led to very good results. The cutting speed could be raised
and wear was decreased. Independent of the machining operation, neutral or even
slightly negative rake angles should be chosen to reinforce the cutting edge. Future
investigations shall comprise the measurement of cutting temperatures and
investigations on the service life of drilling and milling tools.
146
Acknowledgments
The authors gratefully acknowledge the funding of the investigations by the German
Federal Ministry of Education and Research (Bundesministerium für Bildung und
Forschung, BMBF).
References
[1] Bartolotta, P., Barett, J., Kelly, T., Smashey, R.: The use of cast Ti48Al2Cr2Nb in jet
engines. JOM-The journal of the minerals, metals and materials society, 49/5
(1997), p. 48-50
[2] Weinert, K., Biermann, D., Bergmann, S.; Machining of High Strength Light Weight
Alloys for Engine Applications. Annals of the CIRP, 2007, Volume 56/1, p. 105-108
[3] Güther, V., Kerzendorf, G., Lindemann, J., Schillo, E., Viehweger, B., Weinert, K.:
Bericht zur γ-TiAl Herstellung, Bearbeitung und Charakterisierung, Spanende
Fertigung, 4. Ausgabe (2005), p. 363 – 371
[4] Aust, E., Niemann, H.-R.: Machining of γ-TiAl, Advanced Engineering Materials 1,
No. 1 (1999), p. 53-57
[5] Weinert, K., Bergmann, S., Kempmann, C.: Machining Sequence to Manufacture a
γ-TiAl Conrod for Application in Combustion Engines, Advanced Engineering
Materials 8, No. 1-2 (2006), p. 41-47
147
149
150
151
152
153
154
155
156
157
158
159
160
161
BLOCKING AND SELF-LOCKING OF SUPERDISLOCATIONS IN

INTERMETALLICS
B.A. Greenberg1, M.A. Ivanov2, A.M. Patselov1

1
Institute of Metal Physics, Ural Div., Russian Academy of Sciences;
18 S.Kovalevskaya St.; Ekaterinburg, 620241, Russia
2
Institute of Metal Physics, National Academy of Sciences;
36 Vernadskogo blvd.; Kiev, 03142, Ukraine
Keywords: Dislocations, Plastic Deformation, Potential Relief, Shallow Valley, Deep Valley,
Dislocation Blocking, Self-Locking, No-Load Heating.
Abstract
A new concept about the possibility of thermally activated blocking of superdislocations in the
absence of external stresses (self-locking) was proposed. A sufficiently general thermally
activated process, which causes the extension of a dislocation in a preferred direction was
revealed. By its nature, this process represents the flip of a dislocation from a shallow valley to a
deep valley of the potential relief. Reasons for the multivalley relief and the presence of
preferred directions vary for dislocations of different types in different materials. Consecutive
stages of this rearrangement of an initial dislocation with the direction approaching a preferred
one: the formation of a double kink and its subsequent reorientation in a preferred direction. The
driving force of the process was calculated and conditions for its realization in the cases of
perfect and superpartial dislocations were formulated. An experimental proof of the proposed
concept was obtained: self-locking of dislocations, which were induced by preliminary
deformation, was detected in Ni3(Al, Nb) and TiAl during no-load heating.
Introduction
A large translation vector, different types of stacking faults and antiphase boundaries (APB)
determine the diversity of dislocation configurations, both glissile and sessile (blocking), in
intermetallics.
Figure 1. Schematic image of the potential relief: one-valley relief (a), two-valley relief (b).
165
A significant point is that blocking superdislocations, which are formed due to re-splitting of
glissile superdislocations or rearrangement of the superpartial core, have the lowest energy.
Regardless of transformation details, a common feature is that the dislocation energy is gained at
the expense of the dislocation mobility: a glissile dislocation turns to a dislocation barrier, which
either remains indestructible or, under certain conditions, can re-transform to a glissile
configuration. The barrier axis is the preferential direction along which the transformation to a
low-energy configuration is realized. As a result, the potential relief for a dislocation is a multi-
valley one: shallow valleys and a deep valley in some preferred direction (fig. 1).
Flip-process
The flip of a dislocation from a shallow to a deep valley of the potential relief, which causes the
extension of the dislocation in the preferential direction, is a sufficiently general thermally
activated process and constitutes a necessary step in dislocation transformations leading to
blocking.
The flip process includes the formation of a double kink (fig. 2a) and its subsequent reorientation
resulting in the formation of an asymmetric kink (fig. 2b). The internal structure of the
dislocation changes in the preferred direction and, hence, the dislocation energy decreases.
Because this process takes place at different points along the dislocation line, the initial
dislocation is broken down into long blocked segments. The flip process and the subsequent
transfer ultimately determine the temperature dependence of the yield stress σy(T). If the release
from deep valleys is possible, σy(T) will exhibit a normal behavior. If such release is hampered
(indestructible barriers), an anomalous trend of σy(T) will be observed in certain conditions.
Figure 2. Consecutive stages of the rearrangement of the initial dislocation whose direction is
close to the preferred direction: (a) – double kink; (b) – reorientation in the preferred direction
Nucleation And Propagation Of Kinks
Perfect Dislocations
Let us consider a two-valley potential relief (fig 1b). We shall assume for simplicity that the
initial direction and the preferred direction are almost parallel. The double kink consists of initial
dislocation segments located in a shallow valley, a segment of the length d flipped to the deep
valley, and single kinks connecting these segments. According to [1], the energy of the double
kink can be written as the sum of the definite contributions. Furthermore, it is necessary to
consider the change of the linear energy as the dislocation is transferred from a shallow valley to
the deep valley. This contribution, which is connected with different depth of the valleys, was
166
disregarded earlier and distinguishes the present study from other investigations. The critical
configuration of the double kink, which is determined from conditions of the total energy
extremum, has the length dc equal to
Ka 2
dc = , (1)
(σba + ΔE )
ΔE = E0 − Ev , (2)
Here E0 is the energy of the dislocation in a shallow valley, Ev is the energy of the dislocation in
the deep valley (both energies per unit length of the dislocation), K = kμb 2 , μ is the shear
modulus, and k is a coefficient depending on the dislocation orientation.
If the external stress is not applied, the critical configuration appears, as can be seen from (1),
due to an additional driving force proportional to ΔE . If σ =0, the condition for the flip process,
which causes self-locking of the dislocation, is the inequality ΔE > 0 . Obviously, this driving
force simultaneously counteracts the reverse transition from a deep valley to a shallow valley.
Therefore, thermally activated formation of indestructible barriers can be expected during no-
load heating.
Self-locking is still possible if directions, along which shallow and deep valleys are extended,
are not parallel, but the angles between them are not too large (fig. 2b) Then the condition of the
self-locking is that the energy of the dislocation, which is a broken line and consists of a segment
of the length d extended in the preferred direction and a single kink of the length h, is smaller
than the energy of the initial rectilinear dislocation of the length l. This condition can be written
as
Ev d + E0 h < E0l . (3)
Introduce the angle ϕ between the preferred direction and the direction of the initial
dislocation (fig. 2b). It can be easily shown that the limiting angle ϕ for self-locking may be
determined from the equation
cos ϕ + sin ϕ − 1
ΔE / E0 = . (4)
cos ϕ
If ϕ < ϕ flip-process may be realized.
Superpartial Dislocations
It is possible that a preferred direction exists for superpartials connected by the APB band. In this
case, the immersion of the superpartial in the deep valley requires an additional energy
proportional to the area of APB. Then, instead of (3), the condition of self-locking takes the form
( Ed + E0 tgϕ + 1/ 2d ς tgϕ)d < ( E0 / cosϕ)d , (5)
where ς is the APB energy in the respective plane (per unit area).
It may be shown that the flip of the partial dislocation to the deep valley is impossible at
ϕ > ϕ similarly to the perfect dislocation considered above. If ϕ < ϕ the possibility of this
167
process depends on the relationship between ΔE and ς a . Self-locking is possible only if the
condition
ΔE > ς a (6)
is fulfilled. Moreover, it can be easily shown that the additional condition
ϕ < min{ΔE / E0 , ϕ } (7)
should be hold. Therefore, if the inequality (6) is fulfilled, the extension of segments, whose
orientation satisfies (7), becomes possible.
Examples
Self-locking Of Superdislocations
Figure 3. Dislocation structure of [ 2 51] single crystals of Ni3(Al, Nb) after preliminary
deformation and subsequent no-load heating: (a) – deformation at -196°C; (b) – heating at
200°C, 20 min; (c) – heating at (500°C, 1 h + 800°C, 1 h);
(d) – deformation at 800°C; (e, f) – heating at 200°C, 1 h.
168
The experiments on the no-load heating after preliminary deformation (at low and high
temperatures) were realized [2-5]. In the alloy Ni3(Al,Nb) initial superdislocations with Burgers
vectors <101> had curvilinear form. The heating temperatures were lower or on the contrary
higher than the peak temperature of yield stress. Still, whichever the heating temperature,
barriers were formed, but were not destructed in the both cases (fig. 3).
Experiments on no-load heating of pre-deformed TiAl were performed [6]. The self-locking
of superdislocations with Burgers vectors <101] and 1/2 <112] was observed.
Self-locking Of Ordinary Dislocations (TiAl)

The transfer of an ordinary dislocation from a shallow to a deep valley corresponds to the
dislocation core rearrangement [7]. The self-locking of ordinary dislocations was found [6].
Figure 4. Dislocation structure of TiAl after preliminary deformation and subsequent no-load
heating: (a) – deformation at at room temperature; (b) – heating at 400 °C, 1h
Only curvilinear dislocations were observed after deformation at room temperature (fig.
4a). Blocked ordinary dislocations were observed after subsequent no-load heating. The first
stages of extension of ordinary dislocations were proved to be observed, when screw segments
had already rectilinear form, but other segments had still curvilinear form (fig. 4b).
Acknowledgements
This study was performed under the State contract No. 02.467.11.2007 and supported by a grant
from RFBR (No. 07-03-00144, 07-03-96122) and project No. 10 of the Presidium RAS.
References
1. M.S. Duesbery, “The influence of core structure on dislocation mobility,” Phil. Mag., 19 (159)
(1969), 501-526.
2. B.A. Greenberg and M.A. Ivanov, “Some features of formation and destruction of dislocation
barriers in intermetallics. I. Theory,” The Physics of Metals and Metallography, 102 (1) (2006),
61-68.
3. B.A. Greenberg et al., “Some features of formation and destruction of dislocation barriers in
intermetallics. II. Observation of blocking superdislocations after no-load heating,” The Physics
of Metals and Metallography 102 (1) (2006), 69-75.
169
4. A.M. Patselov, et al., “Some features of formation and destruction of dislocation barriers in
intermetallics. III. Thermally activated extension of dislocations along preferred directions in
Ni3Al,” The Physics of Metals and Metallography 104 (5) (2007) (in press).
5. B.A. Greenberg et al., “Deformation behavior of intermetallics: models and experiments,”
Proc. of the 4th Int. Conf. On Mathematical Modelling and Computer Simulation of Material
Technologies (Ariel, Israel, 2006), (1), 122-131.
6. B.A. Greenberg et al., “Some features of formation and destruction of dislocation barriers in
intermetallics. IV. Thermally activated extension of dislocations along preferred directions in
TiAl,” The Physics of Metals and Metallography 105 (5) (2008) (in press).
7. B.A. Greenberg et al., “Possible Factors Affecting the Brittleness of the Intermetallic
Compound TiAl. II. Peierls Manyvalley Relief,” Scripta metall., 22 (6) (1988), 859-864.
170
EFFECT OF THE γ/γγ' LATTICE MISMATCH ON THE CREEP

BEHAVIOUR AT 760°C OF NEW GENERATION SINGLE CRYSTAL
SUPERALLOYS
Pierre Caron1, Frédéric Diologent2

1
ONERA, 29 avenue de la Division Leclerc, Châtillon, 92320, France
2
Laboratoire de Métallurgie Mécanique, EPFL, Lausanne, 1015, Switzerland
Keywords: Superalloy, Creep, Lattice mismatch
Abstract
The constant-load tensile creep behaviour of two fourth generation single crystal nickel-based
superalloys MC534 and MC544 has been evaluated at 760°C and 840 MPa. The higher
amplitude of γ/γ’ lattice mismatch in MC534 promotes glide of dislocations within the γ matrix
and prevents shearing of the γ’ precipitates. That results in a limited primary creep, a low
minimum creep rate and a long creep life. The decorrelated movement of Shockley partials in the
γ phase signs the difficulty for perfect dislocations to move between the precipitates.
Heterogeneous deformation with shearing of γ’ precipitates leads to higher amplitude of primary
creep and shorter creep life for MC544 where the lattice mismatch amplitude is lower.
Introduction
Nickel-base superalloys for single crystal (SC) gas turbine blade applications draw their
outstanding creep resistance from their high volume fraction of ordered L12 γ’-Ni3Al type
precipitates which hinder the motion of a/2<110> dislocations in the f.c.c. γ matrix. The size of
the γ’ precipitates, their volume fraction and their chemistry influence the mobility of the matrix
dislocations and the by-passing mode of the precipitates. Moreover, the γ/γ’ interfaces are highly
coherent with a lattice mismatch of the order of 10-3. The influences of the value and the sign of
the lattice misfit on the creep behaviour of these materials have been widely studied at high
temperatures. However, much less attention was paid to the role of the γ/γ’ lattice misfit in their
creep behaviour at low temperature. The aim of this paper is to analyze the creep behaviour and
the deformation mechanisms at 760°C of two fourth generation SC superalloys with different
values of γ/γ’ mismatch. Previous experiments have indeed shown that these alloys exhibit γ/γ’
mismatch values up to -4.4 x 10-3 and -14.2 x 10-3 respectively and that this parameter must be
seriously considered for interpreting their creep behaviour in the low temperature range [1].
Experimental Procedures
The MC544 and MC534 alloys are fourth generation nickel-base superalloys containing rhenium
and ruthenium additions (Table I) [2]. MC544, also known as MC-NG, is a candidate for
advanced gas turbine engine SC blades [3]. MC534 is an experimental alloy with a high level of
molybdenum aiming at increasing the γ/γ’ lattice mismatch. MC544 <001> SC rods were
provided by Snecma and MC534 <001> SC rods were directionally solidified at ONERA from a
small-scale laboratory heat. The SC rods were fully heat-treated with ageing treatments defined
171
Table I. Nominal chemistries of MC544 and MC534 superalloys (wt.%)
Alloy Ni Cr Mo Re Ru W Al Ti Ta Hf Si
MC544 Base 4 1 5 4 4 6 0,5 5 0.1 0.1
MC534 Base 4 4 5 3 4 5.8 - 6 0.1 0.1
Table II. Heat treatments applied to MC534 and MC544 superalloys (A.C.: air cooled)
Alloy Solution heat treatment Ageing heat treatment
MC544 1310°C/3h, ramp at 3°C.h-1, 1340°C/3h/A.C. 1100°C/4h/A.C. + 850°C/24h/A.C.
MC534 1315°C/3h, ramp at 3°C.h-1, 1345°C/3h/A.C. 1120°C/4h/A.C. + 850°C/24h/A.C.
to get a 310 nm γ’ particle mean size in both alloys (Table II) (Figure 1). The volume fraction of
γ’ phase is about 70% for the two alloys at room temperature and does not vary up to 760°C.
Tensile creep tests were performed in air at 760°C and 840 MPa using constant-load testing
machines. Cylindrical specimens with a gauge length of 20 mm and a gauge diameter of 3 mm
were machined from fully heat-treated SC rods. Thin foils were prepared from interrupted creep
specimens for transmission electron microscopy (TEM) analyses.
Experimental Results
Typical creep curves obtained for both alloys at 760°C and 840 MPa are compared in Figure 2.
The creep curve of MC544 exhibit a large amplitude of primary creep, about 5.9%, a high
minimum creep rate, 2.23 x 10-7s-1, and a high elongation to rupture. On the contrary, the
primary creep strain of MC534 is very limited, only 0.08%, and the minimum creep rate is much
smaller than for MC544, i.e. 0.03 x 10-7s-1. The creep rupture life of MC534 is consequently
dramatically longer than that of MC544.
Dislocation structures observed after a small deformation in the primary creep stage are
illustrated in Figure 3. In MC544, the deformation is concentrated in bands where dislocations
cut the γ’ precipitates by <112> {111} slip, therefore producing extended staking faults (SF)
bands characterised by their typical fringe contrast. The deformation is consequently
heterogeneously distributed in the material. On the other hand, the deformation is
homogeneously distributed in MC534 after a creep deformation of only 0.08%. The γ/γ’
interfaces are covered by a high density of matrix dislocations and no stacking faults are
observed within the γ’ precipitates.
(a) 1 µm
µm (b) 1 µm
Figure 1. γ’ precipitates in fully heat-treated (a) MC544 and (b) MC534 alloys.
172
30
25 MC544
20
Strain (%)
15 MC534
10
5
0
0 500 1000 1500 2000 2500
Time (h)
Figure 2. Creep curves at 760°C and 840 MPa of MC544 and MC534 <001> single crystals.
A more careful analysis of MC534 (001) thin foils evidenced numerous SF flags inclined within
the vertical γ channel (Figure 4a). TEM observations made on {111} foils also evidenced
numerous SF flags in the γ channels (Figure 4b). Moreover, strong fringe contrast is observed at
{001} γ/γ’ interfaces with fringes parallel to the precipitate edges. As reported in binary Ni-6.71
wt.% Al [4] and Udimet 700 [5], these δ-fringe patterns result from a tetragonal distortion of the
γ matrix at the γ/γ’ interface due to the lattice misfit. They must be distinguished from the fringes
associated to α-boundaries such as the SF’s produced in a f.c.c. crystal structure by glide of a/6
or a/3<112> partials. In {111} thin foils, matrix dislocations are also observed to spread laterally
in γ channels by gliding. In Figure 5, an a/2<110> dislocation propagates into different γ
channels. A striking point is the large dissociation of this dislocation when entering into the both
sides of a given channel ( and in Figure 5a). The dislocation is dissociated into two
a/6<112> partials bounding a SF characterized by its fringe contrast. It is noteworthy that this
dislocation is not largely dissociated when entering into another γ matrix channel ( in Figure
5a).
(a) (b)
g 002
0.5 µ m
Figure 3. TEM images after creep at 760°C and 840 MPa of (a) MC544 (t = 1.5 h; ε = 1.46%)
and (b) MC534 ( t = 4.6h; ε = 0.08%); foils normal to the [001] tensile stress axis.
173
(a)
g
111
g
020 200 nm (b) 200 nm
Figure 4. TEM images of MC534 after creep at 760°C and 840 MPa (t = 4.6h; ε = 0.08%): (a)
foil normal to [001]; (b) foil parallel to a {111} plane.
Figure 5. Movement of decorrelated partials in γ channels of MC534 after creep at 760°C and
840 MPa (t = 4.6h; ε = 0.08%): TEM images with two different two-beam diffraction conditions
(foil parallel to a {111} plane).
Discussion
The high creep resistance of MC534 at 760°C and 840 MPa is to be associated to the very low
primary creep amplitude, itself related to the homogeneous character of the deformation which
promotes an efficient strain hardening. This behaviour results from the confinement of the
deformation within the γ channels. On the contrary, the large primary creep extent and the
resulting poor creep resistance of MC544 is linked to the heterogeneous character of the
deformation resulting from the shearing of the γ’ particles by <112>{111} slip. Considering the
characteristics which can play a role in the mobility of the matrix dislocations, the γ/γ’ mismatch
defined as δ = 2(aγ’ – aγ)/(aγ’ + aγ), where aγ’ and aγ are the lattice parameters of the γ’ and γ
phases, is the one which differs the most between the two alloys. Lattice mismatch
measurements of fully heat-treated samples by means of high-energy X-ray diffraction have
indeed given values varying between -0.5 x 10-3 and -4.4 x 10-3 for MC544 and values up to -
14.2 x 10-3 for MC534 [1]. Variation of mismatch within a given sample is due to residual
chemical dendritic segregations. The high δ value in MC534 is due to its high content of Mo
which partitions preferentially to the matrix and thus increases significantly its lattice parameter.
174
The perfect alignment of the γ’ precipitates along <001> directions and their pronounced cubical
morphology evidence the high coherency stresses in MC534. As the volume fraction and the
size of the γ’ particles are the same for the both alloys, the γ channel widths, and therefore the
Orowan stresses, are also similar. The resistance of the γ’ precipitates against shearing is
considered being comparable in both alloys because their chemistries are similar.
The decorrelated motion of a Shockley partial with creation of an extended SF in the γ matrix
was previously observed in the MC2 first generation SC superalloy during in situ straining
experiment at 850°C along <001>, and also post mortem [6]. It has been explained by calculating
and comparing the effective forces acting on each partial of the moving dislocation by taking
into account the difference in flexibility of a perfect a/2<110> dislocation compared to an
a/6<112> partial. If the effective stress acting on an a/2<110> dislocation is not enough to
overcome the threshold stress needed to propagate it in a given γ channel, the leading partial can
move in this channel in a decorrelated manner due to its lower line flexibility. Calculations also
showed that the trailing a/6<112> partial can be stopped at the entrance of a narrow channel, as
observed in MC534 (Figure 5b), even if that causes the formation of an extended SF in the
matrix. SF’s in the matrix of SC superalloys were also reported in the fourth generation TMS-
138 superalloy after low cycle fatigue (LCF) tests at 1073K [7]. The large dissociation of the
matrix dislocations was related to the SF energy decrease caused by the partition of Re, Mo and
Ru into the matrix. The reduction of the matrix dislocation mobility thus explains the high LCF
and creep resistances of TMS-138. SF’s were also observed in the γ phase of experimental Ru-
containing γ-γ’ SC superalloys with high Co and Re contents during creep at 950°C and 290 MPa
[8]. For a given applied stress the density of SF’s increases with the Co and Re contents
indicating that these elements decrease the matrix SF energy. As the minimum creep rate
decreases as the SF density increases, it was suggested that the SF energy reduction inhibits the
climb and cross-slip creep mechanisms which control the mobility of the matrix dislocations.
The difference in creep behaviour at 760°C between MC534 and MC544 is however thought to
be mainly due to the high level of misfit stress in MC534 which adds to the external applied
stress to promote glide of matrix dislocations in the horizontal matrix channels (see in Figure 3b
the high density of dislocations at the γ/γ’ interfaces normal to [001]) [9, 10]. This intense
activity of a/2<110>{111} slip in the MC534 matrix channels as soon as the load is applied
produces dense dislocation networks at the γ/γ’ interfaces which would then act as obstacles for
other dislocations. The stress field at the γ/γ’ interfaces could also prevent matrix dislocations
from cutting the γ’ precipitates. The SF flags are mainly observed in the vertical channels of
MC534 where the misfit stress does not aid the external stress [9, 10]. Referring to [6], the stress
is certainly not sufficient to move an a/2<110> dislocation within the vertical γ channel, but
enough to propagate an a/6<112> one with a higher flexibility. If the SF energy has to be
sufficiently low to allow the decorrelation of the two partials of a perfect matrix dislocation, it is
not thought that this low SF energy is the explanation for the excellent creep resistance of
MC534. Indeed, the presence of SF’s in the γ matrix is more the hallmarks of the difficulty for
matrix dislocations to glide in the highly stressed γ channels of MC534, than a direct cause of the
low mobility of these matrix dislocations. This hypothesis agrees with the fact that no matrix SF
are observed in MC544 where the lattice mismatch is lower. In MC544 the lower misfit stress
permits the a/2<110> matrix dislocations to move in the γ vertical channel. On the other hand the
effective stress on a/2<110> dislocations in the horizontal channels is less than in MC534 and
<110>{111} slip is therefore less active in MC544. Moreover, the matrix dislocations can cut the
γ’ precipitates easily in MC544 due to the lower stress field at the γ/γ’ interfaces. Less glide
175
activity in the matrix and easier γ’ precipitates shearing in MC544 can therefore explain the
heterogeneous character of the deformation and its poor creep resistance at 760°C.
Conclusions
The excellent creep behaviour at 760°C and 840 MPa of the MC534 single crystal superalloy
compared to that of MC544 is related to its higher amplitude of γ/γ’ lattice mismatch. The
resulting coherency stress promotes spreading of the matrix dislocations in the narrow horizontal
γ matrix channels, thus leading to rapid strain hardening, and also inhibits shearing of the γ’
precipitates. The decorrelated movement of Shockley partials in the vertical matrix channels,
with creation of a number of staking faults, signs the difficulty for perfect matrix dislocations to
move between the γ’ precipitates.
References
1. F. Diologent, and P. Caron, “On the creep behaviour at 1033 K of new generation single-
crystal superalloys,” Mat. Sc. Engin., A 385 (2004), 245-257.
2. P. Caron, “High γ’ solvus new generation nickel-based superalloys for single crystal turbine
blade applications,” Superalloys 2000, ed. T.M. Pollock et al. (Warrendale, PA: TMS, 2000),
737-746.
3. D. Argence, C. Vernault, Y. Desvallées, and D. Fournier, “MC-NG, a 4th generation single-

crystal superalloy for future aeronautical turbine blades and vanes,” Superalloys 2000, ed. T.M.
Pollock et al. (Warrendale, PA: TMS, 2000), 829-837.
4. A.J. Ardell, “Diffraction contrast at planar interfaces of large coherent precipitates,” Phil.
Mag., 16 (1967), 147.
5. J.M. Oblak, and B.H. Kear, “Fringe contrast at coherent precipitate interfaces of a nickel-
base alloy,” Trans. ASM, 61 (1968), 519-527.
6. S. Raujol, M. Benyoucef, D. Locq, P. Caron, F. Pettinari, N. Clément, and A. Coujou,

“Decorrelated movements of Shockley partial dislocations in the gamma phase channels of
nickel-based superalloys at intermediate temperature,” Phil. Mag., 9 (21) (2006), 1189-1200.
7. H. Zhou, Y. Ro, H. Harada, Y. Aoki, and M. Arai, “Deformation microstructures after low-
cycle fatigue in a fourth-generation Ni-base SC superalloy TMS-138,” Mat. Sc. Engin., A 381
(2004), 20-27.
8. S. Ma, L. Caroll, and T.M. Pollock, “Development of γ phase stacking faults during high
temperature creep of Ru-containing single crystal superalloys,” Acta Mater., 55 (2007), 5802-
5812.
9. U. Glatzel, and M. Feller-Kniepmeier, “Calculations of internal stresses in the γ/γ’

microstructure of a nickel-base superalloy with high volume fraction of γ’ phase,” Scripta Met.,
23 (1989), 1839-1844.
10. L. Zhou, S.X. Li, C.R. Chen, Y.C. Wang, Q.S. Zang, and K. Lu, “Finite element analysis of
γ' directional coarsening in Ni-based superalloys,” Z. Metallkd., 93 (4) (2002), 315-321.
176
OXIDATION BEHAVIOR OF Mo-Si-B ALLOYS PRODUCED BY

REACTION SYNTHESIS
Michael R. Middlemas1, Joe K. Cochran1
1
Georgia Institute of Technology;
771 Ferst Dr. NW; Atlanta, GA 30332-0245, USA
Keywords: Mo-Si-B Alloys, Nitride Reactions, Oxidation, Powder Processing
Abstract
The oxidation behavior of Mo-Si-B alloys produced from the reaction of molybdenum, Si3N4 and
BN powders has been investigated. This powder metallurgy processing method yields finer
grained microstructures than is achieved from melt processing. Mo-3Si-1B (wt%) compositions,
which lie in the phase field consisting of bcc-Mo and the intermetallics Mo3Si and Mo5SiB2,
were studied. During oxidation, Mo-Si-B alloys undergo an initial period of high weight loss
due to evaporation of MoO3, followed by parabolic oxidation kinetics due to the formation of a
protective borosilicate layer. The formation of borosilicate glass layers was examined under a
reduced PO2. Oxidation resistance in air was examined at 1100°C. The small spacing of the
intermetallic phases significantly reduces the transient weight loss during the initial stages of
oxidation. Using powder metallurgy processing allows the addition of aluminum to the alloy.
The effect of aluminum additions on oxidation resistance was also examined.
Introduction
Current jet engines operate near the temperature limits of the nickel superalloy turbine blades.
The desire for higher jet engine performance and efficiency has created a need for new, higher
temperature alloys. An alloy system which has gained much attention is the Mo-Si-B ternary.
These alloys hold the potential for use in the next generation of jet engines due to their high
temperature mechanical properties and oxidation resistance [1]. Intermetallics of molybdenum,
silicon and boron are known to have excellent oxidation resistance but are too brittle for use in
the high stress environment of turbine engines. Investigations are being performed in the region
of the phase diagram highlighted in Figure 1, consisting of bcc-Mo, Mo3Si (A15) and Mo5SiB2
(T2), where the high temperature fracture toughness is improved by the presence of the ductile
molybdenum phase [2].
0.4 b)
a) MoB 0.6
0.5 0.5
Mo2B
0.6 0.4
X Mo XB
0.7 0.3
T2
0.8 0.2
0.9 0.1
1.0 0.0
0.0 0.1 0.2 0.3 0.4 0.5 0.6
Mo(ss) A15
X Si Mo5Si3
Figure 1. Isothermal section of the Mo-Si-B phase diagram at 1600°C [1].
177
Molybdenum silicides are known for excellent oxidation resistance due to the formation of a
protective silicate scale. In Mo-Si-B alloys, boron lowers the viscosity of the glass sufficiently
to cause flow over the molybdenum regions. During oxidation, the samples undergo a transient
weight loss during the formation of the glass, followed by parabolic oxidation kinetics. At low
temperatures (700-800°C), the borosilicate glass has a low viscosity allowing oxygen to diffuse
inward and MoO3 gas to bubble out. As the temperature increases, the oxygen permittivity of the
glass decreases due to B2O3 evaporation. In this work, the oxidation resistance of a Mo-3Si-1B
(wt%) alloy is examined at 1100°C. To limit the transient weight loss and improve oxidation
resistance, a pre-oxidation treatment in a reduced oxygen environment was developed.
Processing of Mo-Si-B alloys involving melt processing or consolidation of pre-alloyed powders
yields coarse grained microstructures with isolated regions of molybdenum in an intermetallic
matrix [3,4]. For suitable mechanical properties, a continuous molybdenum matrix is required.
To form a continuous, passivating surface layer, a fine dispersion of intermetallic particles is also
required. Unlike other alloys, Mo-Si-B alloys do not lend themselves to microstructural
improvement by heat treating. The compositional homogeneity of the three-phase region
extends over a wide temperature range, eliminating the opportunity to reform the microstructure
via phase transformations. The system has been likened to a ceramic, in that “the initial
synthesis methods largely dictate the final microstructure” [1]. In a powder metallurgy process
developed at Georgia Tech, the reaction between molybdenum, Si3N4 and BN are used to create
Mo-Si-B alloys [5]. The nitrides are stable in oxidizing environment up to 1000ºC, allowing for
processing without formation of silicon and boron oxides. At high temperatures the nitrides have
high equilibrium nitrogen partial pressures and small free energies that promote the formation of
A15 and T2. The resulting microstructures have a fine dispersion of the intermetallic phases in a
continuous molybdenum matrix.
The addition of aluminum to Mo-Si-B alloys could improve oxidation resistance by forming of
an Al2O3 surface layer and decreasing oxygen diffusivity in the borosilicate glass. Mo-Si-B
alloys treated by aluminum pack cementation show near zero mass change when exposed to air
for 50h at temperatures from 732°C -1372°C [6]. Pack cementation only creates a surface
concentration of aluminum, which diffuses inward over time. It would be preferable to have
aluminum distributed throughout the alloy but the addition of aluminum by melt processing
routes is difficult due to the volatility of aluminum at the melting point of Mo-Si-B alloys. Past
attempts to add aluminum to Mo-Si-B alloys by powder processing resulted in the formation of
Al2O3 inclusions, rather than incorporation into the alloy. In this work, by careful controlling the
processing and firing conditions, the formation Mo-Al-Si-B alloys has been accomplished.
Experimental
The raw materials used are listed in
178
Table I. The powders were mixed in acetone with a low molecular weight polymethyl
methacrylate (~10,000) as a dispersant and binder (PMMA 2008, Ineos Acrylics) and stearic acid
as a lubricant. Milling on a high-energy shaker with Al2O3 media was used to break up
agglomerates and improve dispersion. The slurries were spray dried to maintain a uniform
distribution of the nitrides. Powder compacts were pressed in a ½” die. Samples were fired in a
tube furnace with a reducing atmosphere of Ar-10% H2 to reduce surface oxidation on the
molybdenum. Oxygen impurities were removed from the inlet gas by a gettering furnace.
Samples were heated at 3°C/min to 1600°C with a 6h hold.
179
Table I. Properties of raw material powders.
Surface Area Oxygen
Raw Material Grade Purity Particle Size
(m2/g) Content
Mo (Climax) Ultrafine 99.95% 100-500 nm 3.3 0.8 wt%
Si3N4 (UBE) SN-E03 99% ~0.5 μm (APS) 4 0.82 wt%
BN (Cerac) B-1084 99.5% 0.73 μm (APS) 6.7 N/A
Al (Amer. Elements) Al-M-03 99.9% 1-3 μm (APS) N/A N/A
A Mo-3Al-1Si-1B (wt%) alloy was prepared by mixing Mo, Al, Si3N4 and BN powders using a
mortar and pestle. The mixture was pressed into compacts and fired in Ar-10% H2. Spray
drying was avoided to prevent the formation of Al2O3. Reaction between the molybdenum and
aluminum at 600°C causes a large volume expansion, reducing the densities of the pellets. A
sample prepared by this method was used for oxidation testing. In later experiments the
molybdenum and aluminum powders were pre-reacted at 900°C for 2 hours, creating a Mo-
Mo3Al mixture which was dry ball milled with the Si3N4 and BN powders. Samples fired at
1600°C-6h yielded a combination of Mo, A15 and T2 with aluminum in solution. No Al2O3 was
detected using XRD.
The XRD analysis program Jade was used for phase identification. Quantitative XRD phase
analysis was used to determine the phase volume fractions, using the Rietveld analysis program
MAUD. SEM analysis was performed on a LEO 1550 FE electron microscope. Further
microstructure examination was done using a combination of electron-backscatter diffraction
(EBSD) and EDS mapping, performed by EBSD Analytical (Lehi, UT). The EBSD analysis was
used to determine the particle size distributions of the three phases in the Mo-3Si-1B sample and
also to verify their volume fractions. Elemental analysis was provided by Dirats Laboratories
(Westfield, MA).
Oxidation resistance requires that a continuous surface glass be formed. Pre-oxidation of a Mo-
3Si-1B sample was used to create a protective glass layer while minimizing the transient weigh
loss. Samples were pre-oxidized in an Ar-0.1% O2 mixture at 1300°C for 3 hours. Isothermal
oxidation tests were conducted in a box furnace and the samples were removed at periodic
intervals for weighing.
Results
An EBSD map is shown in Figure 2a for a Mo-3Si-1B sample fired at 1600°C for 6 hours.
There is a fine dispersion of intermetallics in a continuous molybdenum matrix. The grain size
distributions of the individual phases are shown in Figure 2b. The density is 8.72g/cc which
corresponds to 91.4% dense, assuming a T.D. of 9.54 g/cc. Oxygen and carbon impurity
contents were measured at 0.04% O2 and 0.004% C. The volume fractions of the phases were
determined by the Rietveld method and from the EBSD analysis. They are compared to those
estimated from the phase diagram for a Mo-3Si-1B alloy in Table II. The values from the
different measurement techniques are within 3% of each other. Rietveld analysis for the Mo-
3Al-1Si-1B gives phase fractions of 72.5vol% Mo and 27.5vol% T2.
180
Molybdenum
Mo5SiB2 1
Mo3Si
0.8
Area Fraction
0.6
0.4
Mo
0.2 A15
T2
0
0 2 4 6 8 10 12
Grain Diameter (μm)
Figure 2. (a) EBSD map of the Mo-3Si-1B (wt%) alloy and (b) Cumulative particle size distributions of
the Mo, A15 and T2 phases.
TABLE II. Measured Phase Volumes by Percentage for the Mo-3Si-1B (wt%) Alloy.
Estimated Rietveld EBSD
Mo 56.8 55.9 57.5
A15 16.0 17.9 18.3
T2 27.2 26.2 24.2
Isothermal oxidation tests were conducted at 1100°C for untreated and pre-oxidized Mo-3Si-1B
samples, and a Mo-3Al-1Si-1B sample. Figure 3 plots the weight change per unit area as a
function of time. The transient weight loss is low due to the close spacing of the intermetallic
particles. The pre-oxidation treatment greatly improves oxidation resistance, reducing the mass
loss to 22μg/cm2*h as compared to a loss of 350μg/cm2*h for the untreated sample. The Mo-Al-
Si-B sample has a higher initial weight loss than the untreated Mo-Si-B sample due to higher a
porosity, but a lower steady state mass loss rate (140μg/cm2*h). Porosity hinders the formation
of a continuous glass layer. In the future, work will focus on achieving fully dense samples to
improve oxidation resistance.
0 5 10 15 20 25 30
0
-10
Weight Change (mg/cm )
2
-20
-30
-40
Mo-3Si-1B
-50
-60 Mo-3Si-1B -
Pre-Oxidized
-70 Mo-3Al-1Si-1B
-80
Time (hours)
Figure 3. Comparison of samples oxidized in air at 1100°C.
181
SEM micrographs in Figure 4 compare the cross-sections of the oxidized surfaces of the
untreated Mo-Si-B and the pre-oxidized sample before and after further oxidation.
(a) (b) (c)
Figure 4. Cross-sections of oxidized Mo-3Si-1B samples: (a) Untreated sample oxidized in air for 9h, and
a pre-oxidized sample (b) before and (c) after oxidation in air for 30h.
For the untreated sample, a continuous glass layer up to 25μm thick has formed after 9h in air.
The pre-oxidation treatment forms a glass layer with an average thickness of 8μm. Beneath this
is a mixed layer of molybdenum and borosilicate glass that forms as oxygen diffused through the
glass reacts preferentially with silicon and boron. The pockets of glass form where the
intermetallic regions once were. The specific volume increase resulting from oxidation of the
intermetallics to form borosilicate glass causes the glass to be forced to the surface and provides
a mechanism for the surface oxide layer to thicken. After 30h in air at 1100°C, there is little
change in the surface of the pre-oxidized sample.
Conclusions
The formation of Mo-Mo3Si-Mo5SiB2 alloys from the nitride reactants provides a method for
creating Mo-Si-B alloys in a much less complex and expensive manner than has been previously
demonstrated. The combination of closely spaced intermetallics and a continuous molybdenum
matrix is likely to lead to a mixture of good mechanical properties and oxidation resistance.
Isothermal oxidation tests of the Mo-3Si-1B alloy show that after the formation of a continuous
glass layer, isothermal oxidation rates as low as 22μg/cm2*h can be achieved. This powder
metallurgy method also allows for the addition of aluminum to the alloy. Future work will focus
on improving the dispersion of the intermetallic phases and using hot-isostatic pressing to
achieve full density.
Acknowledgments
This work is funded by ONR under a NAVAIR Grant monitored by Dave Shifler and Robert
Kowalik. Advice was provided by Doug Berzcik of Pratt & Whitney.
182
References
1. J.H. Perepezko and D.M. Dimiduk, “Mo-Si-B alloys: Developing a Revolutionary Turbine-
Engine Material”, MRS Bulletin, 28 (9) (2003), 639-645.
2. J.J. Kruzic, J.H. Schneibel, and R.O. Ritchie, “Fracture and Fatigue Resistance of Mo-Si-B
Alloys for Ultrahigh-Temperature Structural Applications,” Scripta Materialia, 50 (2004),
459-464.
3. C.A. Nunes et al., “Liquidus Projection for the Mo-rich Portion of the Mo-Si-B Ternary
System,” Intermetallics, 8 (4) (2000), 327-337.
4. P. Jéhanno et al., “Assessment of a Powder Met. Processing Route for Refractory Metal
Silicide Alloys,” Met. and Mat. Transactions, 36A (3) (2005) 515-523.
5. M. R. Middlemas, J.K. Cochran, “ A Nitride Based Reaction for the Formation of a Three-
Phase Mo-Si-B Alloy,” (Paper presented at the TMS Annual Meeting, Orlando, Florida, 1
March 2006).
6. R. Sakidja, F. Rioult, J. Werner, and J.H. Perepezko, “Aluminum pack cementation of Mo–
Si–B alloys,” Scripta Materialia, 55 (2006), 903–906.
183
PILE-UP/SINK-IN IN NANOINDENTATION RATE SENSITIVE

CREEPING SOLIDS
A.A. Elmustafa
Dept. of Mechanical Engineering
Old Dominion University and The Applied Research Center
238 Kaufman Hall, Norfolk, VA 23529
Keywords: Nanoindentation, Pile-up, ABAQUS, Creep
Abstract
The measurement of the hardness is influenced by an accurate account of the contact area of
indentation particularly in nanoindentation when the indents become significantly small. In order
to determine accurately the contact area, formations of pile-ups and sink-ins must be accounted
for. In this paper, we use the commercial finite element code ABAQUS to study the effect of
strain rate, work hardening, and creeping time on pile-ups and sink-ins of creeping solids during
the indentation process. We simulate materials of variable hardness, work hardening
exponent, χ = ∂ ln σ / ∂ ln ε of 0.1-0.3 and a strain rate sensitivity of von Mises stress,
ν σ = ∂ ln σ / ∂ ln ε of 0.08-0.16 to estimate pile-ups and sink-ins during indentation creep and
compare the results with literature data. We report that materials pile-up for ν H /ν σ ≥ 1.0 and
sink-in for ν H /ν σ < 1.0 , ν H , is the strain rate sensitivity of the hardness. This is consistent with
the fact that ν H /ν σ approaches 1 for small H / E * , i.e., soft materials and deformation is
intimately dominated by pile-up. On the other hand when ν H /ν σ approaches 0 for large H / E * it
corresponds to purely elastic deformation and is apparently dominated by sink-in in a manner
prescribed by Herizian contact mechanics.
Introduction
Mechanical properties at the nanoscale are important in microscopic systems such as
tribological coatings, microelectronic interconnects, and micro-electro-mechanical-systems
(MEMS). It is now possible to customarily measure the hardness, Young’s modulus, and strain
rate sensitivity parameter for very small volumes of material. To engineers, the yield stress is an
important parameter in structural design. Scientists consider the flow stress an essential
parameter in the study of flow (plastic) properties of crystalline materials. Nanoindentation
hardness has become an integral tool to test metallization in electronic packaging, delamination
in Al-Li alloys, measure of wear and surface properties, and to determine the mechanical
properties nanophase materials.
The contact area resulting from an indentation penetration is measured using surface
visualization techniques such as optical and scanning microscopy. The contact area is influenced
by the formation of pile-ups and sink-ins during the indentation process. To accurately measure
the indentation contact area, pile-ups/sinks-ins should be appropriately accounted for. The
contact area addressed in this research is resulting from a nanoindentation creep experiments.
Creep within a specimen occurs during the hold time of the loading phase of nanoindentation
testing and manifests itself as a change of indentation depth with the force kept constant. It is
postulated that the stress fields in the material underneath the indenter develop a chemical
potential gradient that leads to a thermally activated diffusional flux of atoms moving from
below the indenter to the surface and along the interface between the indenter and the specimen,
even under an elastic contact (Pelletier, Krier et al. 2000). The presence of creep during
185
nanoindentation has an effect on pile-up, which results in incorrect measurement of the material
properties. It is reported in the literature that when pile-ups/sink-ins are not accounted for, the
elastic modulus is much less than anticipated (Fischer-Cripps 2004). Rar, Sohn et al. 2005
observed that the same material when allowed to creep for a long duration produced a higher
value of pile-up/sink-in indicating a switch from an initial elastic sink-in to a plastic pile-up. This
is contrary to what we observe here in this research for rate sensitive solids, we notice that
creeping time has no impact on the pile-up/sink-in of rate sensitive materials.
It is generally difficult to account accurately for the contact area between the indenter tip
and the material surface. While the shape of the indenter (conical, spherical, asymmetric cross-
sections, etc.) can make a universal equation difficult to produce without correction factors, it is
the pile-up and sink-in of the material that makes the procedure most difficult. This is because
the contact area may be increasing or decreasing due to material movement, and it is
unaccounted for in the equations. This change in contact area can yield inaccurate material
properties that might be inaccurate by as much as 60 percent Fischer-Cripps 2004.
In an indentation creep experiments, the hardness, H and the Young’s Modulus, E, of the
material are given by
H = P / A, (1)
and
πS
E* = , (2)
2 A
where P is the indentation load, A is the projected contact area and S is the contact stiffness
obtained from the elastic loading curve. E * is the indentation effective modulus and is given by
the plane-strain modulus for isotropic materials as:
E
E* = , (3)
1 −ν 2
The contact area for a conical indenter is given by:
A = π a 2 = π (tan θ ) 2 hC2 , (4)
where a is the contact radius, θ is the indenter angle and hC is the contact indentation depth,
which is given by:
hC = h + hP (5)
where h is the indentation depth with reference to the original surface and hP is the pile-up
height (or sink-in depth, if it is negative).
The purpose of the present work is to explore, using FEM, the relationship between pile-
up/sink-in and the fundamental properties of rate sensitive materials such as the effective
modulus, hardness, rate sensitivity, and the work hardening in nanoindentation creep for a wide
range of soft to hard materials. Rate insensitive constitutive relations were used to study pile-
ups/sink-ins during indentation Taljat and Pharr 2004, Tang and Ngan 2003, Feng and Ngan
2001, Mesarovic and Fleck 1999, and Cheng and Cheng 1998.
Numerical Model
The model of the indentation creep simulations consists of a deformable half-space
indented with a rigid conical indenter with with a semi angle of 67.5o at the apex. The sample is
modeled as an axisymmetric elastic-plastic von Mises material. The axisymmetric CAX4H
elements were used to model the semi-infinite medium. These elements are four-node bilinear,
hybrid with constant pressure and are used to model axisymmetric problems which do not
involve a twisting moment. Contact between the rigid conical indenter tip and the axisymmetric
186
quadrilateral specimen is modeled using a hard contact formulation and the interaction between
the contact pair is assumed frictionless, Figure 1. Two programs, GENMESH2D and
GENMPC2D, were used, to generate the mesh and to write the multi-point constraints (MPCs).
These programs, GENMESH2D and GENMPC2D, made it possible to systematically refine the
mesh. The boundary conditions used to define the problem are shown in Figure 2. Only vertical
movement of material is allowed along the symmetry axis. The bottom surface of the sample is
permitted movement only in the horizontal direction and the top and side surfaces do not have
any constraints specified on them. Another code, GETPILEUP, was written to calculate
maximum pile/sink-in height, pileup/sink-in area, and average pileup-sink-in height. The
indentation process was simulated in four different steps: in the first step, contact between the tip
and the sample was established. In the second step, the indenter was pushed into the sample 1-
3 μm depending on the convergence of the particular model, then the indentation load was
maintained constant and the sample was allowed to creep for 3, 9, and 17 seconds respectively,
and finally the indenter was withdrawn from the sample, allowing the material to relax.
Figure 1 Finite element model for indentation
Simulation of the entire process was performed using an elastoplastic constitutive law
available in ABAQUS finite element code. The contact between the indenter and the sample was
modeled as frictionless with slip tolerance of 0.005. The material was treated as homogenous,
isotropic and having properties that are scale-independent so that there was no indentation size
effect. Since the stress state changes during the analysis, the power-law creep model shown in
Equation 6 was used as the constitutive law for the finite element simulation. Although, the
range of applications using this model is limited, it is a viable option to use this model because of
the low stresses involved and its simplicity.
1
ε cr = (κσ n [(m + 1)ε cr ] m ) m +1 , (6)

where ε cr is the equivalent creep strain
2 cr cr
ε cr is the uniaxial equivalent creep strain rate ε : ε
3
σ is the uniaxial equivalent deviatoric stress
κ , m and n are material constants with -1 < m ≤ 0.
187
The values of m and n are related through the strain rate sensitivity of flow stress, ν σ and the
work hardening exponent, χ as,
m +1
νσ = , (7)
n
and
∂ ln σ m
χ= =− , (8)
∂ ln ε n
respectively.
In this case, the values of ν σ and χ are varied between 0.08-0.16 and 0.1-0.3 respectively.
m and n were determined according to Equations 7 and 8. Along with m and n , the values of
the constant, κ , the strain hardening coefficient (Aghaie-Khafri and Mahmudi 1998) were varied
to obtain different material properties (i.e., hardness values). The values of κ used in this
simulation range between 1.6 × 10 −15 and 1.6 × 10 3 GPa − n sec − (1+ m ) . E was assumed 100 GPa and
Poisson’s ratio, ν was kept constant at 0.3, as Mesarovic and Fleck 1999 demonstrated that
changing ν has little or no effect on the material properties under static indentation.
Pile-ups and sink-ins are measured as the ratio hC / h , where hC is the depth of indentation of
the deformed surface and h is the depth to the original surface as given by Equation 5. The
contact depth hC is a function of the Young’s modulus, E , Poisson’s ration, ν , yield stress, Y ,
work hardening exponent, n , depth of the indentation, h , and the angle of the cone, θ (Cheng
and Cheng 1998). hC / h is a dimensionless quantity and is a function of H / E * , ν σ , and χ .
The ratio hC / h is greater than one in the case of surface pile-ups and less than one when the
surface suffers sink-in. To test the effect of creeping time on the amount of pile-up/sink-in, two
materials, a soft one represented by
n = 2.17, m = −0.652,ν σ = 0.16, χ = 0.3, k = 1.6 × 10 −8 GPa −2.17 s −0.348 and a hard one represented by
n = 5.56, m = −0.556,ν σ = 0.08, χ = 0.1, k = 1.6 × 10 −7 GPa −5.56 s −0.444 were simulated. Both materials were
allowed to creep for 3, 9, and 17 seconds respectively. Figure 2 shows Hardness vs. strain rate
sensitivity of the hardness for the soft and hard materials generated during creep of step 3. In
order to plot the two sets of data together, the hardness of the softer material has been multiplied
by 10. It can be seen from Figures 2 that the slopes of the curves remain (i.e., hardness vs. ν H )
unchanged for different creeping times and the normalized pile-up/sink-in height hC / h is not
affected by creeping time, Figure 3.
188
n m νσ χ
5.56 -0.556 0.08 0.1
100
Hardness (GPa)
101 3 s hold time

9 s hold time
17 s hold time
H 10 3 s hold time
9 s hold time
17 s hold time 5.56 -0.556 0.08 0.1
10-1
νσ χ
hC/h
n m
2.17 -0.652 0.16 0.3
-2
10
n m νσ χ
2.17 -0.652 0.16 0.3
100
-3 -2 -1 0 1 10-3
10 10 10 10 10 100 101 102
ε H (s )
-1
Creeping time (s)
Figure 2 Hardness versus strain rate sensitivity Figure 3 Effect of creeping time on
of the hardness. normalized pile-up/sink-in height.
1.4
End of creep
1.2 1.1
1.0 1.0
n m χ νσ
5.56 -0.556 0.1 0.08
0.8 0.9 2.78 -0.556 0.2 0.16
hc/h
hc/h
2.63 -0.789 0.3 0.08

2.17 -0.652 0.3 0.16
0.6
n m χ νσ 0.8
5.56 -0.556 0.1 0.08
0.4 2.78 -0.556 0.2 0.16
2.63 -0.789 0.3 0.08
2.17 -0.652 0.3 0.16 0.7
0.2
0.6
0.0
10-3 10-2 10-1 0.0 0.2 0.4 0.6 0.8 1.0
H/E* νH/νσ
Figure 7 Normalized pile-up/sink-in height for Figure 8 Normalized pile-up/sink-in height
elastic, plastic, and elastic-plastic solids. for rate sensitive materials.
The normalized pile-up/sink-in height hC / h at the end of creep is plotted versus the normalized
hardness H / E * in Figure 4. It is observed that materials with high H / E * , i.e., hard materials
undergo sink-in whereas materials pile-up for low H / E * , i.e., soft materials. In general it is
also observed that in the case when H / E * is high (hard materials), materials undergo sink-ins
regardless of work hardening and strain rate sensitivity and all materials collapse to a single
curve, Figure 4. In addition, for materials with low H / E * , soft materials, pile-up depends on the
degree of work hardening. Softer materials, i.e., low H / E * , possess a plastic zone, which is
hemispherical in shape and meet the surface well outside the radius of the circle of contact and
pile-up is expected in these materials. On the other hand, for materials with high values of
H / E * , i.e. harder materials, the plastic zone is contained within the boundary of the circle of
contact and the elastic deformations that accommodate the volume of indentation are spread at a
greater distance from the indenter. Higher stresses are expected in high H / E * , hard materials,
and high stress concentrations develop towards the indenter tip, whereas in case of low H / E * ,
189
soft materials, the stresses are lower and are distributed more evenly across the cross-section of
the material (Fischer-Cripps 2004). Rate sensitive materials experience less pile-up compared to
rate insensitive materials due strain hardening. Cheng and Cheng 1998 reported a 22% pile-up
for a work hardening exponent, χ = 0.1 and only sink-in was detected when the work hardening
exponent reached χ = 0.5 . Rate sensitive materials undergo a 15% pile-up when the work
hardening exponent increased from χ = 0.1 to χ = 0.3 . For rate sensitive materials, it is evident
from Figure 7 that all data collapse to a single value of hC / h when H / E * becomes large, i.e.,
materials become purely elastic and hence undergo sink-in. Similar results were observed for
other work hardening exponents as depicted by Figure 7. Previously Elmustafa, Kose et al. 2007
employed finite element simulations to illustrate the relationship between the strain rate
sensitivity of the hardness, ν H and the strain rate sensitivity of the flow stress,ν σ . It was found
that the ratio ν H /ν σ depends on H / E * ; it decreases from 1 at low hardness to 0 at high
hardness and is insensitive to other parameters including ν σ (0.04<ν σ <0.2) and the work
hardening exponent, χ (0< χ <0.1). To examine the effect of the strain rate sensitivity,ν σ on pile-
up/sink-in, we plot the normalized pile-up/sink-in height hC / h versus the ratioν H /ν σ , Figure 8.
Materials pile-up with the increase of the ratio ν H /ν σ , i.e., soft materials while hard materials
sink-in when ν H /ν σ decreases significantly. Materials pile-up for ν H /ν σ ≥ 1.0 and sink-in for
ν H /ν σ < 1.0 . This is consistent with the fact that ν H /ν σ approaches 1 for small H / E * , i.e.,
soft materials and deformation is intimately dominated by pile-up (Hill, Storakers et al. 1989;
Biwa and Storakers 1995). On the other hand when ν H /ν σ approaches 0 for large H / E * it
corresponds to purely elastic deformation and is apparently dominated by sink-in in a manner
prescribed by Herizian contact mechanics (Hertz 1896).
Conclusion
A finite element based simulation was used to study the effect of pile-up/sink-in during
indentation creep. Materials with high H / E * , i.e., purely elastic endure sink-ins whereas
materials with low H / E * , i.e., elastic/plastic experience pile-up/sink-ins and the fully plastic
materials undergo pile-ups. Rate sensitive solids experience pile-ups when the ratio ν H /ν σ ≥ 1.0
and sink-in when the ratio ν H /ν σ < 1.0 . Changing the strain rate sensitivity has little impact on
the magnitude of pile-ups/sink-ins for a work hardening exponent, χ = 0 of material with high
H / E * , i.e., purely elastic solids.
References
1. Aghaie-Khafri, M. and R. Mahmudi (1998). "Flow localization and plastic instability during
the tensile deformation of Al alloy sheet." JOM 50(11): 50-2.
2. Biwa, S. and B. Storakers (1995). "Analysis of fully plastic Brinell indentation." Journal of
the Mechanics and Physics of Solids 43(8): 1303.
3. Cheng, Y.-T. and C.-M. Cheng (1998). "Effects of `sinking in' and `piling up' on estimating
the contact area under load in indentation." Philosophical Magazine Letters 78(2): 115-120.
4. Cheng, Y. T. and C. M. Cheng (1998). Scaling relationships in conical indentation in elastic-
plastic solids with work-hardening, San Francisco, CA, USA, Mater. Res. Soc.
5. Elmustafa, A. A., S. Kose, et al. (2007). "The strain-rate sensitivity of the hardness in
indentation creep." Journal of Materials Research 22(4): 926-936.
190
6. Feng, G. and A. H. W. Ngan (2001). "Creep and strain burst in indium and aluminium during
nanoindentation." Scripta Materialia 45(8): 971-976.
7. Fischer-Cripps, A. C. (2004). "A simple phenomenological approach to nanoindentation
creep." Materials Science & Engineering A (Structural Materials: Properties,
Microstructure and Processing) A385(1-2): 74-82.
8. Hertz, H. (1896). "Miscellaneous Papers by H. Hertz." Macmillan
9. Hill, R., B. Storakers, et al. (1989). "A theoretical study of the Brinell hardness test."
Proceedings of the Royal Society of London, Series A (Mathematical and Physical Sciences)
423(1865): 301-30.
10. Mesarovic, S. D. and N. A. Fleck (1999). "Spherical indentation of elastic-plastic solids."
Proceedings of the Royal Society of London, Series A (Mathematical, Physical and
Engineering Sciences) 455(1987): 2707-28.
11. Pelletier, H., J. Krier, et al. (2000). "Limits of using bilinear stress-strain curve for finite
element modeling of nanoindentation response on bulk materials." Thin Solid Films 379(1-
2): 147-55.
12. Rar, A., S. Sohn, et al. (2005). On the measurement of creep by nanoindentation with
continuous stiffness techniques, Boston, MA, USA, Materials Research Society.
13. Taljat, B. and G. M. Pharr (2004). "Development of pile-up during spherical indentation of
elastic-plastic solids." International Journal of Solids and Structures 41(14): 3891-904.
14. Tang, B. and A. H. W. Ngan (2003). "Accurate measurement of tip - Sample contact size
during nanoindentation of viscoelastic materials." Journal of Materials Research 18(5): 1141-
1148.
191
RESEARCHES CONCERNING THE STRUCTURAL

CHARACTERIZATION OF HYBRID COMPOSITE MATERIALS
Petru Moldovan1, Gabriela Popescu1, Cristian Popescu1, Brandusa Ghiban1
1
University “POLITEHNICA” of Bucharest, Romania
Keywords: Hybrid Composites, Aluminum Alloy Matrices, SiC and Al2O3 Reinforcements
Abstract
The paper aim is to present the processing and characterization of hybrid composite materials.
The hybrid composites were realized using aluminum alloys as matrices and silicon carbide and
aluminum oxide particles as reinforcements. The ceramic particles used in composite materials
had different rates in case of SiC (5, 10 and respectively 15%) and was constant in case of Al2O3
(3%).
Were analyzed the processes that take place at the interface between matrix and reinforcements,
as well as the wetability of ceramic particles by the melt.
Structural analyses of hybrid composites were realized using optical and electron microscopy.
The matrix nature and compounds have been investigated using an electron-probe microanalyzer
and EDS analysis.
Introduction
Aluminum based composites are good promise for transport industry, successfully replacing a
series of ferrous and nonferrous alloys. The composite materials have an improved mechanical
resistance in comparison with unreinforced materials.
Studying the specialty literature we can remark that the researches regarding processing and
characterization of hybrid composite materials, with special application in automotive industry,
are only a few. This is due to the difficulty of their production. Considering this point of view
was chose an aluminum based alloy as matrix for processing hybrid composites. The reason for
chose this alloy was that: is one of the most used alloys in automotive industry with success, has
high resistance at high temperatures, good fluidity, high dimensional stability and can be treated
by heating in order to improve mechanical characteristics.
Obtaining of composite materials with aluminum based matrix reinforced with ceramic particles,
as well as physical-mechanical and tribological properties are dependent on the solidification
phenomena, especially by those at the interfaces, which are inherent and sometimes lead to
macro- and microstructural defects. The interface phenomena have taken the attention by a
numerous number of researchers1-7 which throws out often contradictory opinions. The processes
which take place at the interfaces are based on the physical, chemical or physical-chemical
phenomena. The wetting of reinforcements (solid ceramic particles) by the liquid metallic matrix
has an important role in forming of the bond between matrix and ceramic particles. This depends
strongly by combining heat, electronic structure and crystallography of the reinforced particles.
The aim of the paper is to put in evidence the nature of the interfaces between ceramic reinforced
particles and aluminum matrix in case of some hybrid composite materials with aluminum alloy
matrix (AlSi12CuNiMg) reinforced with SiC and Al2O3. At the processing temperature of
composite materials the SiC particles are weak wet by the metallic aluminum matrix. The
addition of Al2O3 particles improves the wetability in liquid state through forming of interfaces
with small wetting angle (θ < 900C). This was the reason of chosen alumina and silicon carbide
as reinforcements for processing of hybrid composites. Structural analysis of the hybrid
composites offer important observations concerning the solidification phenomena, especially at
193
the interface, which have a special influence on the mechanical and tribological properties of
these materials.
Materials and Experimental procedure
For processing of hybrid composite materials was used a complex device composed from an
electric furnace with Kanthal resistance and graphite crucible, mechanical stirring of the melt
mixture and a powder particles rotated injector.
As raw materials for processing of hybrid composites were used AlSi12CuNiMg alloy as matrix
(table 1) and silicon carbide, with 10 to 100 μm size, and alumina, with ~10μm size as
reinforcement’s. The reinforcement volume fraction used in experiments was 5, 10 and
respectively 15 wt.% in case of SiC particles and 3wt.% for Al2O3 particles. Alumina and silicon
carbide particles were homogenized in a ball mill and preheated before their adding into the
melt8. At the same time with ceramic particles injection in the melt were add, in small portions,
0.5% Mg, which has the role to reduce the wetting angle without to decrease the magnesium
content from the alloy matrix.
The obtained hybrid composites are presented in table 2.
Table I: Chemical composition of the matrix
Chemical composition, wt.%
Matrix Si Cu Mn Mg Fe Ni Ti Al
AlSi12CuNiMg 11,85 0,81 0,02 0,40 0,20 0,85 0,025 balance
(M0)
Table II: Chemical composition of the

hybrid composites
Hybrid composite material Symbol
AlSi12CuNiMg/5%SiC/3%Al2O3 M1
Processing of hybrid composites in open furnaces can lead to formation of a dense and compact
aluminum oxide film at the melt surface. This film can be an obstacle for ceramic particles
movment in the melt. For this reason the processing atmosphere was an inert one.
The structural analyses were realized on a metallographic microscope, electron microscope and
electron-probe microanalyzer.
Experimental results and Discussions
Metallographic analysis of the experimental composites may reveal a microstructure formed by
aluminum based α solid solution, with laced eutectic (α solid solution + Si), interdendritic
precipitates (light colored nickel compounds and dark colored manganese and iron compounds)
as we can see in figure 1.
The main compounds which may appear at the equilibrium in AlSi12CuNiMg alloy are:
(FeMn)3Si2Al15, Mg2Si, Cu2Mg8Si6Al5, (CuNi)2FeAl7, Cu4NiAl7. The images capture different
structural features in different fields. In such matrix the interfaces are simple both, among
particles and matrix, and among eutectic and matrix.
194
Fig.1. Structural aspect of the AlSi12CuNiMg matrix alloy
The nature of the matrix and compounds was investigated through analysis at electron
microanalyzer. The obtained results are presented in figures 2 and 3.
Electron microsonde analysis may reveal in the alloy matrix a dendritic structure (compo image
in fig.2), with microporosities and a separation compounds of the alloying elements (Mg, Ni, Si,
Cu, Mn) as can be observed in figure 3.
Cu X ray image
Compo image Si X ray image
Ni X ray image Mg X ray image Mn X ray image

Fig.2. Electron microscopy of the AlSi12CuNiMg matrix alloy realized with a micro analyzer; x 600.
Compo image + Mg Mg + Mn profile Ni + Cu profile Fe + Si profile

profile
Fig.3. Electron microscopy of the AlSi12CuNiMg matrix alloy realized with a micro analyzer for alloying
elements profiles; x 600.
In case of hybrid composites there are a higher number of interfaces comparing with simple
composites. Possible interfaces in Al-Si system, hipo, eutectic or hypereutectic alloys, are:
• between the α - solid solution of aluminum matrix and reinforcing particle;
• between the silicon primary crystal and reinforcing particle;
• between the eutectic (α +Si) and reinforcing particle;
• between Al2O3 and SiC particles.
195
The microstructures of obtained hybrid composites are presented in figure 4 and it put in
evidence the presence of silicon carbide and aluminum oxide as precipitates both by silicon
carbides or, discontinuous at grain boundary.
The particles and matrix nature were very well put in evidence by the electron microscopy. So,
silicon carbides have polyhedral crystal shape, well defined and designed, being the possibilities
of precipitates at the interfaces of Al2O3 particles. These features are put in evidence in figures 5
and 6.
It was observed the presence of spinel fine particles (Al2MgO4) between SiC particles. Alumina,
which is stable in the aluminum matrix, can turn in unstable form in pre presence of magnesium
(<8%) according to reaction:
Al2O3 + MgO = Al2MgO4
The spinel may be thermodynamically formed in solid state if alumina may remain nonstable
below the solidus line. Practically, we may consider the extension of this reaction at higher range
of temperatures.
(a) (b) (c)

Fig 4. Samples microstructures of AlSi12CuNiMg/SiC/Al2O3; (a) 5%SiC and 3%
Al2O3; (b) 10%SiC and 3% Al2O3; (c) 15%SiC and 3% Al2O3; x 100.
The nature of interfaces between aluminum matrix and silicon carbide, which was investigated
by microscopic analysis, put in evidence in figure 7, the presence of primary and eutectic silicon,
which can nucleate on dark silicon carbides.
Compo image Si X ray image Mg X ray image Mg + Si profile

Fig.5. Electron microscopy of AlSi12CuNiMg/5%SiC/3%Al2O3 composite realized with a micro
analyzer; x 300.
Compo image Si X ray image Mg X ray image Mg + Fe profile

Fig.6. Electron microscopy of AlSi12CuNiMg/15%SiC/3%Al2O3 composite realized with a micro
analyzer; x 300.
196
Fig.7. Optical microstructure of AlSi12CuNiMg/10%SiC/3%Al2O3 composite; x 500.
The chemical composition analysis and the reinforcement particle interfaces nature is the same in
all studied hybrid composites and is present suggestive through electron microscopy in figure 8.
(a)
(b)
Fig.8. Structural analysis of AlSi12CuNiMg/10%SiC/3%Al2O3 composite (a) (BSE, x 3000) and EDS
analysis on the central particle (b).
The particles nature which is put in evidence by EDS analysis may confirm that these particles
are obvious silicon carbide and also alumina. The interfaces between reinforcement particles,
both SiC and Al2O3, and aluminum matrix are simple, well defined, the so-called noncoherent
interfaces. An example of structural analyses of hybrid composite materials is given in figure 9.
(a)
(b)
(d)
(c)
Fig.9. SEM image (a) and EDS analysis of AlSi12CuNiMg/15%SiC/3%Al2O3; (b) analysis on SiC
particle; (c) analysis on Al2O3 particle; (d) analysis on aluminum matrix.
197
The careful analysis of these figures may reveal firstly that the structures of these hybrid
composite materials have a uniform distribution of the reinforcement particles in all processed
composites. And secondly, by compositional analysis, in all compositional types, both on matrix
and reinforcement particles was demonstrated the presence of reinforced particles in aluminum
matrix in a well defined manner.
Conclusions
1. Hybrid composite materials with AlSi12CuNiMg matrix and silicon carbide and alumina
particles as reinforcements were processed in liquid state.
2. SEM microscopy realized on the aluminum alloy matrix put in evidence the dendritic
structure of the solid solution, as well as the dendritic separation of the alloying elements.
3. The chemical composition of the hybrid experimental composite were matrix of
AlSi12CuNiMg and SiC carbides in proportion of 5%, 10% respectievely 15% and 3%
Al2O3, .
4. Optical, electron microscopy and EDS analysis realized on these hybrid composites put in
evidence the presence of both silicon carbide and aluminum oxide as precipitates.
5. Similar aspects were put in evidence by the electron-probe microanalyzer, as well as the
presence of fine particles of spinel (MgAl2O4) between SiC particles.
References
1. P.K. Rohatgi, S. Ray, R. Asthana, C.S. Narendranath, “Interfaces in cast metal- matrix
composites”, Materials Science and Engineering, A 162, 163-174, (1993).
2. S. Li, R. J. Arsenault and P. Jena, “Cast reinforced metal composites”, in S. G. Fishman and
A. K. Dhingra (eds.), Proc. Int .Symp. on Advances in Cast Reinforced Metal Composites,
World Materials Congress, Chicago, 1L, USA, September24-30,1988, ASM International, p.
33, (1988).
3. A. Mortensen, Proc. of ASM Int. Conf. on Fabrication on Particulate Reinforced Metal
Composites, Montreal, Canada, September 1990, p. 217.
4. P. K. Rohatgi, “Interfaces in metal-matrix composites”, in A.K. Dhingra and S. G. Fishman
(eds.), Proc. of Symp. sponsored by the AIME-American Society of Metals Composite
Committee, Annual Meeting of the Metallurgical Society, NewOrleans, LA, March 2-6,1986,
AIME, p. 185, (1986).
5. P.K. Ghosh and S. Ray, in P. K. Rohatgi (ed.), “Solidification of Metal Matrix Composites”,
TMS, p. 205, (1990).
6. Lloyd D. J.,Jin I., in Comprehensive Composite Materials, Vol. 3: Metal Matrix Composites,
Chap 21 p 5. Clyne, T.W. (ed.), Elsevier, Amsterdam (2000). Han, D. S.; Jones, H.; Atkinson
H. G., J. Mater. Sci., 28, 2654, (1993).
7. J.T. Al-Haidarz, A.S. Jabur, Al-Kaaby- “Evaluation study of cast Al-SiCp composites, Jordan,
(2006).
8. Gabriela Popescu, P.Moldovan, Microstructure- property studies of AlSiMg/SiCp composite
obtained by Vortex technique, UPB Scientific Bulletin, vol.62, p.71-81, (2000).
198
QUANTITATIVE EVALUATION OF CREEP CURVE

OF ALLOY-TYPE AND METAL-TYPE CREEP
IN MAGNESIUM-ALUMINUM BINARY ALLOYS AT AROUND 0.6Tm
Hiroyuki Sato
Graduate School of Science and Technology, Hirosaki University

Bunkyo-3, Hirosaki-shi, Aomori, 036-8561 JAPAN
Keywords: high temperature deformation, creep transition, stability of strain rate, life prediction
Abstract
Evaluation of creep curve is an important subject for life prediction of materials used in severe
environment. Although, minimum creep rate is one of the major parameter used for
characterization of high temperature deformation behavior of materials, the values are evaluated
from a part of creep curve. For precise analysis and prediction, not only the minimum creep rate,
but also a parameter that reflects shape of creep curve should also be considered. In this report,
author proposes a parameter that reflects shape of creep curve, analyzes its stress dependence
and compare with creep characteristics based on the minimum creep rates. Magnesium-
aluminum alloys are one of the alloys whose creep characteristics are investigated and divided
into classes with its stress dependence of minimum creep rates. The magnitude of change in
strain-rate near minimum strain rates is quantitatively evaluated and different stress dependence
of the parameter in Alloy-type regime and Metal-type regime has been found.
Introduction
It is well accepted that the creep characteristics are determined mainly by minimum creep rate,
ε&m , or by steady-state creep rate, ε& s . In crystalline materials, it is well known that the creep
rates show power-law as a function of the applied stress, σ, furthermore, Mukherjee, et al., led
the classical constitutive law of steady-state creep rate as following equation (1) [1].
AD0 Gb ⎛ b ⎞ ⎛ σ ⎞
p n
⎛ Q ⎞
ε& = ⎜ ⎟ ⎜ ⎟ exp⎜ − ⎟ (1)
kT ⎝ d ⎠ ⎝ G ⎠ ⎝ RT ⎠
Here, A, D0, G, b, k and R are a numerical constant, pre-exponential term of diffusion coefficient,
shear modulus, the magnitude of Burgers vector, the Boltzmann's constant and the gas constant,
respectively. The values T and σ are the absolute temperature and the applied stress which
determine the creep conditions. The value p, n and Q characterize the creep behavior and are the
grain size exponent, the stress exponent and the apparent activation energy of creep, respectively.
These values are determined experimentally.
In coarse grained solid solutions, minimum creep rates or steady-state creep rates can be
described by following equation (2), when the activation energy of creep is similar to that for
diffusion.
DGb − m ⎛ σ ⎞
n
ε& = A' N ⎜ ⎟ (2)

kT ⎝G⎠
199
In coarse grained materials, grain size exponent, p, can be assumed to be null, and the effects of
solute concentration on constant, A, are included as a power function of solute concentration, N.
At a temperature around 0.6Tm (Tm: the absolute melting temperature) where the activation
energy of creep are similar to that for diffusion, typical solid solutions like Al-Mg and Mg-Al,
show two types of creep behavior characterized by the concentration exponent, m, and the stress
exponent, n[2,3]. One is the Alloy-type behavior that is appropriate to solid solutions, and
another is the Metal-type behavior that is similar to the behavior of pure metals. The stress and
concentration exponents of Mg-Al binary solid solutions are summarized in Table 1.
Table 1. Creep parameters of Mg-Al solid solution alloys at 600K

Stress Region Lower Higher
Type of Behavior Alloy Metal
Stress exponent, n 4 6
Concentration exponent, m 1 2
Activation energy of creep, Qc Qc≈Q D~ Qc≈QDself
Around a normalized stress level of σ / G ≈10-3, creep behavior changes from Alloy-type to
Metal-type with increasing the applied stress. It is understood by change of rate-controlling
mechanisms from viscous glide of dislocations with solute atoms to recovery controlled creep
similar to pure metal.
The minimum creep rates and the steady-state creep rates are a part of parameters those can be
evaluated from creep curves, and reflect parts of information of creep curves. The minimum or
steady-state creep rate is one of representative value under the state defined by the applied stress
and temperature, and the same creep rates could be determined with different creep curve with
different shape. Although, time to failure, tr, is another parameter that reflects shape of creep
curve, it is evaluated after completion of creep experiment. Thus, it is not a state values as a
function of time, t, nor strain, ε.
Methods of analysis of whole creep curve have been proposed [4,5], and improvements of the
methods are also proposed [6,7]. These methods, however, reconstruct creep curve by defined
parameters, and the minimum creep rates are evaluated indirectly from the parameters. In those
cases, defined parameters correspond to one creep curve are not state variable as a function of
time, nor strain.
In this paper, author proposes a simpler parameter that reflects shape of creep curve in secondary
creep, and compare with the creep behavior of the alloys whose creep characteristics have been
determined.
Experiments and creep behavior
Creep curves and creep behavior

Creep curves used in this paper are that obtained from magnesium-aluminum solid solutions [3].
Table 2 Alloy designation and impurities (mass%)
Alloy Al (mol%) Fe Mn Cu Ni Zn
Mg-0.6Al 0.59 0.005 0.007 0.001 <0.001 0.017
Mg-1Al 1.04 0.006 0.007 0.001 <0.001 0.020
Mg-3Al 2.97 0.007 0.006 0.001 <0.001 0.019
200
Tensile creep experiments were performed under constant true stress in the air at 600K that
corresponds to 0.65Tm. Table 2 shows designation of alloys. The applied stress, σ, are ranged
from 5MPa to 50MPa, that corresponds to normalized stress, σ / G , of 4x10-4 to 4x10-3.
Figure 1 shows an example of creep curve of Mg-Al solid solutions at 600K. Typical creep
curve of normal type has been observed. Strain rates calculated by means of moving average of
finite differences are shown on the upper part of the figure. Under the condition, strain rate
looks almost stable in secondary creep stage, and the minimum creep rate can be determined
easily from the creep curve.
–2
10
10
–5
. Mg–Al 600K
ε
–1
–t –3
10
strain rate / s
Metal–type 6~7
–4
10 1
–1
10
–6
strain rate / s
–1 Alloy–Metal
εm / s
–5
10
・
1
0.3
ε
Mg–0.6Al 600K 10MPa
–t
4
true strain
–6
0.2 10 Alloy
○ Mg–0.6Al
0.1 Mg–0.6Al –7 □ Mg–1Al
10
600K 10MPa Alloy–type △ Mg–3Al
0 –8
0 50 100 10 3
t / ks 5 10 20 50 100
σ / MPa
Figure 1 Example of creep curve. Figure 2 Stress dependence of the minimum creep
rate. Arrows show the transition conditons.
Figure 2 shows the stress dependence of the alloys used in this analysis. It can be seen the two
stress regions corresponds to the Alloy-type behavior and the Metal-type behavior. Stress
dependence of the minimum-creep rate is described by equation (2) and the stress exponent, n,
increases with increasing the applied stress. The arrows show the transition conditions from
Alloy-type to the Metal-type of each alloy. The transition stress increases with increasing the
solute concentration.
Analysis and results
Proposal of the characteristic value, α

In this report, author proposes a simpler characteristic value, α that reflects shape of creep curves
at secondary creep. Here, the value is defined as the curvature of common logarithm of the
strain rate as a function of the creep strain at the minimum creep rate. It is defined by following
equation (3).
α=
d2
dε 2
(
log10 ε& / s −1 ) (3)
ε&min
It is the second order differential of strain rate as a function of strain, thus the values evaluated
by means of finite differential vary and spread widely from negative to positive value depending
201
on the precision of calculation. To avoid the difficulty of evaluation of the differential, least
square spline interpolation has been applied for calculation of strain rate, and related derivatives.
Figure 3 shows typical example of strain-rate as a function of strain of the alloy. Upper figure
shows strain rate calculated by means of moving finite differential, and lower shows strain rate
evaluated by means of fitting technique with least square spline approximation.
–5
10
Mg–0.6Al 600K 10MPa
–1
strain rate / s
–6 Moving finite differential

10
–5
10
Secondary creep
–1
strain rate / s
–6 Least square spline

10
0 0.1 0.2 0.3
strain
Figure 3 Example of difference of variation
of derivatives between by finite Figure 4 Schematic diagram of flow of
differential and by least cubic fitting. numerical evaluation of derivatives.
Figure 4 shows the flow of evaluation of the second order derivative of strain-rate as a function
of creep strain, ε. First, creep strain as a function of time is fitted to least square cubic spline,
and strain rate as a derivative of creep curve is evaluated. Then, the common logarithm of the
strain rate is fitted to least square cubic spline as a function of strain, with assumption that the
common logarithm of strain rate be the dependent value. Finally, the first and the second order
derivatives are evaluated as a function of strain. The characteristic value, α, is defined at the
strain corresponds to the minimum creep rate.
Figure 5 shows an example of evaluation of α for alloys at the same applied stress. The
characteristic value corresponds to the curvature of the figure are summarized in Table 3. It is
evident that part of shape of the creep curves can be numerically evaluated by the characteristic
value, α, and vary with alloys and deformation conditions.
–3
10
Mg–Al 600K 20MPa
. –1
strain rate , ε / s
–4
10
–5
10
○ 0.6Al
□ 1 Al
△ 3 Al
–6
10
0 0.1 0.2 0.3
creep strain , ε
Figure 5 Example of common logarithm of strain-rate as a function of strain. Curvature of the
plot at minimum creep rate corresponds to the characteristic value (Table 3).
202
Table 3 Evaluated parameter α for the alloys at 600K, 20MPa
Alloy α
Mg-0.6Al 14.6
Mg-1Al 32.7
Mg-3Al 69.5
Stress dependence of the characteristic value, α

Figure 6 shows stress dependence of the characteristic value, α, as a function of the applied
stress at 600K. The values increase with increasing solute concentration in all stress ranges. At
the stress corresponds to lower stress range, i.e. attributed to the Alloy-type with stress
dependence and the concentration dependence of the minimum creep rate, show positive stress
dependence. By contrast, at the higher stress range attributed to the Metal-type behavior, stress
dependence looks different and has no or negative stress dependence. At around the transition
stress of creep behavior from Alloy-type to Metal-type, the characteristic value, α, takes
approximately maximum and the stress dependence changes. It shows that the shape of the creep
curve depends on the applied stress. Moreover, it suggests that at the critical condition that
corresponds to the change of rate controlling mechanism, the strain rate is more sensitive with
deformation.
It is evident that the shape of creep curve depends on alloys and deformation condition and can
be characterized bye the proposed parameter, α, at minimum creep rate as a state variable.
）
Mg–Al 600K
. –1
2
2 log10 ε / s
10
（
Alloy Metal
3Al
1Al
2
__
dε
d
0.6Al
characteristic value, α,
1
10
9 10 20 30 40 50 60 70
stress σ / MPa
Figure 6 Stress dependence of the characteristic value, α. Arrows show the transition stress of
the minimum creep rate from Alloy-type to Metal-type. Solid marks show the
conditions correspond to the Alloy-type regime, and open marks to Metal-type regime.
Conclusions
1. Author proposes characteristic value that reflects shape of creep curve around minimum creep
rate in secondary creep, as a state variable.
203
2. The proposed characteristic value corresponds to the curvature of common logarithm of strain
rate as a function of strain. Least square spline technique improves accuracy of second and
third order derivatives of strain and numerically illuminates change of strain rate and shape of
creep curves.
3. The stress dependence of the proposed characteristic value, α, is different in Alloy-type creep
regime and Metal-type creep regime in magnesium-aluminum solid solutions. The maximum
value of the characteristic value, α, appear at approximately the transition stress from Alloy-
type to Metal-type. Stress dependence of shape of creep curves can be numerically represented
by simple state variable.
Acknowledgement
Part of the results in this research has been obtained using supercomputing resources at
Information Synergy Center, Tohoku University, Sendai, Japan.
References
1. A.K. Mukherjee, et al., The Interaction Between Dislocations and Point Defects, Vol. II, Part
III, ed. by B.L. Eyre, Atomic Energy Authority, Harwell, UK, (1968), 422-495.
2. Hiroyuki Sato, et. al., Effect of Stressing Direction in Compression and Tensile Creep
Behavior of Magnesium-Aluminum Solid Solution Alloys at around 600K, The Fourth Pacific
Rim International Conference on Advanced Materials and Processing (PRICM4), Eds. by
S. Hanada, et. al., JIM, (2001), 1155-1158
3. H. Sato and H. Oikawa, Transition of Creep Characteristics of HCP Mg-Al Solid Solutions at
600-650K, Strength of Metals and Alloys, Eds. by D.G. Brandon, et al., Freund Publishing
House, Ltd., U.K., (1991), 463-470.
4. R.W. Evans, et. al., Recent Advances in Creep and Fracture of Engineering Materials and
Structures, Ed. by B. Wilshire and D.R.J. Owen, Pineridge Press, U.K., (1982), p135
5. M. Prager, The Omega Method - An Effective Method for Life and Damage Prediction in
Creep Tests and Service, Strength of Materials, Eds. by H. Oikawa, et. al., JIM, (1984), 571-
574.
6. K. Maruyama and H. Oikawa, An Extrapolation Procedure of Creep Data for St
Determination: With Special Reference to Cr-Mo-V Steel, J. Pressure Vessel Tech., 109, (1987),
142-146
7. K. Maruyama, et. al., Improvement of Omega Method for Creep Life Prediction, ISIJ
International, 37 (1997), 419-423.
204
Properties of Titanium Oxide Films Deposited by the

Sol-Gel
Pablo Favilla1,2, Miguel Alterach1,3, Mario Rosenberger1,3, Alicia Ares1,3, Carlos Schvezov1,2,3,
Osvaldo Amerio4
1
Prog. Materiales, Modelización y Metrología, FCEQyN, UNaM. Félix de Azara 1552, (3300),
Posadas-Misiones, Argentina.
2
CEDIT. Félix de Azara 1890 - 5to. Piso. (3300), Posadas-Misiones, Argentina.
3
CONICET. Rivadavia 1917, (1033), Buenos Aires, Argentina
4
Sanatorio Integral IOT. Bolívar 2376 (3300), Posadas-Misiones, Argentina.
Keywords: Sol-Gel, Titanium oxide, Ti-6Al-4V, Films.
Abstract
In the development of new materials for use in mechanical heart valves there are conditions that
must be satisfied. In particular for the present report the focus is, particularly, in good surface
quality, mechanical and corrosion resistance and biocompatibility for the intended period of use.
The material object of this investigation is titanium oxide deposited on a substrate of Ti-6Al-4V.
The oxide films were deposited by the sol-gel technique by dip-coating, withdrawing at a
constant velocity, drying and thermal treatment.
The films were characterized by optical and scanning microscopy observations and test of
adhesion. The adhesion of the films were determined as a function of the number of layers
deposited and also in relation with the surface morphology. The results show that the mono-layer
films have much better adhesion than the multilayer films.
The films show cracks in the border of the samples which density number was reduced using a 6
months aged sol and covering the border with an acrylic resin.
Introduction
The fabrication of metallic made heart valves requires a finishing process such as the production
of a film on the surface device in order to provide a good hemocompatibility, in addition to an
adequate surface finishing, good mechanical, wear and corrosion resistance in order to obtain a
durable device. Titanium oxide is one of the alternative materials which satisfy the requirements
particularly, films deposited by the sol gel technique [1, 2].
The dip coating sol gel technique [3], basically consists in dipping the substrate material in a
colloidal dispersion (sol), withdrawing the substrate vertically at a constant velocity, depositing
the film, and drying the solvent.
The objective of the present research is to produce a titanium oxide film on Ti-6Al-4V alloys
which satisfy the requirements described above. In this report it is presented the characteristics of
the films after each processing step and under different conditions. The analysis of the surface of
the films and the substrate was performed using optical and scanning electron microscopy. In
addition it is presented the results of the scratch test [4] performed to determine the degree of
adhesion of the film are presented.
Experimental Methods
Sample Preparation and TiO2 Deposition
A total of fifteen samples of Ti-6Al-4V were deposited with a TiO2 film. The samples were first
mounted with an acrylic resin, polished with emery paper and finished with a combination of
0.05 µm alumina suspension, 10 volume H2O2 solution, and 1 µm or 0.25 µm diamond paste.
205
The sol consisted of a dispersion of a hybrid polymer of Ti and O which was prepared using the
following components: titanium butoxide, as a precursor of the TiO2, desmineralized water,
isopropanol, chloridric acid and ethyl acetoacetate. The composition of the colloidal suspension
in molar relations were; water/titanium butoxide:1, ethyl acetoacetate/titanium butoxide:0.5,
chloridric acid/titanium butoxide:0.0195 and isopropanol/ titanium butoxide:20. The sol gelified
7 months after preparation.
The TiO2 films were obtained in all cases by dip coating in the sol at a velocity of 0.33 mm/s and
ambient temperature (between 23 and 27ºC). Samples with one or more than one layer films
were obtained.
Films were deposited on substrates with different surface finishing and sol aging, as listed in
Table 1. All samples, except number 6, were deposited on both sides. In the case of sample
number 6 before deposition, one of the faces and the borders were covered with acrylic.
Table 1. Characteristics of the samples.
Sample Surface Finishing Number Sol Aging
of Layers
1 600 1 15 days
2 1500 1 15 days
3 Diamond paste, 1 µm 1 15 days
4 Diamond paste, 0.25 µm 1 15 days
5 Diamond paste, 1 µm 1 3 months
(Covered with Acrylic)
10 Diamond paste, 0,25 µm 3 3 months
11 Diamond paste, 0,25 µm 1 3 months
12 Diamond paste, 1 µm 3 15 days
After deposition the samples were dried in air at ambient temperature (approximately 25ºC)
inside a container. After drying, the samples were heat treated for one hour at 600ºC. The heating
speed was 10ºC/min. In the case of multilayer deposition, the samples were heat treated after
each deposition. The heat treatment was performed in order to produce a crystalline TiO2 film,
which expected structure is a mixed of anatase and rutile [1, 5]. The heating speed applied
reduced the number of cracks that may form due to deformation and stress [1, 6].
Scratch Adhesion Test
The scratch adhesion test [4] consists in passing an indenter on the surface of the film with a
vertical load which increases at a constant speed as the indenter moves on top of the surface and
depresses the surface in a degree that becomes more severe as the load increases. The result is a
line with two distinct zones; one for low loads where the film is depressed and a second for
higher loads in which the film is removed and the substrate is depressed. The load at which this
transition occurs determines the relative degree of adhesion of each film.
For the scratch test a CSEM Revetest was used with a Rockwell C a diamond indenter of 0.2 mm
in diameter. The applied loads varied from 0 to 20 N and the lengths of the lines were 4.5 mm
approximately. In all cases two tests were performed in the central regions of the samples.
206
The films were analyzed with optical and scanning microscopy for surface quality and by scratch
test for film adhesion
Surface Quality
During the process and soon after withdrawing from the dispersion the samples start to change
their colours which are attributed to the drying process. Near the borders of the samples it is
observed colour fringes which are attributed to the sliding down of the dispersion and an
accumulation at the border hold by surface tension.
The colour of the samples differs depending on the step in the process and the number of films
deposited.
The colours of the films before and after the heat treatment depend on the number of layers
deposited; films with one layer before of the heat treatment are yellow and after are blue, while
the films with three layers are purple before and after the heat treatment.
Observation in the Optical Microscope
The effect of the surface finishing of the substrate on the quality of the film was determined
depositing the films on two substrates which were polished with emery paper with a
granulometry of up to a grade of 600 and 1500 corresponding to samples 1 and 2, respectively.
The results are shown in Figure 1 where it is observed a smeared and scratched surface in sample
1 (Figure 1 a) and in sample 2 (Figure 1 b), in both cases due to cold work [7]. The films show in
the central part of the samples non-uniformity in the colouring which is a qualitative indication
of films with poor quality. Meanwhile, substrates polished with diamond paste up to 1 µm and
0.25 µm presented uniform films, except for the border effect, which shows that finishing with 1
µm diamond is adequate.
In the case of sample 6, the substrate was mounted in acrylic, finished with 1 µm diamond paste
and deposited. The objective was to eliminate the border and determine the effect. The result is
shown in Figure 2 in which an important reduction of cracks and fringes are observed, indicating
the importance of the border effect.
In addition, the effect of sol aging on film quality was determined in three samples 13, 14 and 15
using a sol aged during six months, twice as much as in most of the other samples. In these cases
it is observed that the area with fringes is reduced to a half of what it is observed in samples
which were normally treated with a sol aged during 15 days or 3 months and equivalent surface
finishing as in samples 3, 4, 5, 9 and 11. Moreover, the improvement in surface quality is
indicated by the practical absence of cracks in the border regions, as can be observed in Figure 3
for sample 13.
Smeared
Material Smeared
Material
400 µm 400 µm
(a) (b)
Figure 1. Effect of cold work due to polishing. Samples 1 (a), 600 paper; and 2 (b), 1500 paper.
207
Colour
Fringes
400 µm
400 µm
Figure 2. Sample 6 with less
fringes in the border. Figure 3. Sample 13. Effect of sol
aging with less fringes and no cracks
200 µm 400 µm
(a) (b)
Figure 4. Appearance to the optical microscope of the central region in a) Sample 13 and b) Sample 9
with one layer each.
The other samples show a central region free of cracks and uniform colour as shown in Figure 4
for both, one layer and three layer films. On the contrary, the samples usually present cracks and
colours fringes at the borders as shown in Figure 5 for both types of films, confirming the visual
observation. It is noted that the fringes and the cracks are mutually associated and they appear
after drying and heat treatment [3]. However the cracks density at the borders increases after heat
treatment. The formation of cracks has been associated to thermal expansion during the heating
process and contraction during the cooling process [6], the temperature gradients and probable
thickness gradients at the borders as well, which may produce levels of stress high enough to
produce the cracks.
Colour
Cracks Fringes
Cracks
400 µm 400 µm
(a) (b)
Figure 5. Presence of colour fringes in the borders and cracks after drying (a) Sample 12, and heat
treatment, (b) Sample 9.
Observations with Scanning Electron Microscopy (SEM)

The observations with the SEM using the “back scattered electrons” configuration show the
microstructure of both, the substrate and the film.
208
In Figure 6 (a) the two phases of the titanium alloy, β (light) and α (dark) are observed as
reported previously [8]. In Figure 6 (b), a region of the border with a high density of cracks is
shown.
Film
30 µm 30 µm
Cracks
(a) (b)
Figure 6. SEM image showing the α (dark) and β (light) phases (a); and cracks in the sample borders (b).
Adhesion Test
The scratch tests performed to determine the adhesion of the film to the substrate show different
behaviour depending on the number of layers. In the case of the films deposited with three
successive layers (samples 7 and 8) and for the test conditions employed, it is observed that the
film fails from the start of the test as shown in Figure 7 (a) for sample 7. On the contrary, for
films with one layer the results differ from sample to sample showing in some cases that the film
fails from a position in the scratch after a given degree of deformation, showing a uniform
degree of adhesion as shown in Figure 7 (b) for sample 5; or in other cases the film fails
discontinuously showing a non-uniform degree of adhesion of the film. However, in general
terms, it is shown that the one layer films have a much better adhesion than the three layer films.
No failure Partial failure Total failure

Partial failure Total failure
300 µm 300 µm
(a) (b)
Figure 7. Micrographs showing the different behaviours of the samples during the scratch tests. (a)
Failure from the start for a three layer film, and (b) failure at the middle of the scratch for a one layer film.
Conclusions
The conclusions of the present advances in the production of titanium dioxide film on a Ti-6Al-
4V alloy substrate by means of sol gel technique are the following:
1- The films obtained on smeared and scratched surfaces were not acceptable due to their
inhomogeneity, while those obtained on surfaces polished up to diamond paste of 1 µm
and 0.25 µm in size have an acceptable uniformity.
2- In almost all cases uniform films were obtained on the substrates, mostly on the substrate
surface with the exception of the sample borders where some imperfections appear. The
blue colour of the films in all cases is uniform.
3- The borders presented border fringers indicating a non-uniform film thickness and cracks
associated with the fringes.
4- The density of cracks and fringers decrease substantially in films deposited on mounted
samples or when six-month-old sol was used.
209
5- Producing a film with three layers after successive deposition do not improve the quality
of the film.
6- The scratch test results show that the three layer films have a weaker adhesion to the
substrate than the one layer film.
References
1. J. Liu, D. Yang, F. Shi and Y. Cai “Sol-Gel deposited TiO2 film on NiTi surgical alloy for
biocompatibility improvement”; Thin Solid Films, Vol. 429 (2003), p. 225-230.
2. E. Eisenbarth, D. Velten, K. Schenk-Meuser, P. Linez, V. Biehl, H. Duschner, J. Breme and
H. Hildebrand. “Interactions between cells and titanium surfaces”; Biomolecular
Engineering, Vol. 19 (2002), p. 243-249.
3. C. J. Brinker, A. J. Hurd “Fundamentals of sol-gel dip-coating”, Journal Physics III France,
Vol 4 (1994), p. 1231-1242.
4. S. Jacobsson, M. Olsson, P. Hedenqvist and O. Vingsbo, “Scratch Testing”; ASM
Handbook, Vol. 18 (1997), p. 820-837.
5. M. Keshmiri and M. Mohseni and T. Troczynski, “Development of novel TiO2 sol-gel-
derived composite and its photocatalytic activities for trichloroethylene oxidation”; Applied
Catalysis B: Environmental, Vol. 53 (2004), p. 209-219.
6. B. Surowska, J. Bieniaś, M. Walczak, K. Sangwall and A. Stoch, “Microstructure and
mechanical properties of ceramics coatings on Ti and Ti-based alloy”; Applied Surface
Science, Vol. 238 (2004), p. 288-294.
7. L.M. Gammon, R.D. Briggs, J.M. Packard, K.W. Batson, R. Boyer, C.W. Domby,
“Metallography and Microstructures of Titanium and Its Alloys”, Vol. 9 (2004), ASM
Handbook, p. 899–917.
210
MICROSTRUCTURAL AND MECHANICAL PROPERTIES OF

ALUMINA COATINGS PRODUCED BY MICROARC OXIDATION
TECHNIQUE ON 7039 ALUMINUM ALLOY SUBSTRATE
Aytekin Polat1, Juhi Baxi2 , Yusuf Kar 2 Metin Usta1, Murat Makaraci 3, Hong Liang2, A.
Hikmet Ucisik4
1
Department of Material Science and Engineering, Gebze Institute of Technology, Gebze-
Kocaeli, 41400, Turkey
2
Department of Mechanical Engineering, Texas A&M University, College Station, TX, USA
3
Department of Mechanical Engineering, Kocaeli University, Kocaeli, Turkey
4
Department of Prostheses, Materials and Artificial Organs, Bogazici University, Institute of
Biomedical Engineering, 34342 Bebek-Istanbul, Turkey
Keywords: Microarc Oxidation Method, Alumina Coating, Artificial Implants
Abstract
Aluminum alloy (7039) was coated using a microarc oxidation (MAO) process in an alkali
solution. To vary the coating’s microstructure and thickness, various current densities and
duration were used. The microstructure was studied using a scanning electron microscope and X-
Ray Diffraction. Surface roughness was measured using a surface profilometer. Micro hardness
measurements on the coated layer, and tribological investigation in biofluids were also
performed. The results showed that the coating consists of α-Al2O3, γ-Al2O3 and mullite phase. It
was found that the high hardness and thickness are associated with the high concentration of α-
Al2O3, resulted from the increased current density. MAO coatings typically exhibit micro
hardness gradient across the coating thickness. Results also showed that the thicker the coating,
the higher the surface roughness. Tribological experiments indicated that this coating is stable
and relatively wear resistant in synthetic biofluids.
Introduction
Aluminum and its alloys are attractive engineering materials for many applications such as
chemical, aeronautical, automotive, marine and aerospace industries, due to their low density in
combination with good mechanical properties and good resistance to degradation in some
corrosive environments. However, they often suffer severe damage under the synergistic attack
of wear and corrosion in some aggressive media, regardless of their good corrosion resistance.
Relatively low hardness and poor wear resistance without protective coatings on the surface
seriously limit the use of these alloys in extensive applications. A number of techniques have
been investigated to produce thicker protective coating on aluminum components such as arc-
discharge plasma, gas-flame spray, vacuum deposition methods and high temperature glass
enamelling [1]. These techniques require a high substrate temperature to provide adequate
coating adhesion at high contact loads. A relatively novel method, called microarc oxidation
(MAO) has been developed to produce ceramic coatings on Al, Ti, Mg and their alloys [2, 3].
The microarc oxidation method is based on the anodic polarization of processing materials in
aqueous electrolyte solution under plasma discharge conditions on the surface of anode. This
condition arises after exceeding the critical values of the polarization potential. The process
consists of numerous simultaneous plasma discharges over the whole surface of anode. This
method combines the electrochemical oxidation with a high voltage spark treatment (about 450-
600 V), and can provide the coating with excellent physiochemical properties [4]. The local
instantaneous temperature and pressure inside these microarc discharge channels can reach 103-
211
104 oK and 102-103 MPa, respectively [5]. As a result, oxide-based layers are formed on the
anode surface, which have special properties different from those of conventional anodic films.
The coating produced through the MAO process have exhibited improved mechanical properties
compared with anodic oxide coatings, and adhesive strength superior to plasma sprayed ceramic
coatings[6].
The primary objective of this paper is to study (i) the surface and mechanical properties of MAO
coating formed on Al 7039 alloy, and (ii) the tribological characteristics; friction and wear
studies, which are important to find its feasibility as an implant material.
Rectangular samples of aluminum alloy (Al-7039) were used as substrate; the nominal
composition of this alloy (wt. % ) is 0.068% Si, 0.139% Fe, 0.081% Cu, 0.266% Mn, 2.25 %
Mg, 0.198 % Cr, 4.12 % Zn, 0.012 % Ti and Al balance. Ceramic coatings were deposited on the
Al alloy specimens in weak alkaline electrolyte with a 100 kW micro-arc oxidation equipment
consisting of an ac power supply, a stainless steel container with a sample holder used as an
electrolyte cell, stirring and cooling systems. The Al alloy specimen and the wall of the stainless
steel container were used as the anode and the cathode, respectively. The electrolyte was
prepared from a solution of 9.5 g/l Na2SiO3.5H2O and 2 g/l KOH in distilled water. The
electrolyte temperature was controlled to remain lower than 35°C during treatment, by cooling
the electrolyte solution with a heat exchanger placed in the electrolytic cell. Different time
periods of 30, 60, 90, 120, 150 minutes and current densities of 0.125 A/cm2 and 0.150 A/cm2
were chosen to produce coatings. The film thickness, the presence and phase composition, the
micro hardness, the microstructure and the surface roughness of coated sample were analyzed
using an eddy current coating thickness measurement gauge (Fisher, Germany), Rigaku X-ray
diffractometer (XRD), Anton Paar micro hardness tester, Philips scanning electron microscope
and Veeco Dektak(Sloan Technology), respectively. A ball-on-disk tribometer (CSM
Instruments) was used for carrying out the friction and wear tests. The counter face sliding
partner was a silicon nitride ball of 6mm diameter. Silicon nitride was chosen as the pin due to
its high load bearing property and availability. The simulated body fluid (SBF) was added drop
by drop during the entire tests to simulate the body conditions. The tests were carried out at a
normal load of 5 N for 8 hours (28800s) at 25° C with a maximum sliding speed of 2.5 cm/s and
amplitude of 6mm. The relative humidity was between 52%-83%.
Results and Discussions
The Composition of MAO Coating
Fig. 1 illustrates the influence of the current densities and treatment times on XRD patterns of
coating deposited on Al 7039 alloys. The coatings produced at 0.125 A/cm2 current density are
only composed of γ-Al2O3 and mullite (Al6Si2O13) phases, while the coatings produced at 0.150
A/cm2 current density are γ-Al2O3, α-Al2O3 and mullite phases. The amount of these phases and
their contents vary with coating thickness. The coating thickness gradually increases with
oxidation time and current densities. The relative ratio of harder and denser α-Al2O3 phase was
increased with increasing current density and coating thickness. The content of α-Al2O3 or γ-
Al2O3 is defined by the cooling rate of the molten alumina in the microarc zone. The porous
outer layers directly connected with electrolyte solution have a higher cooling rate, which
promotes the formation of γ-Al2O3 phase during the solidification of alumina. However, the low
thermal conductivity of alumina causes the underlying layers of coatings to remain hotter and the
temperature sufficiently high to cause the transformation of originally formed γ-Al2O3 to α-
Al2O3. Thus, it is expected that the amount of α-Al2O3 will continuously increase towards the
212
coating-substrate interface [7]. Meta-stable phase γ-Al2O3 can be easily formed in interior of the
discharge channel and on the coating surface. However, mullite phase can only be formed on the
coating surface. The existing silicon in the form of mullite phase comes from the electrolyte
constituents during the plasma chemical reaction. It can be said that the current density is more
effective than oxidation time to obtain MAO coatings with high α-Al2O3 content.
(a) (b)
Fig.1.The influence of the current densities and treatment times on XRD patterns of coating: (a) 0.125 A/cm2; (b) 0.150 A/cm2.
Morphologies of Coating
SEM micrograph of the cross-section of samples in the Fig.2 reveals that the coating contains
three layers: a porous outer layer(1) consisting of low temperature phase, a compact inner
layer(2) formed by high temperature modifications, and a thin, interfacial layer(3) below the
compact layer consisting of complex phases of the substrate alloying elements.
(a) (b)
Fig.2.The cross-sections of the coatings deposited at different current densities: (a) 0.125 A/cm2, 2.5 hr; (b) 0.150 A/cm2, 2.5 hr.
The relative thickness of the layers, their structure and composition are substantially influenced
by deposition time and current density. The amount of more compact region (2) was increased by
increasing deposition time and current density. It is clear that the interface of substrate and
coating are well metallurgically bonded. No observable voids that would weaken the coating
were seen at the interface and near the interface.
Hardness of Coating
For different current densities, the micro hardness values of coating for 2.5 hour were obtained
by the indentations across the coating section at different distances from the substrate to coating
interface illustrated in Fig. 3.
213
Fig.3. Influence of current density on the hardness profile of oxidation coating.
There is a hardest zone in each curve of micro hardness values vs. distance from interface to
coating surface for different current density. As the current density increased, the coating
thickness for the same treatment time of MAO increased and the position of maximum hardness
moved away from the interface. A decrease in hardness from the maximum, towards the coating
surface, was measured. This may be due to both phase composition changes and a corresponding
increase in the coating porosity.
Surface Roughness of the Coating
Fig.4 shows the influence of current density and coating time on the surface roughness. It is clear
that in response to the increase in coating time and current density, a simultaneous increase in
both coating thickness and surface roughness is observed. High current density leads to increased
sparking discharge intensity and forms the coarse grains structure of coatings leading to high
surface roughness. In contrast, low current density tends to form the fine grain structure. Because
of the presence of well-distributed discharge channels during the initial stages of process, thinner
coating exhibit lower surface roughness. As the coating thickness increases, the number of such
discharge channels decrease, leading to non-uniformities in the coating which causes a gradual
increase in surface roughness.
Fig.4. Influence of coating time and current density on the surface roughness
Coefficient of Friction
The coefficient of friction was measured using a pin-on-disk tribometer while the tests were
being conducted and plotted against time. Results are shown below in Table I. The table shows
the minimum, maximum and mean coefficient of friction for the two samples. As can be seen the
coefficient of friction is less for the 0.150 A/cm2 sample as compared to the 0.125 A/cm2. The
reason could be because the micro hardness of the 0.125 A/cm2 is harder and so gives more
214
friction. Also due to the presence of the γ-Al2O3 and α-Al2O3 in 0.150 A/cm2 as compared to only
γ-Al2O3 in the 0.125 A/cm2.
Table I. Summary of Friction Results
Sample Start Min Max Mean Std. Dev.
0.125 A/cm2
0.004 0.154 0.381 0.215 0.045
2.5 hr
0.150 A/cm2
0.151 0.084 0.403 0.164 0.050
2.5 hr
Wear Mechanisms
The wear mechanisms were studied using the Scanning Electron Microscope (SEM). The images
of the wear track obtained from the SEM are shown in Fig. 5. Fig. 5 shows the wear track at
2,000X magnification (the scale bar is 16 μm). The sample surface is shown in the right hand
corner, that image is at the same scale. The wear track shows cracks, wear debris and places
where the SBF has solidified. Also as can be seen in the figure, the wear track is smoother than
the surface
Fig.5.The wear track and the surface at 2000 X or 16 microns on the scale bar.
The above results indicate that the coatings are hard and wear resistant in SBF. The coating
obtained at 0.150 A/cm2 at 2.5 hr has a lower coefficient of friction than that at 0.125 A/cm2. Its
average μ is only 0.164 as compared to 0.215 for the 0.125 A/cm2, 2.5 hr. In the SEM image of
wear track, there are visible cracks and large debris. The wear observed is least after 8 hours of
sliding in SBF.
Conclusions
1) The coating composed of α-Al2O3, γ-Al2O3 and mullite phases. The relative ratio of harder
and denser α-Al2O3 phase is increased with increasing current density and coating thickness.
2) MAO coatings typically exhibit micro hardness gradient across the coating thickness with
maximum hardness close to the interface and the lowest hardness at the surface of the
coating.
3) The surface roughness of MAO coatings is a function of final coating thickness and increases
with increasing coating thickness and current density.
4) Tribological results showed that MAO coatings have minimum wear and acceptable friction
in synthetic biofluids and could be a potential biocoating for implants. The friction could be
further reduced through surface polishing. High wear resistance was found to be due to the
increased micro hardness that can be controlled through changing microstructure.
215
Acknowledgements
This work was sponsored by the Gebze Institute of Technology, the NSF 0535578 and the Texas
A&M University.
References
1) Y.C. Wang and S.C. Tung, “Scuffing and Wear Behavior of Aluminum Piston Skirt Coatings
against Aluminum Cylinder Bore,” Wear, 229 (1999), 1100-1107.
2) A.L. Yerokhin, V.V. Lyubimov and R.V. Ashitkov, “Phase Formation in Ceramic Coatings
during Plasma Electrolytic Oxidation of Aluminum Alloys,” Ceram. Int., 24 (1998), 1-6.
3) G.L. Yang, X.Y. Lu, Y.Zh. Bai, H.F. Cui, Z.S. Jin, “The Effects of Current Density on the
Phase Composition and Micro Structure Properties of Micro-arc Oxidation Coating,” J. Alloys
Comp, 345 (2002), 196-200.
4) A.L. Yerokhin et al., “Characterisation of Oxide Films Produced by Plasma Electrolytic
Oxidation of a Ti–6Al–4V Alloy,” Surf. Coat. Technol, 130 (2000), 195-206.
5) M.D. Klapkiv, “State of an Electrolytic Plasma in the Process of Synthesis of Oxides Based
on Aluminum,” Mater. Sci, 31 (1995), 494.
6) G. Sundararajan and L. Rama Krishna, “Mechanisms Underlying the Formation of Thick
Alumina Coatings through the MAO Coating Technology,” Surf. Coat. Technol, 167 (2003),
269-277.
7) J. Tian et al., “Structure and Antiwear Behavior of Micro-arc Oxidized Coatings on
Aluminum Alloy,” Surf. Coat. Technol, 154 (2002), 1-7.
216
EFFECTS OF LATTICE DEFECTS INDUCED BY HYDROGEN AND

STRESS ON ENVIRONMENTAL DEGRADATION OF METALS
K.Takai1 , H.Shoda2
1
Department of Mechanical Engineering, Sophia University
7-1,Kioi-cho, Chiyoda-ku, Tokyo 102-8554, Japan
2
Graduate student, Sophia University
Keywords: hydrogen, degradation, lattice defect, vacancy, dislocation, thermal desorption

analysis
Abstract
Hydrogen absorbed during corrosion causes the environmental degradation of mechanical

properties. The principal factor causing the degradation was investigated using Inconel 625 as
an face-centered-cubic (fcc) metal and pure iron as a body-centered-cubic (bcc) metal to clarify
the role of hydrogen. When Inconel 625 with zero hydrogen content was subjected to a strain of
up to 0.02, the stress was relieved, and the specimens was then charged by hydrogen, the
hydrogen content was 20 mass ppm. In contrast, when the Inconel 625 containing hydrogen was
subjected to a strain of up to 0.20, the stress was relieved, and the specimen was charged by
hydrogen, the hydrogen content was 29 mass ppm. A similar tendency was observed for pure
iron. These results suggest that both hydrogen and strain induce the formation of lattice defects
in metals. To identify the type of lattice defect causing hydrogen degradation, various
mechanical tests were conducted by the slow strain rate technique (SSRT). The ductility did not
recover when the Inconel 625 containing hydrogen was subjected to a strain of up to 0.02, the
stress was relieved, the specimens was maintained at 30 °C to release all the hydrogen, and stress
was applied again. In contrast, the ductility completely recovered when the Inconel 625
containing hydrogen was subjected to a strain of up to 0.02, the stress was relieved, the specimen
was maintained at 200 °C to release all the hydrogen, and stress was reapplied. A similar
tendency was observed for pure iron. These results suggest that the principal factor causing
hydrogen degradation is the formation of vacancies and vacancy clusters induced by hydrogen
and strain, since maintaining the specimens at 200°C results in the annihilation of vacancies and
vacancy clusters.
Introduction
Developing high-strength steels to reduce the weight of cars results in the saving energy.
However, the susceptibility to hydrogen degradation increases with the tensile strength of the
steels. Hydrogen fuel-cell systems are expected to be used as a next-generation source of clean
energy. The pressure of hydrogen in more recent fuel-cell vehicles has tended to increase from
35 MPa to 70 MPa, so that the vehicle can be driven for long distances. In addition, the pressure
of hydrogen at refuelling stations is as high as 100 MPa. Therefore, the development of fcc and
bcc metals that are highly resistant to hydrogen degradation is required, since many materials are
deteriorated by hydrogen.
Although a large number of studies have been carried out on hydrogen degradation over many
years, there is little agreement as to its mechanism, for example, lattice decohesion theory [1],
217
hydrogen enhanced local plasticity theory [2], absorption-induced dislocation emission theory
[3], and vacancy contribution theory [4] have all been suggested as mechanism.
The thermal desorption analysis (TDA) of hydrogen in high-strength steels representing bcc
metals [5,6] and stainless steels representing fcc metals [7] has been performed extensively over
the past few years to measure the hydrogen content and analyze the trapping states of metals.
This method of hydrogen analysis can be applied to clarify the mechanism by combining with
the result of slow strain rate technique (SSRT).
With this background, to clarify the role of hydrogen in mechanical degradation during
deformation, Inconel 625 as an fcc metal and pure iron as a bcc metal were prepared. The two
principal features of this study are (1) the acceleration of lattice defect formation induced by
hydrogen and strain, and (2) the identification of the factor causing hydrogen degradation by
TDA and SSRT. On the basis of our results, the mechanism of hydrogen degradation is
discussed.
Experimental
Materials
The Ni-based alloy, Inconel 625 (Ni:60.8%, Cr:21.5%, Mo:9.0%, Fe:3.9%, Nb:3.5%) as an fcc
metal and 99.99% pure iron as a bcc metal were employed in the present study. Inconel 625 was
solution-treated at 1150 °C and the pure iron was annealed at 900 °C.
Hydrogen charging
Hydrogen was introduced into the specimens by cathodic charging, which was performed at
constant current density under galvanostatic control. The charging was carried out in an aqueous
solution of pH 2.5 H2SO4 adding 0.09 mass% NH4SCN at a current density of 50A/m2, and at a
temperature of 90 °C for Inconel 625 and 30 °C for pure iron.
TDA
The TDA apparatus consists of a gas chromatograph, a thermal conductivity detector, a heating
unit, and a recorder. The gas chromatograph was calibrated using standard gas mixture (Ar + 50
vol ppm H2) to quantify the hydrogen content in the specimens. TDA was conducted in the
temperature range from 25°C to 800°C. The sensitivity limit for the detection of hydrogen is
0.01 mass ppm in this method.
Hydrogen degradation evaluation
Hydrogen degradation of the mechanical properties was evaluated as the decrease in fracture
strain during the application of tensile stress by SSRT. SSRT was conducted at a strain rate of
8.3×10-6 /s for Inconel 625 in air because of the low diffusion coefficient of hydrogen, whereas
SSRT was conducted at a strain rate of 4.2×10-6 /s for pure iron while performing cathodic
charging to prevent the release of hydrogen because of the high diffusion coefficient of hydrogen
in pure iron.
Acceleration of lattice defect formation induced by hydrogen and strain
218
Inconel 625, pure Fe 0.6
Inconel 625 (strain: 0.02)
Hydrogen Evolution Rate, R /mass ppm min–1

H charging
Strain [H+strain]
29 ppm
Strain
0.4
[strain] [strain]
[no strain] [H+strain]
20 ppm
Stress
Stress
Stress
0.2 [no strain]

18 ppm
Strain Strain H charging Strain
H charging (constant condition: 50 A/m2)
TDA (H content increase= lattice defect increase) 0

0 100 200 300
Temperature, T/ °C
Figure 1. Procedure to clarify interaction between Figure 2. TDA profiles and hydrogen content of
hydrogen and strain. Inconel 625.
Figure 1 shows procedure followed to clarify the interaction between hydrogen and strain. The
[no stain] specimen is neither subjected to applied strain nor to hydrogen charging. The [strain]
specimen is subjected to applied constant strain without hydrogen charging, then stress relieved.
The [H+strain] specimen is charged hydrogen, applied constant strain, and then the stress is
relieved. These three specimens were charged by hydrogen until saturation under a constant
condition of 50A/m2, then the hydrogen content was measured using TDA. The total hydrogen
charging time and charging conditions were kept constant. The hydrogen content increases with
the degree of cold-drawing in pure iron and eutectoid steel. The lattice defect density increases
with the degree of cold-drawing. Therefore, a high hydrogen content means a high density of
trapping sites, that is, lattice defects are formed with a high density during the deformation.
Figure 2 shows the TDA profiles and hydrogen content of Inconel 625. The hydrogen content of
the [strain] specimen for which tensile stress is applied until up to a strain of 0.02 is greater than
that of the [no strain] specimen. This increase
0.1
in hydrogen content corresponds to that of the Pure Fe (strain: 0.20)
Hydrogen Evolution Rate, R /mass ppm min–1
density of lattice defects formed by plastic

deformation. Furthermore, the hydrogen [H+strain]
content of the [H+strain] specimen is greater 4.1 ppm
than that of the [strain] specimen. This increase
in hydrogen content in spite of the same strain 0.05
[strain]
of 0.02 means that the hydrogen accelerates the 1.5 ppm
formation of lattice defects, such as dislocations
and vacancies, in Inconel 625. [no strain]
Figure 3 shows the TDA profiles and hydrogen 0.8 ppm
content of pure iron. The hydrogen content of
0 100
the [strain] specimen for which tensile stress is 0
applied up to until a strain of 0.20 is also greater Temperature, T/ °C
than that of the [no strain] specimen. Figure 3. TDA profiles and hydrogen content of pure
Furthermore, the hydrogen content of the iron.
[H+strain] specimen is greater than that of
219
Inconel 625 , pure Fe
the [strain] specimen. For not only
the fcc metal but also the bcc metal, H charging H charging
hydrogen accelerates the formation
of lattice defects such as dislocations prestrain prestrain prestrain
and vacancies during deformation.
Holding at 30 °C or 200 °C
From these results, the role of
hydrogen is to accelerate the (a) without H (b) with H (c) 30 °C, 0 ppm H (d) 200 °C, 0 ppm H
formation of lattice defects such as

dislocations and vacancies during restrained until failure by SSRT
deformation under constant strain.
H is not
released
Stress
Stress
Stress
Identification of factor causing H released at
30 °C or 200 °C
hydrogen degradation
Strain H charging H charging
Strain Strain
To clarify which factors affect Figure 4. Procedure to identify the lattice defect causing hydrogen
hydrogen degradation directly, degradation of Inconel 625 and pure iron.
specimens treated under various
procedures were prepared. Figure 4 shows the procedure used to identify the lattice defect that
causes the hydrogen degradation of Inconel 625 and pure iron. For specimen (a), constant
prestrain is applied without charging by hydrogen, then the stress is relieved. Specimen (b) is
charged by hydrogen, constant prestrain is applied, then the stress is relieved. Specimen (c) is
charged by hydrogen, constant prestrain is applied, then the stress is relieved, and the specimen
is maintained at 30°C to desorb all hydrogen. Specimen (d) is charged by hydrogen, constant
prestrain is applied, then the stress is relieved, and the specimen is maintained at 200°C to desorb
all hydrogen. Finally, all the specimens are resubjected to strain by SSRT until failure.
Figure 5 shows the stress-strain curves, hydrogen content, and degradation susceptibility (DS) of
Inconel 625 specimens. In the case of all Inconel 625 specimens, prestrain is applied up to a
value of 0.02, then the stress is relieved, and the specimen is resubjected to strain until failure.
600 200
(c) 30 °C Inconel 625 Pure Fe
(0 ppm, DS: 0.57)
500
stress
Nominal stress, σ /MPa
relieving
400
(a)without H
restrain
(0 ppm, DS: 1.0)
300 100
(a)without H
200 stress
relieving
100 (d) 200 °C (b) with H
(b) with H (0 ppm, DS: 0.99) (0.8ppm, DS: 0.71)
(40 ppm, DS: 0.08)
0 0
0 0.1 0.2 0 0.1 0.2 0.3 0.4
N omina l st ra in, ε
Nominal strain, ε Nominal strain, ε
Figure 5. Stress-strain curves, hydrogen content, and Figure 6. Stress-strain curves, hydrogen
degradation susceptibility (DS) of Inconel 625 content, and DS values of pure iron.
specimens.
220
The fracture strain of specimen (a) is about 0.3, which is determined as standard value for
comparison. The degradation susceptibility of specimens is defined as fracture strain after
hydrogen charging divided by fracture strain without hydrogen charging. When the DS value is
one, this means no decrease in ductility. When the DS value is lower than one, there is a
decrease in ductility. The DS value of specimen (b) is 0.08, since it absorbs hydrogen to a
concentration of 40 ppm. The DS value of the specimen (c) is 0.57 even though all the hydrogen
is released by maintaining the specimen at 30°C. The DS value of specimen (d) is 0.99.
The result for specimen (c) which includes vacancies and dislocations accelerated by interaction
between prestrain and hydrogen, indicates that it is not necessary for hydrogen to be present in
metals for fracture to occur due to the degradation of ductility. The specimen (c) retains its
decrease in ductility regardless of there being no hydrogen present. This suggests that hydrogen
does not reduce the lattice strength and break the lattice bonding directly, but hydrogen enhances
lattice defect formation during prestrain as shown in Fig.2, and the accumulation of the lattice
defects in the metal causes the decrease in ductility.
The result for specimen (d) indicates that the ductility recovers completely after the specimen is
maintained at 200°C to that of the specimen (a). Maintaining the specimen at 200°C results in
hydrogen desorption and the annihilation of vacancies and their clusters. Therefore, the
complete recovery of ductility indicates that the vacancies and their clusters induced during
prestrain with hydrogen are the most important factors causing the hydrogen degradation of the
fcc metal.
Figure 6 shows the stress-strain curves, hydrogen content, and DS values of pure iron, which is a
bcc metal. In the case of pure iron, prestrain is applied up to a value of 0.15, then the stress is
relieved, and the specimen is resubjected to strain until failure. The fracture strain of the
specimen (a) is about 0.4, which is determined as the standard value for comparison. The DS
value of the specimen (b) is 0.71, since it absorbs hydrogen to a concentration of 0.8 ppm.
Figure 7 shows the stress-strain curves, hydrogen content, and DS values of pure iron maintained
at 30°C for 168 h to release all the hydrogen. The standard stress-strain curve of pure iron
changes upon maintaining the specimen at 30°C after prestrain, as shown in Fig.7, due to the
Cottrell effect. The DS value of the specimen (c) is 0.81 although all the hydrogen is released by
maintaining the specimen at 30°C.
200 200
Pure Fe Pure Fe
restrain
restrain
100 100
(a)without H
(a)without H stress (200°Cx2h)
stress (30°Cx168h) relieving
relieving
(d) 200 °C
(c) 30 °C (0ppm, DS: 0.97)
(0ppm, DS: 0.81)
0 0
0 0.1 0.2 0.3 0.4 0 0.1 0.2 0.3 0.4
Nominal strain, ε Nominal strain, ε
Figure 7. Stress-strain curves, hydrogen content, Figure 8. Stress-strain curves, hydrogen

and DS values of pure iron maintained at 30°C for content, and DS values of pure iron maintained
168 h to release all the hydrogen. at 200°C for 2 h to release all the hydrogen.
221
Figure 8 shows the stress-strain curves, hydrogen content, and DS values of pure iron maintained
at 200°C for 3h to release all the hydrogen. The DS value of specimen (d) is 0.97.
The increases in the densities of vacancies and clusters enhanced by the interaction between the
strain and the hydrogen play a common important role in the hydrogen degradation of both fcc
and bcc metals.
Conclusions
The role of hydrogen and the identification of the factor causing the hydrogen degradation of
Inconel 625, an fcc metal, and pure iron, a bcc metal, have were investigated using TDA and
SSRT. The results obtained in the present study can be summarized as follows:
(1) The role of hydrogen is to accelerate the formation of lattice defects such as dislocations and
vacancies during deformation under constant strain.
(2) The vacancies and their clusters formed during prestrain with hydrogen are the most
important factors causing the hydrogen degradation.
Acknowledgements
This study was supported by Industrial Technology Research Grant Program in 2006 from New
Energy and Industrial Technology Development Organization (NEDO) of Japan.
References
1. R. A. Oriani and P. H. Josephic, “Equilibrium Aspects of Hydrogen-Induced Cracking of

Steels”, Acta Metall. , 22 (1974), 1065-1074.
2. H. K. Birnbaum and P. Sofronis, “Hydrogen-Enhanced Localized Plasticity – A Mechanism

for Hydrogen Related Fracture”, Materials Science and Engineering, A176 (1994), 191-202.
3. S. P. Lynch, “Environmentally Assisted Cracking: Overview of Evidence for An Adsorption-

Induced Localised-Slip Process”, Acta Metall., 36 (1988), 2639-2661.
4. M. Nagumo, “Hydrogen Related Failure of Steels – A New Aspect”, Materials Science and
Technology, 20 (2004), 940-950.
5. K. Takai and R. Watanuki, “Hydrogen in Trapping States Innocuous to Environmental

Degradation of High-Strength Steels”, ISIJ International, 43 (2003), 520-526.
6. K. Takai, Y. Chiba, K. Noguchi, and A. Nozue, “Visualization of Hydrogen Desorption

Process from Ferrite, Pearlite and Graphite by Secondary Ion Mass Spectrometry”, Metall. Mater.
Trans. A, 33A (2002), 2659-2665.
7. K. Takai, “Hydrogen Degradation and its Mechanism in Fcc Metals for High-Pressure
Hydrogen Storage Tank”, Advances in Materials Science, 7 (2007), 205-210.
222
BRITTLE CRACK SUSCEPTIBILITY OF LOW TEMPERATURE

SEPARATOR VESSEL MATERIAL
Ahmad Ahsan Nawaz
1
TMS (The Minerals, Metals & Materials Society);
184 Thorn Hill Rd.; Warrendale, PA 15086-7514, USA
Ghulam Ishaq Khan Institute, House no.66, Street no.6, G-8/2, Islamabad, Capital, 44000,
Pakistan
Keywords: Parent Metal, Post Weld Heat Treated Metal, Heat Affected Zone
Abstract
Low temperature separator (LTS) vessel made from High Strength Low Alloy (HSLA) steel
grade A516-70, is used in gas sector following the JT valve or the turbo-expander. Being at very
low temperature (-21.6°C to -25 °C), it is susceptible to brittle fracture due to ductile to brittle
transition. The influence of temperature on the failure behavior of this material has been studied.
Moreover, since the low temperature separator is manufactured from welded sheets, therefore,
affect of temperature on the failure behavior on the post weld heat treated (PWHT) sample have
also been carried out. In particular, SEM examination revealed the type of fracture that occurred
in the parent metal as well as PWHT sample. A significant increase in the impact toughness of
the PWHT samples as compared to the parent metal was observed which was explained by
optical micrographs as well as SEM examination.
1. Introduction
The LTS is made from SA 516-70N (Steel). Its operating conditions are fairly different from
other high-pressure vessels. It operates at 850 psi pressure and -210C. Depending on the weather
conditions its operating temperature becomes even lower. During the gas production processes,
cold process gas stream from the turbo expander enters the low temperature separator at about -
21.6°C to -25 °C, and increases as it enters and exits the LTS because of the environment effects.
It is a vertical, two phase separator. Under such extreme conditions LTS is susceptible to brittle
fracture. An important measure of the susceptibility of LTS to fracture under such conditions is
to determine the Ductile to brittle transition temperature (DBTT) range. As a matter of fact the
LTS is constructed by welding large metal plates (normally 96 inch * 72 inch). It was therefore
equally important to determine the DBTT of the welded portion of the material. For this purpose
the welded samples have to post weld heat treated for stress relieving. A specific post weld heat
treatment was used to relieve the stresses and improve the toughness even more than the parent
metal. For this purpose Charpy V-notch test is used to characterize the DBTT.
2. Experimental and results
2.1 Optical microscopy of A 516-70 steel
Anisotropy results in properties of the sample being different in different directions. 516-70
grade steel of the low temperature pressure vessel is a rolled HSLA steel. Because of the rolling,
anisotropy has been introduced into the samples. Optical microscopy was initially done to verify
the rolling direction of the steel sample. Non-metallic inclusions MnS stringers along rolling
direction can be seen as shown in figure 1a and 1b.
2.2 Welding
For charpy test on welded material, the plate of the sample was cut perpendicular to the rolling
direction and then V-grove for welding was prepared using band saw to ensure accuracy.
223
Submerged metal arc welding (SMAW) procedure was used for welding. The plate was
prevented from warpage during welding, by applying small tack weld at the sides. This produced
stresses in the steel plate, which were removed by subsequent specialized/localized stress
relieving.
Figure 1a Figure 1b
Optical micrographs of the cross section of A516-70 samples at different
magnifications. Figure a 100X figure b at 800X magnification, clearly shows the
rolling direction and the banded structure of Pearlite and Ferrite.
2.3 Stress relieving cycle
Special heat treatment equipment was used to perform heat treatment. Very specialized and
localized Stress relieving of only the welded portion of the metal plate was done. The stress
relieving diagram below shows
Figure 2. Stress relieving diagram for the welded plate

Initially the temperature is increased up to 300°C at a heating rate of 200°C per minute for 30
minutes. The temperature is then further increased at a rate of 100°C per minute up to 610°C.
The temperature increase rate was decreased in order to keep uniformity of microstructure. After
60 minutes at 610°C is followed by staying at treatment at 300°C for 30 minutes and then the
plate removed from the equipment and then air cooled.
2.4 Optical microscopy of post weld heat treated samples
3a shows a banded structure of the base metal region of the Welded sample. The dark regions
depicted by the arrow represent the elongated pearlite region and the bright regions are ferrite
grains. Peculiarity in figure 3c is an acicular structure can be seen. Figure 3(c) shows the acicular
bainitic ferrite structure.
224
2.7 Hardness testing
Vickers testing of base metal, heat affected zone (HAZ) and the welded zone was carried out and
plotted as a graph for comparison. The hardness of the HAZ is the highest owing to the thermal
stresses induced because of the welded region.
Figure 3(a)base metal Figure 3(b)heat affected Zone Figure 3(c)weld zone
2.8 Spectrometric analysis
Table I: Spectrometric results of A516-70 Steel
C Si Mn P S N Al
0.17 0.317 1.1 0.007 0.0006 0.0043 0.037
Mo Ni Cr V Nb Sn Cu
0.04 0.053 0.052 0.00 0.00 0.00 0.041
2.8.1 Parent metal: The samples (ASTM E-23) were tested over a temperature range of +40°C to
-90°C. The upper shelf fluctuates between an impact energy ranges of 35J-40J. The steel appears
to be completely ductile at temperatures up to -50 to -55 °C and goes very brittle at temperatures
as below as -90°C.
2.8.2 Charpy V-notch impact testing
At and below the Transition temperature, a brittle cleavage fracture initiates from the
discontinuities and the non-metallic inclusions, and as the stress approaches the yield strength,
the volume of material surrounding the discontinuity forms a microvoid and this is clearly
depicted from the SEM micrographs in figure 7(a). the microvoid formation and the crack once
initiated, brittle fracture propagated through regions of the entire structure.
2.8.3 Post weld heat treated samples: From the impact energy values, it is established that the
ferrite pearlite microstructure has changed to acicular structure i.e., bainite structure. This
transformation is because of the PWHT cycle. The upper shelf energy is around 160J and lower
shelf energy ranges below 10J. Up to -25°C the welded samples seem to be completely ductile
and below -60°C it has gone brittle.
2.9 Fractography
The arrows in SEM image 7(a)show that ductile failures occur through micro void coalescence.
MnS result in microvoid formation. The dark and comparatively flat regions show the Pearlite
structure and the other Ferritic regions show dimples which are a characteristic of ductile
fractures. SEM micrograph 7(b) is taken from the fractured surface of a sample at -55 ºC, which
the critical temperature where transition from ductile to brittle takes place. Figure 7c shows a
pure microvoid coalescence phenomenon depicting ductile fracture at 0 ºC, at -55 ºC, the arrow
on the left in figure 8(b) shows flat surfaces and the other arrow indicates presence of dimples. It
225
is a mixture of ductile and brittle fracture. Flat surfaces in 8(c) indicates pure brittleness at -90
ºC.
Table II: Hardness values of different regions Figure 4. Hardness values of PWHT samples
3. Discussion
Presence of significant amount of carbon and other alloying elements result in a very sharp
transition curve. The transition of the parent metal as well as the post weld heat treated sample
occurred roughly with 25ºC temperature range. SEM micrographs of the PWHT sample show
purely ductile fracture as shown in figure 8(a), for the sample tested at 0ºC showing microvoid
coalescence, as compared to the SEM micrograph of the parent metal tested at 0ºC, which is
relatively less ductile. When both types of samples, parent metal and PWHT, were impact tested
226
at testing temperature range +40ºC to -90 ºC. The upper self impact energy value for the parent
metal remained inte range of 36J to 38J. However, upper self energy values for the PWHT
samples are in the range of 165J to 168j.
IMPACT ENERGY VS TEMPERATURE IMPACT ENGERY VS TEMPERATURE GRAPH

GRAPH
IMPACT ENERGY
60
ENERGY (J)
60
40
IMPACT
(J)
40
SAMPLE 1 20
20
SAMPLE 2
0 0
-100 -50 0 50 SAMPLE 3 -100 -50 0 50
TEMPERATURE (C) TEMPERATURE (C)
Figure 5(a) and (b) show the DBTT curve for A516-70
Table III: Values of energy absorbed by A516-70 samples
TEMPERATURE SAMPLE 1 SAMPLE 2 SAMPLE 3 AVERAGE
40 36 40 38 38
22 38 35 42 38
0 33 35 39 36
-20 40 34 36 37
-40 38 30 35 34
-55 32 30 37 33
-60 18 24 20 21
-65 14 20 17 17
-70 11.5 11 13 12
-80 12 8 7 9
-90 9 8 6 8
(a) (b) (c)

Figure 6(a) 0ºC at 1000X, (b) -55ºC at 3000X, (c) -90ºC at 3000X
IM PA C T EN ER G Y V S T EM PER A T U R E G R A PH IM PACT ENERGY V S TEM PERATURE GRAPH
18 0
200
IMPACT ENERGY (J)
16 0
14 0
150
12 0 SA MPLE 1
10 0
100 SA MPLE 2
80
60 SA MPLE 3
50
40
20 0
0 -100 -50 0 50
-10 0 -50 0 50
T EM PER A T U R E ( C ) TEM PERATURE (C)
Figure 7(a) and (b) show the DBTT curve for PWHT A516-70 Material
227
Moreover, the hardness values of the welded region also reflect and verify the presence of
bainitic structure. The values of the impact energies of the PWHT samples are very consistent
and the energy depicted by the upper self clearly shows the presence of bainitic structure. Auto
tempering during the controlled temperature resulted in the transformation of the perlitic
structure having banded structure to acicular bainitic structure. Such values of impact energy are
only exhibited by the bainitic steels.
Table IV: values of energy absorbed by PWHT samples at different temperatures
TEMPERATURE SAMPLE 1 SAMPLE 2 SAMPLE 3 AVERAGE
40 168 165 170 168
22 162 169 167 166
0 162 160 164 162
-20 158 164 160 161
-40 135 138 150 141
-55 72 78 80 77
-60 51 53 55 53
-65 22 14 16 17
-70 11.5 8 10 10
-80 11 9 8 9
-90 6 7 5.5 6
(a) (b) (c)

Figure 8(a)0 ºC at 3000X (b) -55 ºC at 1000X, (c) -90 ºC at 3000X
4. Concluding remarks
► Preliminary investigation was carried out to examine the microstructure and fracture
behavior of A516-70 steel used for the fabrication of Low Temperature Separator pressure
vessel used Petrochemical industry.
► The DBTT range of the as-received steel ranges roughly from -50 ºC to -80 ºC
► The DBTT range of the Post Weld Heat Treated samples is from -50 ºC to -80ºC.
► Results show that the welded region has transformed into an acicular and bainitic structure
as compared to the banded ferrite-pearlite structure of the as-received samples.
► The formation of bainitic structure responsible for very high toughness values obtained are
primarily due to very controlled post weld heat treatment.
Acknowledgement
Support and guidance provided by Prof. Dr. Fazal Ahmed Khalid (Dean) and Prof. Dr. Peter H.
Draper of faculty of Metallurgy and Material Engineering at Ghulam Ishaq Khan Institute of
Engineering Sciences and Technology. Also assisted by Mr. Muhammad Nawaz Qureshi,
Muhammad Hassan Yousaf and Tauqir Ahmed Awan.
228
References
1. B.Tanguy , J.Besson, R.Piques, A.Pineau, Ductile to brittle transition of an A508 steel
characterized by Charpy impact test Part II: modeling of the Charpy transition curve,
Engineering Fracture Mechanics ,72 , 2005, pp 413–434.
2. Richard M. Christensen Exploration of ductile, brittle failure characteristics through a two-
parameter yield/failure criterion, Materials Science and Engineering, A 394, 2005, pp 417–
424.
3. P. Hau¡silda,b,, C. Berdinb, P. Bompardb, Prediction of cleavage fracture for a low-alloy
steel in the ductile-to-brittle transition temperature range, Materials Science and Engineering
A 391, 2005, pp 188–197.
4. U. Eisele, J. Schiedermaier, Application of ductile fracture assessment methods for the
assessment of pressure vessels from high strength steels (HSS), International Journal of
Pressure Vessels and Piping, 81, 2004, pp 879–887.
229
DIRECT PRODUCTION OF SUPER-GRADE MATERIALS

IN NANO-PARTICLE BASED FUELS
Liviu Popa-Simil1, Claudiu Muntele2
1
LAVM LLC, Los Alamos, NM 87544
2
Center for Irradiation of Materials, Alabama A&M University, Normal, AL 35762
Keywords: Reactor Fuel, Nanomaterials, Direct Production, Super-Grade
Abstract
Nuclear transmutation reactions are based on the absorption of a smaller particle such as a
neutron, proton, deuteron, alpha, etc. The resulting compound nucleus gets out of its initial
lattice mainly by taking the recoil, also with help from its sudden change in chemical properties.
The recoil implantation is used in correlation with thin and ultra thin materials mainly for
producing radiopharmaceuticals and ultra-thin layer radioactive tracers. In nuclear reactors, the
use of nano-particulate pellets could facilitate the recoil implantation for breeding, transmutation,
and partitioning purposes. Using enriched 238U or 232Th leads to 239Pu and 233U production while
using other actinides such as 240Pu, 241Am etc. leads to actinide burning. When such a lattice is
immersed into a radiation resistant fluid (water, methanol, etc.), the recoiled product is
transferred into the flowing fluid and removed from the hot area using a concentrator/purifier,
thus preventing the occurrence of secondary transmutation reactions.
Introduction
The production of radioisotopes is mainly based on the transmutation reactions that occur when a
nucleus is changing its composition and structure under the influence of an incident neutron. The
nuclear fuel breeding reactions are of great interest for the world’s energy because they offer
total use of the Uranium and Thorium reserves, rather than selected isotopes.
The nuclear reactions desired for nuclear breeding are:
~ 239 ~
92 U → 93 Np + β + ν → 94 Pu + 2 β + 2ν
− −
U + 01n→ 239
238
92
239
(1)
for Plutonium production, and:

~ 233 ~
90Th→ 91 Pa + β + ν → 92 U + 2 β + 2ν
− −
Th + 01n→ 233
232
90
233
(2)
for Uranium production. These reactions are also accompanied by other parasitic reactions
resulting in the production of higher isotopes (see Figure 1). The undesired reactions in the
upper-left side of the picture are due to long exposure inside of the nuclear reactor to the neutron
flux.
The fast removal from the hot zone and good isotopic purity of the newly produced fuel
minimizes the probability of occurrence of undesired reactions and parasitic concentration in the
newly produced fuel.
231
Figure 1. Transmutation reaction diagram.
239
Holding the Pu longer in the nuclear reactor exposes it to fission and n absorption followed by
transmutation [1], according to the reaction:
239
Pu (n, γ )240 Pu (n, γ )241 Pu ⎯β⎯
(14.29 y ) 241
⎯⎯→ Am (3)
235
also shown in part in Fig. 1. Having low enriched Uranium fuel or residual U (0.1-0.5%) in the
depleted Uranium, depending on separation work optimization, results in neutron exposure, with
the probability of neutron absorption becoming important, and thus the occurrence of the
following chain of reactions:
U (n, γ )236U (n, y )237U ⎫

235
⎪ β (6.75 d ) 237
and ⎬ ⎯⎯ ⎯ ⎯→ Np (4)
238
(
U n,2n U ) 237 ⎪
⎭
then
237
Np (n, γ )238 Np ⎯β
⎯→ 238
Pu (5)
238
With a lifetime of 87 years, Pu is a valuable alpha source, mainly used in thermoelectric power
sources for space applications but undesirable in nuclear fuel due to its high associated
spontaneous fission coefficient.
The reactions shown in Eqs. 3-5 are what the new nanostructure-based procedure aims to
minimize, in order to extract a super grade Plutonium or Uranium.
In the current stage the fuel is processed together after a period of cooling of about 5-10 years in
the waste fuel pools by using the known processes Urex and Purex [2] that are based on hard
chemicals and exchanging resins being environmentally hazardous and expensive. The average
actual cost of plutonium WGP class is about $4K/g [3] driving high the price of energy produced
by using such fuels. To avoid the high level of radioactivity and the Plutonium contamination
with undesired isotopes, a procedure in which the fuel to be frequently removed at a period of 2-
3 month have been developed but has the disadvantage of handling to reprocessing high levels of
232
radioactivity. Another solution is to use the recoil nuclear reaction [4] to produce separation [5]
and a training agent to extract it from the hot area [6].
The Nuclear Recoil
There are practically 3 types of nuclear reactions of interest for 238U and 232Th:
(a) Absorb fast neutron (100 keV to 1.5 MeV); strictly on geometric grounds, some 40% of
recoils (0.42 to 6.3 keV, that is Rbead = 5 nm > R > Rmin = 2 nm) out of the bead and in the
interstitial fluid, see Figure 2. The fast neutron has to be generated within the same bead,
as any neutron from an adjacent cell would be slowed down in the interstitial
moderator/coolant.
(b) Absorb epithermal neutron (3 to 100 keV); strictly on geometric grounds, some 20%
recoils will have sufficient energy (14 to 420 eV) to get out (close to the bead’s surface,
Rbead = 5 nm > R > Rmin = 4 nm); for the rest, chemical incompatibility will be the main
driving factor. Considering a factor 10 increase in the absorption cross-section for
epithermal neutrons over fast neutrons, then we have an effective factor of 5 increase in
the number of recoils leaving the bead as a result of epithermal neutron capture nuclear
reactions vs. fast neutron capture nuclear reactions. The epithermal neutron could come
either from inside the bead or from near adjacent beads, therefore chances of such recoils
to occur are increasing further (by at least another factor of 6 in a cubic lattice
arrangement) than for the fast neutron case.
(c) Absorb thermal neutron, not enough recoil energy to get out, chemical incompatibility
will be the main driving factor. The thermal neutron could come either from inside the
bead or from near and distant adjacent beads, therefore chances of such absorption to
occur are better than for the epithermal and fast neutron cases. However, all the recoils
formed this way are not energetic enough to exit the bead strictly on kinematics
considerations. Chemical (non-) affinity and diffusion processes should be taken into
account in order to estimate the number of such products leaving the bead. Otherwise,
they are going to degrade and produce fast neutrons contributing to the breeding process
and to maintaining the chain reaction.
Fig. 2 – SRIM-2006 simulation for 238U recoil in 1nm urania and water
a) 239U recoil paths (left) b) 239U ranges and stopping profile (right)
The schematic diagram of the pellet
The ideal case for such a system to operate inside a nuclear reactor is to produce a structure
compatible with the irradiation channel. The most common process is using a plasma torch to
233
produce the urania and thoria powder at below micron particle size. At these dimensions their
buoyancy is different from that of the bigger size particles, being easily dragged by the
coolant/moderator flow.
Fig. 3 – The nano-powder pellet schematic diagram

To further be usable in a nuclear reactor flow there is necessary to produce a pellet/container
with a porosity controlled such that no grain/bead will escape, while allowing for normal flow of
the coolant/moderator fluid. Fig. 3 shows a cylindrical cladding structure that could be used to
contain the nano-powder between the lids formed by a metallic porous foil lids. Because the
diameters of the metallic sheet filters are in the micron range, an agglomeration of particles with
diameter in the micron range could be set in layers with a variation of the PM down to the
operational powder, and pressed inside as detailed in the zoom area in Fig. 3. The materials used
for manufacturing have to be compatible for nuclear reactor applications such as Aluminum,
Zircalloy etc. To compensate the reactor for the high absorption introduced in the channel, heavy
water could be used in order to minimize the undesired absorption and to be a neutron gain
compared with the light water used in rest or the reactor. Several cylindrical pellets could be
bundled together and introduced in an external tube where the collector liquid is slightly re-
circulated serving as a confinement layer with the role of containing the radioisotopes produced
to become open radioactive source and contaminate. The whole assembly is strictly confined in 2
layers with buffer liquid used for continuous contamination analysis. The collection liquids are
passed between the two internal tanks that may be transported into an upper external tank by the
control unit.
Nano-flow and diffusion
A key issue in designing optimal breeding structures is the understanding of the phenomena
inside the cylinder containing the beads, with emphasis on nano-flow and nano-cluster behavior
in intense radiation fields.
The inter-granular space making the flow tube has variable shape and small dimensions such that
a molecular flow regime occurs in some of the spaces, the liquid molecules interacting with the
newly transmuted fuel molecules leaving the grain.
The simulation of nuclear collision and energy transfer shows that the impacted nucleus recoils
in the interstitial space creating a Frenkel defect or leaves small lattices. The Frenkel defect
diffuses, and if no recombination occurs it stops at the lattices boundaries [8]. The nano-grains
234
are self-coated in thin layer to get a hydrophilic shell washed by the collection liquid as soon as
the particles become immersed.
The efficiency of collection depends on particle magnitude and nuclear reaction channel
parameters and on the shape of the neutron flux interacting with the cross sections of the main
elements.
The process prediction is based on a thermal spectrum starting from depleted urania or thoria
nano-powder. For 239Pu the direct recoil extraction rate is about 17% for 238UO2 grains of 5 nm
diameters while the washing factor is brought up to 95% even for bigger particles by enhanced
diffusion due to 239Neptunium incompatibility with the uranium dioxide lattice. Particles of 5 nm
are hard to produce, therefore a structure using particles of 100 nm has been simulated. The
extraction efficiency is better due to diffusion, which places most of the breeding products out of
the interface free to interact with the washing liquid, even at moderate temperatures. There is
also associated a radioactive background of about 10 keV/Pu and fission product background of
100-10 ppm The separation may be performed in-situ by electrolysis, centrifuge, paramagnetic
flotation, sediment accumulator and chemical processing. Other liquids as LBE, organic
compound may be used.
Conclusions
The advantage of the method and device using nano-structures consists in its ability of producing
small amount of isotopic materials easy to separate, using the nuclear reactors, with higher yield
than the accelerator based methods and requiring less chemistry.
The method of nano-breeding is susceptible of changing the productions of the most important
nuclear isotopes 233Uranium obtained from 232Thorium and 239Plutonium obtained from depleted
238
Uranium used in nuclear energy lowering their cost and opening the way for access to the
entire nuclear resources.
References
1. Taube, Plutonium - a general survey. NEA, 1974. wed-database.
2. OECD / NEA, Plutonium fuel - assesment. NEA, 1989. web.
3. NNSA, Weapon-grade plutonium and highly enriched uranium production, in Nuclear
Non-proliferation, U.A.C.a.D. Agency, Editor. 1996: Washington.
4. Muntele C. I., L.P.S., P. M. Racolta, D. Voiculescu,. The recoil implantation technique
developed at the U-120 cyclotron in Bucharest. in AIP. 1999. Denton, Tx.
5. Hoffman D.C., L.C.A., Researchers in California Discover Plutonium-231, The Long-
Sought Isotope. LBNL News, 1999. 1: p. 1-7.
6. Popa-Simil L., Nano-structures materials for Energy Direct Conversion and Fuel
Breeding. Cleantech, 2007. Proceedings(CD).
7. ZIGLER J.F., Stopping of energetic light ions in Elemental Matter. Journal of Applied
Physics, 1999. 85: p. 1249-1272.
8. WHITE R. J., The development of grain-face porosity in irradiated oxide fuel. Journal of
Nuclear Materials, 2004. 325(1): p. 61-77.
235
Synthesis and Microstructure of Si3N4-TiN nanocomposites
Mei Yang, Mingli Lv, Hongmin Zhu
School of Metallurgical and Ecological Engineering,

University of Science & Technology Beijing; Xueyuan Road 30; Beijing, 100083, China
Keywords: Coating, Si3N4-TiN, Conductive.
Abstract
Si3N4-TiN nanocomposite was prepared by in situ coating in liquid ammonia using TiCl4 and
Si3N4 as starting materials. The reduction reaction of TiCl4 by sodium was performed at around -
40°C and resulted TiN nano-powders which nuclei and grew on the surface of Si3N4 particles.
The composite powder was consolidated through spark plasma sintering (SPS) at 1600°C and
dense compact (>98% of theoretical) with grain size of less than 500 nanometers was obtained.
By compositing 20vol. % TiN to Si3N4, the electrical resistivity of the compact was reduced to
small enough value (3.6×10-3Ω·cm) for electrical discharge machining (EDM).
Introduction
Silicon nitride (Si3N4) is one of the most promising high temperature structural material in many
fields, such as aviation and aerospace [1], gas turbine engine [2-3]. However, due to its strong
hardness and strength, it’s difficult to machine this material to a complicated shape by traditional
technique. TiN shows a specific electrical conductivity like metal as well as good mechanical
properties and compatibility with Si3N4 [4-5]. Therefore, preparation of highly electroconductive
Si3N4-TiN composite through addition of TiN is helpful to machine it as desired by electrical
discharge machining (EDM). However, owing to its weak resistance to oxidation around 600°C
[6]
, reduction of TiN amount is preferable. Actually, current hot researches focus on fabrication of
highly conductive ceramic with least TiN amount. In-situ coating method using nanopowders as
second phase attracts great interest recently, because it saves TiN due to the large surface area of
nanopowders and improves the distribution of second phase to form a conductive network. TiN
amount from ≥30vol.% prepared by a mechanical mixture [7-8] was decreased to 25vol.%
prepared from TiN coating on Si3N4 surface [9-10]. In this method, TiN was formed from the
reaction of TiO2 with N2 or NH3 gas at 700-1000°C for three hours or even longer. Therefore, the
growth, agglomeration and impurity are still unavoidable during the process. According to the
report by Shimada et al [11], 17.5vol.% TiN is the least amount using Ti(O-i-C3H7)4 as source,
however, its relative density was also comparative low (under 60% theoretical density).
In this paper, an in-situ coating method of Si3N4-TiN nanocomposite powders directly at -40°C
in liquid ammonia was developed and spark plasma sintering (SPS) technique with short
sintering time and rapid rate of calefaction was used to limit the growth of TiN.
Synthesis of Si3N4-TiN nanocomposite powder

The staring materials used were titanium chloride and silicon nitride (average diameters: 0.3μm),
and sodium was used as reduction agent. The Si3N4 and TiCl4 were feed into one of double-
chamber flask and sodium was put into another one in the proportion of TiN volume in a glove
237
box. Liquid ammonia was added by evaporation-condensation transfer respectively and two
solutions of TiCl4-NH3 and Na-NH3 were formed at -40°C. By continuous stirring, Si3N4
powders were distributed uniformly in the solution. By mixing the two solutions, the reaction
occurred immediately, and TiN nanopowders deposited on the Si3N4 particles. The by-product of
sodium chloride was filtered and separated by liquid ammonia, and the Si3N4-TiN
nanocomposite powders were obtained.
Consolidation of Si3N4-TiN
A desired amount of TiN/Si3N4 nanocomposite powders (about 2g) under inert atmosphere were
put into a graphite die (15mm in diameter) and consolidated with Dr. Sinter 1050 spark plasma
sintering system (Sumitomo Coal Mining Co., Tokyo, Japan). The sample was heat in vacuum
(<10Pa) to 1450-1650°C at 100-200°C /min and held for 3-5min. The pressure was applied from
1000 and maintained at 50Mpa. For comparison, the composite powders of 20vol.%TiN/Si3N4
by milling using the nano TiN (prepared by liquid reduction, described in reference [12]) and the
same Si3N4 powders as starting materials were consolidated via the same sintering routes.
Characterization
The phase of powders and bulks with various TiN contents was analyzed with X-ray
diffractometer (MXP21VAHF, MAC science Corp., Japan) operated at 100kV and using CuKα
radiation (λ=1.5418Å). The coating morphology with maps of Ti, Si elements and microstructure
were observed by transmission and scan-transmission electron microscopy (JEM-2010cx, JEOL,
Japan，VG-HB603, Vacuum Generators, Hastings, UK) and Scanning electron microscopy
(SUPRA-55, ZEISS, Germany).
Using the Archimedes immersion method with distilled water as medium, the relative densities
of the bulks were calculated. The electrical conductivities of the composites were measured by a
four-point probe method. The effect of in-situ coating method on electrical resistivity was
analyzed comparing with mix method.
Figure1 shows the X-ray diffraction patterns of Si3N4-TiN composite powders with various TiN
contents respectively. The starting material as nuclei can be detected from the results of no TiN
content and be assigned to α-typed Si3N4. When the content of TiN (e.g. 10vol.%) was low, the
intensity of TiN’s peaks was weak and not distinct. With the increase of TiN content (to 20vol.
%), the board peaks appeared in highly accordance with cubic TiN. And the more content was,
the stronger its intensity was. It can be seen that composites are composed of α-typed Si3N4 and
TiN, which indicated that TiN powders were obtained from the reduction process, described in
ref. [12] and no other product was found. Judging from the figure, the broadening of TiN peaks
without any shift of location is attributed to the refinement of crystalline size. From classical
Scherrer equation, the diameter of TiN powders can be estimated and only equals to 12.1nm.
238
Fig.1 XRD of Si3N4-TiN nanocomposite powders with various TiN contents;
Morphologies of the starting materials-Si3N4 were shown in figure 2. The size of square Si3N4
particles is sub-micrometers about 0.1-0.3μm. The coating effect, Si3N4-20vol.%TiN as example,
is analyzed by STEM micrograph and X-ray elemental mappings including Si and Ti, shown in
figure 3. Comparing with the smooth surface, as shown in fig.2, the surface of bigger matrix
particles are covered uniformly with some smaller particles with average size of ~10nm after the
in-situ coating process.
Fig. 2 TEM images of Si3N4 powders.
The effect of coating could be approved by locations accordance of Si element and Ti element.
Because Si and Ti element root from Si3N4 and TiN respectively, the locations of elements
represent the locations of corresponding nitrides. Therefore, it can be seen that silicon element
mapping described the outline of Si3N4 particles identical to fig.2, which were used as nuclei.
From Ti elements mapping, it can be observed that TiN particles as coating phase were
distributed uniformly on the surface of Si3N4 powders, which formed a coating morphologies.
When liquid reaction occurred, the solid surface of Si3N4 particle provide nuclei with lower
energy for new phase formation than homogenous system. So, the nanocomposites powders with
coating microstructure were prepared by in situ coating directly.
239
Fig.3 STEM image of Si3N4 coated by 20vol.%TiN powder (a) and elemental mappings of Si (b)
and Ti (c).
In our previous work [13], TiN nanopowders show good sintering ability and densitified by SPS
at 1380°C with a crystalline size in the range of 100-150nm. It’s inevitable that addition of TiN
would facilitate consolidation of Si3N4 matrix and influence on sintering would be more
remarkable with contents of TiN increasing. In order to ensure enough density of bulks, the least
content of TiN (10 vol.%) in this work as criterion was used to estimate sintering conditions. The
sintering process began at 1400°C and densitification finished at around 1500°C. The relative
density was measured and reached 98.1% theoretical density.
Figure 4 shows SEM image of fracture surface of Si3N4-10vol.%TiN powders bulk. It can be
seen that the bulk possess uniform microstructure with the grain size of below 500 nanometers
and no pore was left which implying the dense degree of bulks. Figure 5 shows TEM image of
Si3N4-10vol.% TiN bulk. It can be seen that TiN particles were located in the boundary of grain,
as pointed by arrowheads. Other ratio composites were sintered at 1500-1600°C, which were
enough for consolidation.
240
Fig.4 SEM image of fracture surface of Si3N4-10vol.%TiN bulk
The electrical resistivity of the compacts sintered at 1600°C with a pressure of 50MPa holding
for 3min decreased with the increasing TiN content and met the requirement of EDM (3.6×10-
3
Ω·cm) for compositing 20vol.% TiN to Si3N4. While, for mixture even using nano-sized TiN
powders prepared with the same route, its electrical resistivity reached 107 order Ω·cm, which is
far higher than that of bulks prepared by in-situ coating. The reason may be attributed to easy
agglomeration of nanopowders, and then bad distribution. Therefore, when same sized starting
materials were used, in-situ has a stronger effect on its electrical resistivity.
Fig.5 TEM image of Si3N4-10vol.%TiN bulk
Conclusions
Si3N4-TiN nanocomposite was prepared by in situ coating in liquid ammonia. The reduction
reaction of TiCl4 by sodium at around -40°C was performed and resulted TiN nano-powders
which nuclei and grew on the surface of Si3N4 particle. The composite powder was sintered
though spark plasma sintering (SPS) at 1600°C and dense compact (>98% of theoretical) with a
mean grain size of <500 nanometers was obtained. The electrical resistivity value (3.6×10-3Ω·cm)
enough for electrical discharge machining (EDM) was reached by compositing 20vol.% TiN to
Si3N4.
241
Acknowledge
This research was sponsored by National Basic Research Program of China (973 Program),
2007CB613301 and National Natural Science Foundation of China 50374007.
References
1. J. Barta and M. Manela, “Si3N4 and Si2N2O for high performance radomes,” Mater. Sci. Eng.
71 (1985), p. 265–272.
2. H. Kaya, “The application of ceramic-matrix composites to the automotive ceramic gas
turbine,” Composite Sci. and tech., 59(1999), p861-872.
3. S. R. Choi., J. M. Pereira, L. A. Janosik and R. T. Bhatt, “Foreign object damage in flexure
bars of two gas-turbine grade silicon nitrides,” Mater. Sci. and Eng. A, 379 (2004) p. 411–
419.
4. Japan Metal Soc. ed., Metal Data Handbook (Tokyo: Maruzen Co., Ltd., 1993) p.275.
5. E. Blanquet, A.M. Dutron, V. Ghetta, C. Bernard and R. Madar, “Evaluation of LPCVD Me-
Si-N (Me=Ta, Ti, W, Re) diffusion barriers for Cu metallizations,” Microelectronic Eng.,
37/38 (1997), p.189-195.
6. Y. G. Gogotsi, F. Porz, and G. Dransfield, “Oxidation behavior of monolithic TiN and TiN
dispersed in ceramic matrices,” Oxidation of Metals, 39(1-2) (1993), p. 69-91.
7. A. Bellosi, S. Guicciardi and A. Tampieri, “Development and characterization of
electroconductive Si3N4-TiN composites,” J. Eur. Ceram. Soc., 9(1991), p.83-93.
8. B. T. Lee, “In situ synthesis of TiN-reinforced Si3N4 matrix composites using Si and sponge
Ti powders,” J. Mater. Sci., 34 (1999), p.6169-6176.
9. L. Gao, J.G. Li T. Kusunose and K. Niihara, “Preparation and properties of Si3N4-TiN
composites,” J. Eur. Ceram. Soc., 24 (2004), p. 381-386.
10. S. Kawano, J. Takahashi and S. Shimada, “Fabrication and spark plasma sintering of α-Si3N4
particles coated with nano sized TiN particles,” Key Eng. Mater., 206-213 (2002) , p.1125-
1128.
11. S. Kawano, J. Takahashi and S. Shimada, “The preparation and spark plasma sintering of
silicon nitride-based materials coated with nano-sized TiN,” J. Eur. Ceram. Soc., 24 (2004), p.
309-312.
12. H. M. Zhu, B.Y. Yuan and G. S. Sun, “Method for TiN Nanoparticles by Solution Phase
Reduction,” CN Patent ZL03106286.5
13. L.J. Wang, W. Jiang, L. D. Chen, M. Yang and H.M. Zhu, “Consolidation of nano-sized TiN
powders by spark plasma sintering,” J. Am. Ceram. Soc., 89 (2006), p. 2364-2366.
242
AUSTENITE GRAIN STABILITY OF LOW-MANGANESE, HIGH-

CHROMIUM CARBURIZING STEEL
Takeshi Fujimatsu1, Kazuya Hashimoto1, Shinji Fukumoto2, Atsushi Yamamoto2
1
Sanyo Special Steel Co., Ltd.; 3007 Nakashima Shikama-Ku; Himeji, Hyogo, 672-8677, Japan
2
University of Hyogo;2167 Shosha; Himeji, Hyogo,671-2201, Japan
Keywords: Carburizing Steel, Grain Coarsening, Austenite Grain, Hot Forging
Abstract
Since parts for the automotive drive train require lower cost as well as smaller size and lighter
weight for improvement in fuel consumption, carburizing steel for those parts is expected to have
low cost, high cold formability and machinability and high strength. We found that the steel with
lower manganese and higher chromium than conventional carburizing steel meets these needs. It
was also confirmed that this steel showed higher criterion in austenite grain coarsening
temperature during carburizing than conventional steel. In the present study, the improvement
mechanism of austenite grain coarsening temperature of this steel was discussed.
Introduction
Parts for automotive drive train, e.g. gears and shafts, have required lower cost as well as smaller
size and lighter weight for improvement in fuel consumption. Carburizing steel for those parts is
expected to have low cost, high cold formability and machinability and high strength. Although
additions of nickel and/or molybdenum improve its strength, it causes high cost and deterioration
in formability and machinability. We found that the steel with lower manganese and higher
chromium meets these needs. An increase in chromium content of steel contributed to keep its
hardenability, when manganese content of the steel was lower than conventional steels. In
addition, since chromium has smaller solution strengthening effect than manganese, the steel
with lower manganese and higher chromium shows higher formability and machinability. The
steel also shows high strength, because, in steel with lower manganese, a formation of oxidized
layer, which could be a fracture origin on the surface, during carburizing was alleviated. Since
high temperature treatment shortened the carburizing time, it is preferable from the viewpoint of
production cost. At the same time, since grain size after carburizing strongly affects the strength
of steel, it is important to prevent grain coarsening during carburizing. As a result, higher
criterion in austenite grain coarsening temperature for carburizing steel is required. Bainitic and
martensitic structures are often observed in hot forged steel parts. It is known that the bainite
bearing structure has disadvantage in grain growth stability during carburizing [1]. We have
found that the hot-forged low-manganese, high-chromium carburizing steel shows a higher grain
coarsening temperature than conventional steel. In this study, the microstructures of steels with
different manganese and chromium contents are investigated at various stages from hot forging
to carburizing processes and the improvement mechanism of austenite grain coarsening
temperature is also discussed.
The chemical compositions of steel A, B, C and D are shown in Table 1. The steel B is JIS
SCR420 carburizing steel. In order to provide almost same density of AlN precipitates to
specimens, aluminum and nitrogen contents of steels were made even. Ingots prepared by a
vacuum induction furnace were hot forged to 65mm in diameter of bars after heating at 1523K
243
for 10.8ks, and then normalized at 1173K for 10.8ks followed by air-cooling. For hot forging, the
specimens with 8mm in diameter and 12mm in length were cut out from the middle section of
the bar. Figure 1 shows a hot forging schedule on the forging simulator. After hot forging, almost
all microstructures of these specimens consisted of bainite and martensite. These phases were
confirmed by optical microscope, and by hardness and transformation start temperature. The
prior austenite grain sizes of hot forged specimens were observed by optical microscope at
middle section. To confirm the grain size at initial stage of carburizing, each hot-forged
specimen was reheated to 1123K with 300K/h for 1.8ks and followed by quenching in water.
The average grain size was measured by linear intercept method. For the evaluation of the grain
coarsening temperature, hot-forged specimens were reheated to 1473K
Forging
1223 to 1348 K with 300 K/h for 21.6ks and followed by 1373K
quenching in water. The grain coarsening temperature was 5K/s
determined when the presence of a coarse grain as large as 473K
ASTM No.3. To observe the nucleation site of austenite from 60s 480s 11s 180s
A.C.
hot-forged microstructure, specimens were reheated to 1013 to Fig.1 hot forging process
1083 K with 300 K/h for 180s and followed by quenching in
water and observed the microstructures.
Table 1 Chemical composition of steels (mass%)

Steel C Si Mn P S Ni Cr Al O N
A 0.202 0.20 0.35 0.014 0.012 0.09 2.11 0.027 0.0012 0.0171
B 0.218 0.20 0.82 0.013 0.013 0.09 1.39 0.024 0.0019 0.0193
C 0.215 0.21 0.80 0.014 0.006 0.10 0.92 0.022 0.0016 0.0179
D 0.212 0.23 1.23 0.015 0.013 0.09 0.91 0.025 0.0021 0.0187

Microstructures after hot forging and reaustenitization
Figure 2 shows the prior austenite grains after hot forging. Every specimen had almost the same
sizes of coarse grain. Figure 3 shows the prior austenite grain after reaustenitization at 1123K
and followed by quenching in water. Grain size of reausutenitized specimens was finer than that
of hot-forged specimens. Steel A with low-manganese, high-chromium contents showed
relatively coarse and uniform grains compared with those in the other steels. Steel B, C and D
showed small and non-uniform grains. Especially, steel B had a considerable size variation of
grain. Since grain size of the hot-forged steels was almost the same in specimens, it was
estimated that this size variation of grain was due to the influences of austenite nucleation and
growth behavior during reheating.
(a) (b) (c) (d)
Fig.2 Microstructures of hot forged steels etched with saturated picric acid. 50µm
(a) steel A, (b) steel B, (c) steel C, (d) steel D
244
(a) (b) (c) (d)
(13.8µm) (12.2µm) (12.6µm) (11.4µm)

Fig.3 Microstructures of hot forged steels reheated to 1123K for 1.8ks and quenched in water. Average 50µm
prior austenite grain diameter shown in photos. (a) steel A, (b) steel B, (c) steel C, (d) steel D
Grain coarsening property

Table 2 shows the grain coarsening temperature of each steel. Steel
Table 2 Grain coarsening
A showed the highest grain coarsening temperature, 1348 K, in temperature of steels.
these steels. It was 50K higher than the conventional steel B. As Steel A 1348K
the higher manganese and the lower chromium in steels, the grain Steel B 1298K
coarsening temperature became lower in this study. Steel D had the Steel C 1248K
lowest grain coarsening criterion, 1223K. Since many coarse Steel D 1223K
grains as large as ASTM No.3 were observed in steel D, the grain
coarsening started at lower temperature. It was estimated that higher grain coarsening
temperature in steel A would be caused by relatively coarse and uniform grains. That is, the steel
with coarse and uniform grains has low grain boundary energy [2] and small differences of grain
boundary energy of neighboring grains [3]. Carburizing steel with lower manganese and higher
chromium contents stabilizes the austenite grain during carburizing.
Austenite nucleation and growth from hot-forged microstructure

It was found that relatively coarse and uniform grains were obtained through the hot forging and
reaustenitizing of low-manganese, high-chromium carburizing steel. Figure 4 shows
microstructures of hot-forged steel A and D which were reheated to given temperatures with 300
K/h for 180s and quenched in water. In steel A, austenite nucleated at around 1063K and
relatively coarse, globular martensitic grains were observed along and inside the prior austenite
grain boundary. These martensitic grains transformed from austenite by quenching. At 1083K,
many impingements of grown-up grains were observed. In steel D, austenite nucleation was
observed at 1013K which is lower than that in steel A. At 1033K, small and globular austenite
grains were found along the prior austenite grain boundary. At 1073K, those grains grew slightly
and new small grains precipitated around the grown-up grains. Inside the prior austenite grains
seemed not to be transformed yet. Austenite nucleation and growth behavior of steel C was
similar to steel D and that of steel B was intermediate between steel A and steel C, D.
(a) (b) (c) (d)
Fig.4 Microstructures of the hot forged and reheated steels etched with saturated picric acid. 50µm
Steel A was reheated at (a) 1063K, (b) 1083K and steel D was reheated at (c) 1033K, (d) 1073K.
Heating rate was 300K/h and holding time was 180s and followed by quenching in water.
The difference on austenite formation behavior was clarified by scanning electron microscope
(JEOL JSM-6360). In Fig.5, microstructural differences were observed by etching with saturated
picric acid and 5 % nital. The microstructure inside the prior austenite grain in steel D at 1073K
245
consisted of lamellae structure of ferrite and martensite as shown in Fig.5(d). Martensitic
structures transformed from austenite by quenching. These lamellae structures were also clearly
identified in steel C. Since these structures were formed in prior austenite grain in steel C and D,
the growth of the previously-precipitated austenite grains seemed to be restricted. In
consequence, noticeable non-uniform grains must be provided. Although similar lamellae
structures existed in steel A, it was found that most of microstructure inside the grains consisted
of ferrite and globular martensite as shown in Fig.5(a). In this case, the austenite grains along the
grain boundary seemed to be ready to grow immediately. It was estimated that this favorable
behavior of austenite nucleation and growth was promoted by lower manganese and higher
chromium contents.
(a) (b) (c) (d)
M
M
M
F
M M F M M
F M
Fig.5 Scanning electron micrographs of the hot forged and reheated steels etched with saturated picric 10µm
acid and nital. (a) Steel A was reheated at 1083K, (b) steel B and (c) steel C were reheated at 1063K,
(d) steel D was reheated at 1073K. Heating rate was 300K/h and holding time was 180s and followed by
quenching in water. M represents martensite transformed from austenite by quenching and F represents ferrite.
Improvement mechanism of grain coarsening property

Improvement mechanism of grain coarsening property of hot-forged, low-manganese, high-
chromium carburizing steel was presumed as follows.
• In the initial stage of reaustenitization from hot-forged, bainitic and martensitic structures,
globular austenite grains precipitated along the prior austenite grain boundary and inside
grain. These grains grew immediately until their impingement.
• As a result, relatively coarse and uniform grain structure was formed after completing
austenitization. Total grain boundary energy and the difference of grain boundary energy of
neighboring grains were low due to coarse and uniform grain. In consequence, grain
coarsening is dominantly suppressed during carburizing.
This steel is expected to show the high strength even when high-temperature rapid carburizing is
applied.
Summary
(1) When hot-forged steel with bainitic and martensitic structures was carburized, the steel with
lower manganese and higher chromium contents showed higher grain coarsening temperature.
(2) Since lamellae structure of ferrite and austenite in the prior austenite grain is less likely to
evolve in hot-forged, low-manganese, high-chromium steel, the globular austenite grains
grow immediately and relatively coarse and uniform grains result, where grain coarsening is
less likely to occur.
References
1. T.Tamatani et al., Netsu Shori, 37 (1997), 356-361.
2. S.Takaki, Netsu Shori, 34 (1994), 260-264.
3. T. Gladman, Proc. Roy. Soc. A., 294 (1966), 298-309.
246
Development of High Strength Non-Oriented Electrical Steels
Hee Yong Park1, Sam Kyu Chang1, Bruno De Cooman1

1
Graduate Institute of Ferrous Technology, POSTECH,
San31, Hyoja-dong, Nam-gu, Pohang, Gyungbuk, 790-784, South Korea
Keywords: Non-Oriented Electrical Steel, Yield Strength, Core Loss
Abstract
Non-oriented electrical steel requires high yield strength to withstand the cyclic load when used
in large motors. To achieve high yield strength with the least deterioration of its magnetic
properties, a new-alloyed electrical steel of 2Si-0.7Mn-1.5Al with the addition of elements such
as nickel, niobium, molybdenum and manganese was tested. The optimum level of yield
strength and core loss was obtained by solid solution hardening effect from addition of
manganese.
Introduction
Current electrical steels usually are not fatigue resistant; thus, fatigue failure can occur during
operation, in motors for example, due to cyclic high frequency overload. For electrical steels,
only magnetic properties were considered, and mechanical properties were ignored. However,
in real life non-oriented electrical steels used in motors have forces acting on it; therefore,
mechanical properties should also be considered. For the electrical steels to be implemented in
large motors used in power plants, ship, aircraft and etc, it is essential to overcome this problem
by increasing the yield strength of the electrical steel with the least deterioration of its magnetic
properties.
The present work focuses on developing advanced non-oriented electrical steels, which could be
used in large motors. The reference steel was designed with 2Si-0.7Mn-1.5Al. Some special
elements such as nickel, niobium, molybdenum and manganese were added to increase the yield
strength. Nickel was proven effective in decreasing the core loss and increasing the magnetic
flux density [1]; therefore, it was added to increase the yield strength by solid solution hardening
with less deterioration of magnetic properties. Niobium and molybdenum were added for the
same reason despite the addition of two elements is expected to increase the core loss as a result
of precipitates formed by these added elements. Manganese was also added to increase the
yield strength to determine the effect on the magnetic properties by solid solution hardening.
Four steels were melted in a 30kg vacuum furnace and their chemical compositions are shown in
Table I. Steel A is a reference material and was used to compare to the other three steels to
investigate the effects of added elements on the magnetic properties and yield strength. Ingots
were hot rolled to a thickness of 2.5mm, normalized at 1000°C, and cold rolled to 0.5mm.
Then cold rolled samples were annealed at two conditions: 850°C for three minutes and 950°C
for five minutes.
247
Table I. Chemical composition (wt. %) of test steels
Steel C Si Mn P S T-Al Additional Elements
A 0.0022 1.87 0.701 0.003 <0.003 1.33
B 0.0025 1.98 0.792 0.002 <0.003 1.58 X1 (Ni + Mo)
C 0.0021 2.02 0.699 0.002 <0.003 1.50 X2 (Nb + Mo)
D 0.0075 1.95 X3 0.004 <0.003 1.51
X1, X2 and X3 cannot be opened because of confidential reasons.
Magnetic properties were measured by a single sheet test method, and yield strength was
measured by a tensile test.
Results
1. Magnetic Properties and Anisotropy

Core loss and magnetic flux density are shown in Table II. Steel D annealed at 850°C for five
minutes showed the lowest core loss of 3.034W/kg, and Steel C annealed at 950°C for five
minutes showed the highest core loss of 4.321W/kg. For magnetic flux density, Steel B
annealed at 850°C for three minutes had the highest value of 1.619T, and Steel C annealed at
850°C for three minutes had the lowest value of 1.562T. Compared to the reference Steel A, the
addition of Nb and Mo had a great effect on the reduction of magnetic properties, whereas the
addition of Ni and Mn improved the magnetic properties. Regarding the magnetic anisotropies,
all steels exhibited very low anisotropies of both core loss and magnetic induction.
TABLE II. Core loss and magnetic flux density of test steels
Steel Annealing Core Loss Anisotropy Magnetic Induction Anisotropy
Temperature W15/50 (W/kg) (%) B50 (Tesla) (%)
(°C)
WL[a] WT Mean ΔW[c] BL[b] BT Mean ΔB[d]
A 850-3min 3.609 3.633 3.621 0.33 1.620 1.566 1.593 1.69
B 850-3min 3.228 3.329 3.279 1.54 1.638 1.599 1.619 1.20
C 850-3min 4.144 4.165 4.155 0.25 1.586 1.538 1.562 1.54
D 850-3min 3.016 3.052 3.034 0.59 1.607 1.579 1.593 0.88
A 950-5min 3.234 3.235 3.235 0.02 1.626 1.567 1.597 1.85
B 950-5min 3.340 3.344 3.342 0.06 1.601 1.561 1.581 1.27
C 950-5min 4.257 4.384 4.321 1.47 1.597 1.552 1.575 1.43
D 950-5min 3.070 3.071 3.071 0.02 1.614 1.601 1.607 0.40
[a] WL is longitudinal core loss and WT is transverse core loss.
[b] BL is longitudinal magnetic induction and BT is transverse magnetic induction.
[c] ΔW is core loss anisotropy expressed as |(WL-WT)/(WL+WT)|.
[d] ΔB is magnetic induction anisotropy expressed as |(BL-BT)/(BL+BT)|.
2. Yield Strength
Table III shows the yield strength of different steels. Steel C annealed at 950°C for five minutes
had the highest yield strength of 375.6MPa and Steel A annealed at 950°C for five minutes had
the lowest yield strength of 350.3MPa. Steel B, C and D were all able to obtain higher yield
strength than the reference Steel A. The experiments prove the addition of Mn, Ni, Nb, Mo and
B was all effective in increasing the yield strength; however, Nb and Mo were the most effective.
248
TABLE III. Yield strength of test steels
Steel Annealing Temperature Yield Strength Tensile Strength Uniform Elongation
(°C) (MPa) (MPa) (%)
A 850-3min 333.9 460.1 20.5
B 850-3min 358.0 475.6 16.9
C 850-3min 367.7 502.5 17.9
D 850-3min 369.3 483.8 16.2
A 950-5min 320.3 432.0 16.7
B 950-5min 352.6 468.3 15.8
C 950-5min 375.6 515.5 17.7
D 950-5min 364.3 468.4 14.5
Discussion
1. Effects of the Alloys on Magnetic Properties

The reference Steel A, bearing 1.87% Si, 1.33% Al and 0.701% Mn, shows magnetic induction
of 1.593T and core loss of 3.621W/kg when it was annealed at 850°C for three minutes and
magnetic induction of 1.597T and core loss of 3.235W/kg when it was annealed at 950°C for five
minutes. Of the test steels, Steel D containing Mn had the most desirable magnetic properties
and Steel C containing Nb and Mo had the least desirable magnetic properties. That is, Nb and
Mo form chemical compounds such as carbide precipitates that deteriorate the magnetic
properties of the steel, whereas Ni and Mn does not form carbide precipitates thus does not
hinder magnetization.[1] Therefore, Ni and Mn are presumably effective on permeability and
eddy current because of free carbides compared to Nb and Mo. In case of steel B where Ni, Mo
and B were added, Ni improved the magnetic properties but Mo canceled out its effect. [1]
2. Correlation of Yield Strength with Magnetic Properties

The reference Steel A contains higher content of Mn and Al than the typical electrical steel that is
available in market. Steel A that was annealed at 950°C for five minutes had yield strength of
320.3MPa and core loss of 3.342W/kg. The commercial electrical steel that is in the market
with similar core loss of 3.03W/kg had yield strength of 266.7MPa. The addition of Mn and Al
allowed an increase of yield strength of the electrical steel. Moreover, higher yield strength was
obtained from Steel C and D; nonetheless, Steel C had high core loss whereas Steel D had low
core loss. The yield strength of Steel C was increased due to precipitation hardening resulted
from Nb and Mo addition that forms carbide precipitates that hinder magnetization; consequently,
high core loss was obtained. However, the yield strength of Steel D was increased due to the
solid solution hardening by Mn addition which does not deteriorate the magnetic properties. In
case of Steel B, both solid solution hardening by Ni and precipitation hardening by Mo increased
the yield strength. The addition of Ni increased the magnetic properties but the carbide
precipitates that are formed by addition of Mo deteriorated the magnetic properties. [1]
Conclusions
The effects of the addition of Mn, Ni, Nb and Mo to non-oriented electrical steels on magnetic
properties and yield strength are as follows:
z Addition of Mn and Ni decreases the core loss while addition of Nb and Mo increases
the core loss.
z Addition of all four alloys, Mn, Ni, Nb and Mo, increases the yield strength, but Nb and
Mo were the most effective.
249
Optimum results with high yield strength and low core loss was obtained by using solid solution
hardening by Mn addition.
Reference
[1] S.K. Chang, “Effects of Co, Mo, and Ni on Magnetic Properties in 3Si-0.1Sn-0.08Sb Alloyed
Non-oriented Electrical Steels”, J. Mat Sci (2006) 41:7380-7386
250
CHARACTERISTICS OF HYBRID SOLID SOLUTION LAYER FORMED

ON THE SURFACE OF 316 L AUSTENITIC STAINLESS STEELS
Ozgur Celik, Huseyin Cimenoglu, Eyup Sabri Kayali
Istanbul Technical University; Department of Metallurgy and Materials Engineering; Maslak,

Istanbul, 34469, TURKEY
Keywords: Austenitic Stainless Steel, Nitriding, Wear, Bioactivity
Abstract
Among metallic implant materials, AISI 316L quality austenitic stainless steel is extensively
used in manufacturing of orthopedic implants. Although it exhibits very good corrosion
resistance in many acidic environments, synergetic attack of corrosion and wear in the body
causes severe surface damage and loosening of the implant. It has been reported that surface
modification of austenitic stainless steels by forming nitrogen supersaturated surface layer
through plasma nitriding provides improvement in both wear and corrosion resistances. In the
present study, hybrid nitrogen and carbon supersaturated austenite layer has been formed on the
surface of a 316L quality austenitic stainless steel by nitriding in a fluidized bed reactor. After
nitriding, the steel exhibited superior surface hardness and wear resistance than as-received state
without any significant change in the mechanical properties as well as in vitro bioactivity
behavior.
Introduction
Among the metallic biomaterials, austenitic stainless steels (mostly 316L and Rex 734) are
preferred for load bearing components such as artificial hip joint because of their relatively low
cost, ease of fabrication and good corrosion resistance [1-3]. However, the implantation time of
an orthopedic implant with mobile parts is approximately 10-15 years due mainly to the
combined effect of wear and corrosion progressed in the human body [1]. Figure 1 presents the
micrograph of an austenitic stainless steel femoral head surface, after 17 years of use. Randomly
oriented numerous scratches were produced in vivo. Although the material removed from surface
is not great, the creation of wear debris may result in implant loosening as well as adverse
biological reactions (i.e toxicity and/or allergy) in unsightly staining of tissues surrounding the
implant. Therefore, in order to extend the implantation time of any total joint replacement by
preventing failure of the bone-implant system, wear debris creation must be mitigated [1, 4-6].
The main aim of this work is to improve the wear resistance of a 316L quality austenitic stainless
steel in order to extend the life of the orthopedic implant to 20-25 years through nitriding in a
fluidized bed reactor. Although the surface hardening by conventional nitriding methods is quite
effective process for many steels, it is not convenient for stainless steels due to loss of corrosion
resistance, which arises from precipitation of chromium nitride [7-11]. In 1986 a new plasma
nitriding process which leads enhancement of wear resistance without compromising the
corrosion performance has been proposed for austenitic stainless steels [12-15]. This new plasma
nitriding process has received much interest because of formation of nitrogen supersaturated
austenite layer (expanded austenite) on the surface without precipitation of chromium
nitride [16-20]. Recently, further improvement on surface properties of austenitic stainless steels
has been reported through addition of a small amount of carbon containing gas to the plasma
251
nitriding atmosphere to form an hybrid nitrogen and carbon supersaturated austenite
layer [21, 22].
Figure 1. Scanning electron microscope image of an austenitic stainless steel femoral head
surface after 17 years implantation [4].
Experimental
In the present study 316L quality austenitic stainless steel was nitrided in a fluidized bed reactor
by considering parameters of plasma nitriding process [10,18,23]. Nitriding atmosphere was an
ammonia and nitrogen gas mixture. In the fluidized bed reactor, Al2O3 powders were used as the
gas carrier.
Characterization of the as-received and nitrided alloys was made by microstructural survey,
mechanical tests, and in vitro bioactivity tests. Microstructural survey was carried out by light
optical microscope (LOM) examinations, X-ray diffraction (XRD) and glow discharge optical
spectrometry (GDOS) analysis. LOM studies were performed by utilizing Leica DM 6000M
microscope after etching with 50 % HNO3 + 50 % HCl solution. XRD analysis was carried out
by utilizing CuKα radiation with the incidence beam angle of 2o on a Philips RV 3710
diffractometer. Depth profiles of interstitial atoms in the nitrided layer were obtained by a
JY-5000RF Horiba-Jobin Yvon glow discharge optical spectrometer.
Hardness, tension, bending and wear tests were conducted to compare the mechanical properties
of as-received and nitrided alloys. Hardness measurements were performed on the surfaces of the
alloys with a Vickers pyramid indenter under indentation load of 10 g by using a CSM
microhardness tester. Tensile tests were conducted on Dartec universal testing machine with
strain rate of 10-3 1/s. Three-point bending tests were carried out until the arms of the sample
becomes parallel (bending of 180°) on a Shimadzu universal testing machine. The wear tests
were conducted on a CSM tribometer having ball-on-disc configuration in dry sliding conditions
and in simulated body fluid solution [24] by applying a normal load of 2 N to the surfaces of the
samples with 10 mm diameter Al2O3 ball. The sliding speed of the ball on the surfaces of the
samples was 0.15 m/s for a total sliding distance of 300 m. After the wear tests, the wear tracks
formed on the samples were detected by a Veeco Dektak 6M profilometer to quantify the test
results in terms of volume loss. Volume loss values were then converted into Relative Wear
Resistance (RWR) by assuming the RWR of as-received 316L in dry air sliding condition as 1.0.
In vitro bioactivity tests were carried out by immersing the samples in simulated body fluid
(SBF) bath at 37°C. Each sample stored in SBF bath for 30 days, which was continuously stirred
with a speed of 80 rpm. After removing from the SBF bath, samples were washed with distilled
252
water and dried with air. Surfaces of the samples were then investigated by an energy dispersive
spectrometer (EDS) equipped Jeol JSM-7000 F scanning electron microscope (SEM) to detect
formation of hydroxyapatite on the surfaces in vitro.
Microstructure
Figure 2 presents LOM micrograph of the cross-section of the nitrided 316L austenitic stainless
steel. Upon nitriding a 5 µm thick uniform layer formed on the surface. The XRD patterns
presented in Figure 3 display typical austenite peaks for the as-received alloy and expanded
austenite peaks for the nitrided alloy. When compared to the as-received state, nitriding
broadened the austenite peaks by shifting them to lower angles. It should be noted that no
carbide and nitride peaks were appeared on the XRD patterns. Figure 4 depicts profiles of carbon
and nitrogen from surface to the inner sections for the nitrided alloy. Presence of carbon peak at
a certain depth indicates that nitriding in the fluidized bed produced a hybrid-layer with a large
nitrogen enriched layer on top of a thin carbon enriched layer. Carbon accumulation may arise
from the propane gas used for firing of the exhaust gas of the fluidized bed reactor.
20 μm
Figure 2. Cross-sectional LOM micrograph of the nitrided 316L austenitic stainless steel.
Figure 3. XRD patterns of as-received and nitrided 316L austenitic stainless steels (γ and γex
represents austenite and expanded austenite, respectively).
253
Figure 4. Nitrogen and carbon concentration profiles for nitrided 316L austenitic stainless steel.
Mechanical Properties
Mechanical properties of the as-received and nitrided alloys are listed in Table I. The applied
nitriding treatment effectively improved both the surface hardness and the wear resistance of the
examined 316L austenitic stainless steel. When compared to the as-received state, the
improvement of the surface hardness and the wear resistance of the nitrided alloy is more than
five fold. Since no cracking was detected after bending tests, it is interesting to note that such a
remarkable surface hardening did not accompanied by an embrittlement. Although slight
increase in strength along with a small reduction in tensile ductility were detected, tensile
properties of the nitrided alloy meet the required tensile properties of 316L stainless steel
according to ASTM A240 standard.
Table I. Mechanical properties of as-received and nitrided 316L quality stainless steels.
Condition Hardness Tensile Bending Wear Test
Test Test Test (RWR)
Surface Yield Tensile Elongation Reduction 180° Dry Simulated
Hardness Strength Strength at Fracture of Area Bending Air Body
(HV0.01) (MPa) (MPa) (%) (%) Result Fluid
As-received 293 454 592 49 72 No 1.0 1.6
cracking
Nitrided 1535 487 623 44 70 No 7.5 10.3
cracking
In vitro Bioactivity Tests

Figure 5 shows SEM micrographs and EDS analyses of samples immersed in SBF solution for in
vitro bioactivity test. Homogenously distributed precipitates were detected on the surfaces. The
EDS results revealed that these precipitates were composed of Ca and P, which can be
considered as a preliminary signal of bioactivity. Thus, presence of Ca and P in the precipitates
can be associated with hydroxyapatite precipitation onto the surfaces as a result of the reaction of
the surrounding body fluid after immersion in SBF. Finally, it is concluded that the examined
316L austenitic stainless steel exhibited almost similar bioactivity in both as-received and
nitrided states.
254
Condition SEM micrographs EDS analyses
As-
received
Nitrided
Figure 5. SEM micrographs and EDS analyses of 316L austenitic stainless steel samples
immersed in SBF solution.
Conclusion
It is possible to form a hybrid solution layer on the surface of a 316L austenitic stainless steel in
a fluidized bed reactor, without precipitation of chromium nitride and/or carbide. When
compared to the as-received state, the nitrided alloy exhibited superior surface hardness and wear
resistance. It should be noted that the applied nitriding process did not significantly alter the
mechanical (tensile and bending) properties as well as in vitro bioactivity behavior of the
316L austenitic stainless steel.
References
1. B.D. Ratner et al., eds., Biomaterials Science: An Introduction to Materials in Medicine (San
Diego, CA: Academic Press, 1996), 37-50.
2. D.H.Kohn, “Metals in medical applications”, Current Opinion in Solid State and Materials
Science, 3 (1998), 309-316.
3. P.A. Dearnley, “A review of metallic, ceramic and surface-treated metals used for bearing
surfaces in human joint replacements,” Proc Instn Mech Engrs, 213 H (1999), 107-135.
4. P.A. Dearnley, “A brief review of test methodologies for surface-engineered biomedical
implant alloys,” Surface and Coatings Technology, 198 (2005), 483-490.
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stainless steels,” Biomaterials, 22 (2001), 641-647.
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265
Effects of Mo and Ni on Textures and Magnetic Properties in 3%Si Non-

oriented Electrical Steels
S. K. Chang
Graduate Institute of Ferrous Technology, POSTECH, Pohang, 790-784 Korea
Keywords: Magnetic Induction, Core Loss, Magnetic Anisotropy, Texture Factor.
Abstract
With the addition of Mo and Ni to high-alloyed non-oriented electrical steels with 3Si-0.1Sn-
0.08Sb, Ni increased grain size more than Mo. A very low level of core loss (W15/50 = 2.2
Watt/Kg) and high magnetic induction (B50 = 1.7 Tesla) were obtained in the Ni added steel.
However, Mo deteriorated the magnetic properties substantially. With respect to the texture effect
on magnetic properties, core loss decreased and magnetic induction increased proportionally to
texture factor (ratio of the sum of cube and Goss texture to γ fiber), while correlations of
anisotropies of core loss and magnetic induction to the texture factor appeared parabolic.
Introduction
Electrical steels are used as core materials for electrical products such as transformers, motors,
and generators and thus require high magnetic induction and low core energy loss at use. There
are two types of electrical steels, grain-oriented (GO) and non-oriented (NO). GO steels are
grain-oriented in a specific direction consisting mainly of Goss orientation of (110)[001] which
is very favorable to magnetic properties of induction and core loss, and are thus used mainly for
transformer cores. Manufacture of GO steels consists of complicated processes and there are
many difficulties associated with controlling Goss orientation. In contrast, NO steels do not
require a unidirectional orientation because they are used for electrical rotary devices such as
motor cores.
In the present work, the author attempted to develop advanced non-oriented electrical steels
having extremely low core loss, together with high magnetic induction to substitute for grain
oriented steels which are expensive and difficult to manufacture. In order to gain high
magnetically efficient steels, it is necessary to add large quantities of silicon and special elements
in non-oriented steels. The reference steel was designed with 3Si-0.1Sn-0.08Sb. Some special
elements such as molybdenum and nickel were added to maximize magnetic properties. Silicon
is used as a main element in electrical steels because it has high electrical resistivity. Tin and
antimony were proven effective in decreasing core loss and increasing magnetic flux density [1].
Such trial chemistries for non-oriented steels have never been investigated to substitute for grain
oriented steels, nor have additional elements of molybdenum and nickel to non-oriented steels
been tested. Although these elements are known to have lower electrical resistivity than silicon
and similar magnetic anisotropies to silicon, their effects on magnetic properties were not proven
and so must be investigated as well as further evaluation of its relationship with texture is
required.
Chemical compositions of test alloys are shown in Table I. Steel A is a reference material and the
other three alloys are compared with it to evaluate the effects of each element on magnetic
properties. Ingots were hot rolled to a thickness of 2.6 mm, cold rolled to 0.35 mm, and annealed
267
at 1000 °C for two minutes in an oxidation free atmosphere.
Table I. Chemical compositions (wt. %) of test steels

Steel C Mn Si Al Sn Sb Mo Ni
A 0.0058 0.308 2.90 1.52 0.101 0.078
B 0.0039 0.310 2.9 1.52 0.104 0.077 0.053
C 0.0035 0.309 2.92 1.51 0.105 0.078 0.054
Magnetic properties were measured by the single sheet test method. Texture measurements were
performed at the surface of the annealed specimens. The (110), (200), and (211) pole figures
were measured to a maximum tilt angle of 75 degrees by X-ray diffractometer by using Cu Kα
radiation. The ODFs were presented as a plot of constant φ2 section with intensity contours
defining Euler angles of φ1, Φ, and φ2 in the Euler space. Crystallographic textures were
analyzed from the ODFs by using software [2]. Quantitative texture analysis was carried out to
calculate volume fractions of ideal components of all possible crystallographic orientations. The
intensities of the ODFs within 15˚ from the exact point of each texture in the Euler space were
integrated [3]. The texture effect was evaluated as a texture factor expressed as a ratio of the sum
of volume fractions of cube and Goss textures to volume fraction of γ fiber, to weigh texture
effectiveness on magnetic induction and core loss.
Results
Magnetic properties
Core loss and magnetic flux density are shown in Table II. Steel containing Ni showed the lowest
core loss of 2.2 W/Kg but Mo bearing steel showed the highest core loss, 2.4 W/Kg. However,
magnetic flux density is inverse to core loss, that is, Ni-steel showed the highest level of 1.68
Tesla but Mo-steel the lowest level of 1.65 Tesla. Of note, a core loss of 2.2 W/Kg in non-
oriented steels is an extremely low level which has never been obtained. Therefore, Ni is very
effective in lowering core loss and increasing magnetic induction but Mo is ineffective in
improving core loss and magnetic induction.
Table II. Core loss and magnetic flux density of test steels
Steel Core Loss Magnetic Induction
W15/50 (Watt/Kg) B50 (Tesla)
A 2.249 1.671
B 2.402 1.652
C 2.221 1.675
Texture
The results of the calculated volume fractions of texture components from the ODFs are shown
in Table Ⅲ. First of all, regarding the textures influencing significantly the magnetic properties,
cube, Goss, and γ fiber textures are mainly discussed. The volume fractions of cube texture
(001)(100) and Goss texture (110)(001) in Ni-steel are a bit more than Mo-steel as though the
quantity is small. On the other hand, γ fiber (φ1= 0-90˚, Φ=55˚, and φ2=45˚) shows high volume
fractions more than 30% for all steels. Ni-steel reveals noticeably lowest γ fiber in volume
fraction, compared to Mo bearing steel. Therefore, it is obvious that Ni element is more effective
in reducing γ fiber than Mo element. Typical γ fiber, (111) //ND component are very important
factors for controlling magnetic properties. Viewing the effect of annealing on these fiber texture
components, steel C with Ni shows lower γ fiber than Mo containing steel. Figure 1 shows
orientation intensities along ε and γ fibers after annealing. Intensity of ε fiber in Figure 1(a)
268
shows a peak for {111}<112> orientation at Φ = 55° and Mo steel is the highest γ fiber.
{110}<001> Goss orientation at Φ = 90° shows the lowest intensity for Mo steel. Also in Figure
1(b), it is obvious that Mo steel shows the highest γ fiber but Ni steel reveals lower than Mo steel.
From these two graphs, it is distinct that Ni is more effective than Mo steel in increasing Goss
texture but decreasing γ texture, which is certainly a cause for improving magnetic properties by
Ni addition.
Texture factors shown in Table Ⅲ are expressed as a ratio of the sum of cube texture and Goss
texture to γ fiber in order to ascertain effectiveness of the former two textures against the γ fiber.
This is because cube and Goss textures are favorable but γ fiber is unfavorable to magnetic
induction and core loss. Steel containing Ni showed the highest texture factor and Mo-steel
showed the lowest. The large texture factor means that useful textures for magnetic properties are
much and thus can increase magnetic induction and decrease iron loss. As though it was verified
experimentally that Ni enhanced cube and Goss texture and lowered iron loss, it is hardly
explained how Ni element plays a role in developing such textures but this is subject to
investigate in future.
Table III. Texture volume fractions of annealed steels
Texture Orientation Euler Angles Texture Volume Fraction (%)
g=[Φ1 Ф Φ2] Steel A Steel B Steel C
Cube (001)[100] [0 0 0] 2.1 2.2 2.7
Goss (001)[100] [90 90 45] 2.8 1.6 2.1
γ Fiber {111}<uvw> [0-90 55 45] 39.9 43.1 30.5
Texture Factor (%) = (Cube+Goss)/γ 12.3 8.8 15.7
Discussion
Effects of Mo and Ni on Magnetic Properties

Reference steel A, bearing high alloys of 2.9% Si, 1.5% Al, 0.1% Sn, and 0.078% Sb, shows a
high level of magnetic induction and low core loss which is close to the level of magnetic
properties of grain oriented electrical steel. Moreover, addition of Mo and Ni elements to this
steel has a great effect on magnetic properties and texture. Of the four test steels, steel C,
containing Ni, had the best magnetic flux density and core loss, which proves that Ni was more
effective in improving magnetic properties than Mo.
(a) (b)
Figure 1. Intensities of ε fiber along Φ = 0 to 90° (a) and γ fiber along φ1 = 60 to 90° (b).
269
Mo added steel revealed lower magnetic induction and higher core loss than even the reference
steel. Sn and Sb elements contained in the reference steel already proved favorable to the
magnetic properties [1], but the addition of Mo to the reference steel is unfavorable and instead
deteriorates the magnetic properties. Mo and Ni have similar electrical resistivity, but when these
elements are added to steel, their chemical behaviors would react differently in steel and thus
also affect magnetic properties in a different manner. That is, Mo forms chemical compounds
such as carbide precipitates, while Ni does not form carbides and thus does not hinder
magnetization. Therefore, Ni is presumably effective on permeability and eddy current because
of free carbides compared to the other elements. Mo bearing steels showed smaller grain size
than the Ni bearing steel. In general, larger grains show higher magnetic induction and larger
core loss because movement of magnetic domains is more freely active in larger grains and thus
permeability increases as energy loss increases. Shimanaka et al.[4] reported that core loss in
non-oriented electrical steels decreased with an increase of grain size up to 100 ㎛ and
thereafter increased. Their steels showed core loss of only about 3 Watt/Kg for 2.8% Si steel
without special elements such as Sn, Sb, Mo or Ni, but our Ni added steel revealed a much lower
core loss of 2.2 Watt/Kg. Therefore, the fact that Ni added steel has even larger grains but shows
lower core loss than other steels is a new result which is quite different from findings to date.
Correlation of Texture with Magnetic Properties

Magnetic properties are concomitant with crystal texture [1], that is, cube and Goss texture are
favorable to magnetic properties but γ fiber is unfavorable. The Ni added steel exhibited a high
texture factor compared to other steels. The Mo added steel exhibited a lower texture factor than
the reference steel, because Mo forms carbides and thus presumably hinder the development of
cube and Goss texture. Correlations of texture factor with both magnetic flux density and core
loss are shown in Figure 2. The magnetic flux density increases proportionally with texture factor.
On the other hand, core loss also decreases proportionally with texture factor. These results on
the relationship between texture factor and magnetic properties prove that magnetic induction
and core loss are directly related to texture factor.
Conclusions
The effects of Mo and Ni addition to high-alloyed non-orientation steels with 2.9Si-0.1Sn-

0.08Sb on magnetic properties and texture are as follows;
(1) Ni bearing steel exhibits a larger grain size than Mo addition.
(2) Ni addition substantially decreases core loss to 2.22 W/Kg at W15/50 and increases magnetic
flux density to a high level of 1.68 Tesla at B50, while Mo increases core loss and decreases
magnetic flux density.
(3) Volume fractions of cube and Goss textures are similar for all steels, but γ fiber volume is
lower in Ni-steel than other steels.
(4) Magnetic flux density increases proportionally with texture factor and core loss also
decreases linearly.
270
1.695
Magnetic flux density (B50), Tesla

1.69
1.685
1.68
1.675
1.67
y = 0.0035x + 1.623
1.665
1.66
1.655
1.65
1.645
4 9 14 19
Texture factor ( %)
(a)
2.6
2.55
2.5
2.45
Core loss, W/Kg
2.4
2.35
2.3 y = -0.0275x + 2.636
2.25
2.2
2.15
4 9 14 19
Texture factor (%)
(b)
Figure 2. Correlation of texture factor with (a) magnetic flux density and (b) core loss.
References
1. S.K. Chang and W.Y. Huang, “Texture Effect on Magnetic Properties by Alloying Specific
Elements in Non-Grain Oriented Silicon Steels”, ISIJ Intenational, Vol. 45, No.6 (2005),
918-922.
2. Texture measurement software, Res-Mat Co, McGill University.
3. W.C. Liu and J.G.. Morris, “Quantitative Analysis of Texture Evolution in Cold-Rolled,
Continuous-Cast AA 5XXX-Series Aluminum Alloys”, Met. and Mat. Trans. A, 35A(2004),
265.-277.
4. H. Shimanaka, Y. Ito, K. Matsumura, and B. Fukuda, “Recent Development of Non-Oriented
Electrical Steel Sheets”, J. of Magnetism and Magnetic Materials, 26(1982), 57-64.
271
AN OPTIMIZATION STUDY FOR AN EFFICIENT HYDROGEN

REMOVAL DURING TWIN ROLL CASTING
Aziz Dursun, B. Çorlu, M. Dündar, R. Erdoğan
Assan Aluminyum, İstanbul, Turkey
Keywords : Degassing, Twin Roll Casting
Abstract
Aluminum alloys can dissolve excessive amount of hydrogen gas in their molten state.
Since its solubility decrease with decreasing temperature, gas bubbles are formed and entrapped
within the solid structure during solidification. Existance of such imperfections can cause serious
failures during manufacturing of sheet and foil products. There exist many methods to remove
hydrogen gas from liquid aluminum. The efficiency of removal depends mainly on operational
parameters. Inert gas flow rate and rotational speed of the rotor are among those for the systems
employing injection and shearing of the gas bubbles for gas removal mechanism. In this study
we aimed at determining the optimum argon flow rate and the rotor speed for the SNIF system
which will result in the most efficient hydrogen removal rate within the liquid metal. The
measurements were conducted during 1050 and 3003 aluminium alloy castings. Nine different
gas flow rate-rotor speed combinations determined from Design of Experiments(DOE) were
applied during castings. A mathematical equation estimating the hydrogen content as a function
of flow rate and rotor speed has been developed using a statistical software. The optimum flow
rate/rotor speed combinations were determined for the most effective hydrogen gas removal and
implemented in real scale production.
Introduction
The quality of cast products depends primarily on the cleanliness of the melt. Amount of
hydrogen gas entrapped during castings is one of the indiciations showing the quality of the cast
products particularly in aluminium. Aluminium alloys dissolve excessive amount of hydrogen
gas in their molten state. While the solubility of hydrogen in liquid aluminium is 0.7 ml/100g,
that of in solid state drops to a value 0.02 ml/100g Al[1]. Therefore during solidification,
dissolved hydrogen in excess of the maximum solid solubility rejected by the solid phase and
precipitate out in the form of hydrogen gas. Presence of excessive amounts of hydrogen porosity
within the cast products strongly influence the mechanical properties of the alloy castings and
therefore cause series failures during manufacturing of sheet and foil products. Many melt
treatment methods has been developed and implemented to reduce the amount of hydrogen
concentration in the melts during casting[1-3]. The rotary impeller degassing method(SNIF
system) which is schematically shown in Figure 1 is in widespread use by the aluminium
production industry.
275
Figure 1. Schematic represantation of the rotary impeller degassing method.
In this method, an inert gas is injected through a rotating ceramic shaft and released into
the liquid metal from the fine openings at the bottom of the shaft. Rotation of the impeler
between 250-450 rpm shears the inert gas bubbles creating large active surface areas for
dissolved hydrogen atoms to attach and remove from the melt. The efficiency of the hydrogen
removal by rotary degasser depends on the surface to volume ratio of the inert gas bubbles
created and the dsitribution of those bubles throughout the melt pool. These two parameters are
directly related to the rotation speed of the impeller and the rate at which the inert gas is injected
into the rotating shaft.
The present study is aimed at optimization of the rotary degasser, used in our plant,
during 1050 and 3003 aluminium alloys by determining the optimum inert gas flow rate and
rotor speed which result in the most efficient hydrogen removal from the liquid metal.
All measurements were done using a hydrogen analyzer unit based on CHAPEL method
(Continuous Hydrogen Analysis by Pressure Evaluation in Liquids)[4]. The technique is based
on measuring continuous hydrogen content by pressure evaluation in liquid metals. The unit
consists of a gas-tight ceramic tube with a porous graphite disc connected to a pressure-
measuring instrument. When the probe is immersed into the liquid metal, the graphite disc
behaves like an “artificial bubble” into which hydrogen from the melt diffuse until the pressure
in the probe and the hydrogen partial pressure in the melt is in equilibrium. The hydrogen
concentration is then calculated by Sievert’s law[5];
cHeq ( pH 2 , T , A) = co pH 2 α ( A)κ (T )
Where co is the solubility of hydrogen in pure aluminum at 973 K (0.92 ml/100 g)
cHeq is the hydrogen concentration dissolved in the melt
pH 2 is the equilibrium hydrogen partial pressure in equilibrium with the hydrogen pressure
dissolved in the melt,
α ( A) is the correction factor for alloy composition. It is 1 for pure aluminum and expressed as:
log α ( A) = cMg % Mg + cMn % Mn + cCu %Cu + cSi % Si
276
cMg, cMn, cCu and cSi are the activity coefficients. κ (T ) is the correction factor for melt
temperature. It is 1 at 700 C and increases with temperature.
The data was taken continuously for the entire casting campaign unless unplanned stop of the
casting line. This allows us to in-situ monitoring of the changes in the melt conditions and the
level of dissolved hydrogen as different rotor speed and/or argon flow rates are set. Hydrogen
content was monitored at 30 minutes intervals over a period of 24 hours using a printer
connected to the analyzer. The hydrogen concentration for that specific rotor speed-flow rate
combination was taken as the value which remained constant over the entire 24 hrs
measurement.
A simple and practical method was employed in order to evaluate the quality of the sheets cast at
certain rotor speed-argon flow rates. The method involves first cold rolling a sample of sheet into
a final gauge (~200 µm) and then annealing it at high temperatures for a period of time.
Annealing at high temperatures cause to expand the gas bubbles located near the surface and
therefore makes them visible by bare eyes. Then the surface of the samples was examined for
possible trace of bubbles (Figure 2). The rotor speed-flow rate which almost caused in bubble
formation on the sheet surface is considered to be the critical (threshold) rotor speed-flow rate
that would be applied during casting for an efficient hydrogen removal.
Figure 2. Hydrogen bubbles formed after annealing of aluminum foil sheet.
The Methodology and Results

All the experimental work was performed at one casting line and measurements were done after
SNIF unit and filtration box. The measurements were conducted during casting of 1050 and 3003
aluminium alloys. Although the metal flow rate can have an effect on the measurements, they
were held relatively constant throughout the experiments. Since only one nozzle system has been
used in our foundry practices, the experimental data were gathered with only one nozzle
operating. A commercial software was used in order to determine “design of experiments”
followed during the measurements. The minimum and maximum values for the rotor speed and
the argon flow rates were set as an input into the software and nine different gas flow rate-rotor
speed combinations were determined using “response surface” design methodology. The rotor
speed-argon flow rates applied during casting of both aluminum alloys were tabulated in Table I.
277
Table I. Design of Experiments
Argon flow rate Rotor speed
1.0 250
1.0 325
1.0 400
1.2 250
1.2 325
1.2 400
1.5 250
1.5 325
1.5 400
The hydrogen concentrations measured during casting of 1050 (% 0.25 Si, 0.4 Fe, 0.05 Cu, 0.05
Mn, 0.05 Mg, 0.07 Zn) and 3003 (% 0.6 Si, 0.7 Fe, 0.1 Cu, 1-1.5 Mn, 0.1 Zn) Al alloys at the
given rotor speed-argon flow rates are shown in Table II and III.
Table II.Measured hydrogen concentrations at the given rotor speed-argon flow rates for 1050.
Argon Flow Rotor Pressure Temp C H2 cc/100 mg Correction H2 cc/100
rate speed mbar Factor (F) mg
T=700
1.0 250 21.6 706 0.129 1.041 0.124
1.0 325 22.6 704 0.130 1.028 0.126
1.0 400 23.1 703 0.130 1.021 0.127
1.2 250 17.2 700 0.110 1.00 0.111
1.2 325 18.0 704 0.116 1.028 0.113
1.2 400 19.4 704 0.120 1.028 0.116
1.5 250 13.1 708 0.101 1.055 0.096
1.5 325 13.8 704 0.101 1.028 0.098
1.5 400 15.8 705 0.109 1.035 0.105
Before Degassing - - - - 0.240
Table III.Measured hydrogen concentrations at the given rotor speed-argon flow rates for 3003.
Argon Motor Pressure Temp C H2 cc/100 mg Correction Factor H2 cc/100 mg
Debisi Devir mbar (F)
hızı T=700
1.0 250 25 707 0.130 1.04776 0.124
1.0 325 29.2 714 0.146 1.09707 0.133
1.0 400 30.9 707 0.144 1.04776 0.137
1.2 250 17.2 703 0.105 1.02028 0.103
1.2 325 16.3 705 0.103 1.034 0.099
1.2 400 15 705 0.099 1.034 0.096
1.5 250 14.3 705 0.097 1.034 0.094
1.5 325 11.1 705 0.085 1.034 0.082
1.5 400 11.6 708 0.089 1.0547 0.084
Before Degassing - - - - 0.253
Figure 3 illustrates the measured hydrogen concentrations as a function of argon flow rates at the
given rotor speeds for 1050 Al alloy.
278
0,140
0,135 Rotor Speed, rpm

250
0,130 325
400
0,125
0,120
0,115
0,110
0,105
0,100
0,095
0,090
0,085
0,080
1,0 1,1 1,2 1,3 1,4 1,5

Argon Flow rate, Nm3/h
Figure 3. Variation of the measured hydrogen concentration with the argon flow rate at three different
rotor speeds for 1050 Al alloy.
The most efficient hydrogen removal was obtained at 250 rpm/min for all the argon flow rates
applied (Figure 3). It is known that as the rotoation of the nozzle increases, the efficiency of
hydrogen removal also increases. High rotation of the nozzle generates large amount of fine
argon bubbles dispersed within the liquid metal. Dissolved hydrogen atoms then form diatomic
hydrogen gas at the surface of the rising inert gas bubbes and they are removed from the liquid
metal as the bubbles are relaesed from the liquid metal surface. In our case, high rotation of the
nozzle did not result in an efficient hydrogen removal. This behavior is attributed to the
vortexing created due to high-speed rotation of the nozzle. The vortexing created within the
liquid metal would probably reach the surface and result in absorbing humidity and oxides from
the surface into the liquid metal.
Figure 4 shows the variation of the hydrogen concentrations with the argon flow rate at three
different rotor speeds for 3003 Al alloy. As opposed to 1050 alloy, the most efficient hydrogen
removal was obtained at 400 rpm/min excluding the one applied with 1 N/m3 argon flow rate
during 3003 Al alloy casting. While high speed rotations result in lower hydrogen removal
efficiency for 1050, it results in higher removal efficiency in the case of 3003. This discrepancy
observed in the hydrogen removal efficiency during 1050 and 3003 Al alloy castings could be
attributed to the viscosity of the liquid metal. Due to alloying element additions, 3003 Al alloy
considered to have a higher viscosity. 3003 Al Alloy melt tends to be less vortexing at high-
speed rotations compared to 1050 Al alloy melt. Even though there are some contradictory
results about the effects of individual alloying elements on the viscosity of the Al Alloy in the
literature, it is known that the viscosity of aluminum decreases as the purity of the metal
increases [6-8].
279
0,140
Rotor Speed,rpm
0,135 250
0,130 325
400
0,125
0,120
H2 conc, cc/100 mg
0,115
0,110
0,105
0,100
0,095
0,090
0,085
0,080
1,0 1,1 1,2 1,3 1,4 1,5

Argon Flow rate, Nm3/h
Figure 4. Variation of the measured hydrogen concentration with the argon flow rate at three different
rotor speeds for 3003 Al alloy.
The correlation between measured hydrogen concentrations and the Al sheet products cast at
the given rotor speed-argon flow rate combinations.
Existance of hydrogen within the solidifed metal can cause serious failures during down
processing of thin foil products. Rolling of metal sheets during down processing of metal sheets
results in closing the gas bubbles and creating two seperate surfaces with incomplete bond.
Further rolling operations will then create short streaks parallel to the direction of rolling
resulting in small holes. Therefore it is important to eliminate or at least minimize the gas
entrapment within the solidifed metal sheets in terms of the quality and productivity. There exists
many methods to quantify the hydrogen bubbles entrapped within the solidified metal. Due to
time and equipment requirements, a simple and fast method was used to correlate between the
measured hydrogen concentrations and the Al sheet products. Samples of the Al sheets, cast at
the given rotor speed-argon flow rates were rolled down to 200 μ m using a lab scale cold rolling
instrument. The samples were then annealed at 580 C for 4 hours and examined visually.
Annealing process will cause, if any, closed gas space expand and make them visible.
No bubble formation has been observed on the surfaces of 3003 Al alloy, cast at all the rotor
speed-argon flow rate combinations. On the other hand, small amount of hydrogen bubbles have
been observed on the surfaces of 1050 Al alloys, cast only at 1 N/m3 argon flow rates for all
rotor speeds. The most efficient hydrogen removal has been achieved with 1.2 N/m3-250 rpm and
1.5 N/m3–250 rpm argon flow rates and rotor speed combinations for 1050 Al Alloy. Application
of 1.2 N/m3 argon flow rate is preferred considering the argon gas consumption. Operation of
the gas removal unit at lower rotation speeds also increases the service life of the graphite rotor.
Even though no bubble formation has been observed on the surfaces of 3003 Al alloy products
cast at all the rotor speed-argon flow rates combinations, 1.2/250 has been chosen and
implemented in real scale production considering the issues on gas consumption and service life
of the graphite rotor.
280
In order to express the hydrogen concentrations as a function of argon flow rates and rotor
speeds with an empirical equation, experimentally measured hydrogen concentraion datas were
fitted a model using surface response design methodology[9].
The following equations have been derived for 1050 and 3003 Al alloy, respectively.
H 2 conc = 0.2577 − 0.1779 ar − 0.0001mo + 0.0427 ar 2 + 0.0001ar × mo R2 = 99.8
H 2 conc = 0.4615 − 0.584ar + 0.00034 mo + 0.23ar 2 − 0.00028ar × mo R2 = 97.8
Where “ar” and “mo” are the argon flow rate and rotor speed,respectively.
Figure 5 shows a three-dimensional view and corresponding contour plots of the surface
responses expressed with the above equation. R2 is indicates the percentage of response variable
variation. In general the higher the R2, the better the model fits the data. Higher values of R2 in
our case indicates how well the model fits our measured data.
400
0.118
380
0.115
360
0.113
Rotor Speed, rpm
340 0.110
320 0.108
0.12
0.115
300 0.105
H2,cc 100 mg 0.11
0.105
280 0.103
0.1
1 400
1.1
350 260
1.2 0.1
1.3
300
Argon Flow Rate,Nm3 h1.4 Rotor Speed,rpm
1 1.1 1.2 1.3 1.4 1.5
250
1.5 Argon Flow Rate, Nm3 h
Figure 5. 3-D view and corresponding contour plots of the surface responses for 1050 Al alloy. Hydrogen
concentrations have been shown on the contour lines.
400
0.125
380
0.115
360 0.105
0.095
Rotor Speed, d dk
340
0.090
320
0.085
0.12
300
H2,cc 100 mg 0.1 0.080
0.08
280
1 400
1.1
1.2 350
260
1.3 300
Argon Flow Rate,Nm31.4
h Rotor Speed,rpm
250
1.5 1 1.1 1.2 1.3 1.4 1.5
Argon Flow Rate, Nm3 h
Figure 6. 3-D view and corresponding contour plots of the surface responses for 3003 Al alloy. Hydrogen
concentrations have been shown on the contour lines.
281
SUMMARY
The influence of degasser process parameters namely argon flow rate and rotor speed on
degassing efficiency was investigated. Optimum argon flow rate and rotor speed were
determined for both 1050 and 3003 alloys. The type of the alloy and therefore the viscosity of the
melt was found to be a critical factor in determining the optimum degasser process parameters.
While higher rotation speeds results in an efficient hydrogen removal rate during 3003
aluminium alloy which has a higher viscosity, it results in poor hydrogen removal during 1050
most probably due to vortexing created during degassing operation. An emprical equation has
also been derived by fitting the experimental data to a model using surface response design
methodology.
REFERENCES
1. Makhlouf M., W.L., Apelian D, Hydrogen in Aluminum Alloys-Its measurement and its
removal. A Monograph, AFS, Des Plaines II, 1998.
2. Gruzleski, J.E., The Treatment of Liquids Aluminium-Silicon Alloys. Des Plaines, 1990: p.
143-181.
3. Maniruzamman M., M.M., Phase Separation Technology in Aluminum Melt Treatment.
A Monograph, AFS, Des Plaines II, 2000.
4. Fromm, E., Aluminium 1989. 65: p. 1240-43.
5. Ransley C.E., T.D.E.J., J.Inst.Met, 1984. 84: p. 445-452.
6. Arsent'ev P.P., P.K.I., Russ.Metall, 1977. 2: p. 54-.
7. Vignau J.M., A.P., Bastein P., Compte Rendu Acad.Sci., 1967. 264(part 2): p. 174-.
8. Dinsdale, A.T. and P.N. Quested, The viscosity of aluminium and its alloys--A review of
data and models. Journal of Materials Science, 2004. 39(24): p. 7221-7228.
9. Myers, R.H. and D.C. Montgomery, Response Surface Methodology: Process and
Product in Optimization Using Designed Experiments. 1995: John Wiley & Sons, Inc.
New York, NY, USA.
282
METHODS OF MANGANESE ALLOYING TO ALUMINIUM AND THEIR

IMPACT ON MELT QUALITY
Dr. Volker Ohm and Dr. Reiner Bauer
HOESCH Metallurgie GmbH

Birkesdorfer Strasse 5
D-52353 Dueren, Germany
Keywords: Alloying, Alloying Additions, Melt Quality, Dissolution Speed
Introduction
Melt quality in general is coming more and more into focus, since aluminium alloys are
becoming more tailor made and are facing strong competition from composite materials. As an
example, the amount of aluminium is being reduced from around 70% to about 25% of modern
aircrafts weight, like Boeing 787 [1]. These challenges will not only require development of
advanced materials, but also require a more special focus on melt quality and melt quality
control.
Alloying is a major step in production of aluminium based alloys. Due to commercial reasons, a
high recovery rate and a fast dissolution is desirable. There are various publications related to
that issue, highlighting the mechanism of dissolution of high concentrated powder compacts and
recommending a best alloying practice with regard to these results [2,3,4,5]. In addition, the
impact on the dissolution speed and recovery rate of the remainder in the compact, commonly
flux or aluminium, was investigated [3].
However, to our knowledge the impact on the melt quality of the various kinds of alloying
additions was not investigated systematically. Thus, in this paper we present results from
systematical laboratory trials on Mn alloying additions. Dissolution characteristics according to
the AA TP-2 test [6] were carried out, but in addition the hydrogen contents before and after
alloying was determined using an AAScan™ device and the inclusions were determined using a
Prefil® including a metallographic investigation of the filter.
Alloying of Manganese
Dissolution Characteristics
Cast master alloys Mn20 (waffle) and Mn60 (splatters), pure electrolytical Mn flakes and powder
compacts Mn80Al20, Mn80flux20 and Mn80Al10flux10 were investigated in this comparative
test.
The tests were carried out in a resistance furnace with approx. 20 kg of primary aluminium
99.7%. The target Mn content was around 1% and temperature 732°C (1350°F).
283
recovery [%]
100,00
90,00
80,00
70,00
60,00
50,00
40,00
AlMn60 Splatter
30,00
Mn Flakes 1000
AlMn20 waffle
20,00
Mn80flux20
10,00 Mn80Al20
Mn80Al10flux10
0,00
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 32 34 36 38 40 42 44 46 48 50 52 54 56 58 60
time[min]
Figure 1: dissolution curves
740
temperature [ºC]
735
730
725
720
715
710
705
AlMn60 Splatters
Mn Flakes 1000
700 AlMn20 waffle
Mn80flux20
695 Mn80Al20
Mn80Al10flux10
690
0 5 10 15 20 25 30 35 40
time [min]
Figure 2: temperature during alloying
As can be seen from the graph, all alloying additions achieve a recovery rate of > 95%, but
significant differences must be stated in terms of dissolution speed. The powder compacts and
the Mn60 splatters show an acceptable dissolution speed and the flux containing compacts show
even an excellent dissolution speed, which is likely related to the low melting point of the flux,
supporting fast disintegration and fast cracking of the Mn oxide layer present on every Mn
particle due to the non noble property of the Mn metal.
The very low and in practice unacceptable dissolution speed of the Mn flakes could be expected.
The low dissolution rate of the low concentrated Mn20 master alloy instead is surprising.
However, this can be explained by reviewing the temperature of the melt (figure 2) after addition
of the alloying material. To achieve the target of around 1% Mn, the fourfold amount of Mn20
must be added to the melt compared to the 80% Mn containing compacts. This leads to an initial
decrease of the temperature, followed by a decrease of the significantly temperature dependant
dissolution rate [7].
Impact On Hydrogen Content

The hydrogen content of the melt was determined with an AAScan™ initially and after achieving
the alloying target.
284
Table I: Impact on hydrogen content after application of different Mn alloying products
AlMn60 Mn Flakes AlMn20 Mn80 Mn80 Mn80Al10
Splatters 1000 waffle flux20 Al20 flux10
before 0.137 0.144 0.127 0.136 0.150 0.145
after 0.134 0.142 0.125 0.135 0.158 0.144
From table I it can be deduced, that there is no significant difference between the products in the
test. After addition the hydrogen content is in any case at a usual level and far away from the
saturation, which is at 700°C at around 0.92 ml / 100 g Al [8]. With normal degassing procedures
applied in casthouses, the hydrogen content can be decreased below specification levels.
Impact On Inclusions Level

60 minutes after starting the alloying procedure (in case of pure Al 60 minutes after the metal has
melted completely), a Prefil® measurement has been carried out; the resulting Prefil® curves t vs.
filtrated metal are shown in figure 3.
filtered metal [kg]
1,5
1,4
1,3
1,2
1,1
0,9
0,8
0,7
0,6
0,5
0,4
0,3 Al 99,7 AlMn60 Splatters AlMn20 waffle
0,2 Mn Flakes 1000 Mn80Al20 Mn80flux20
0,1 Mn80Al10flux10
0
0 10 20 30 40 50 60 70 80 90 100 110 120 130 140 150 160
time [sec]
®
Figure 3: Prefil curves
150
3,500
140
130
3,000
120
aluminium oxide films concentration (#/kg)
Gamma Alumina
110
inclusions concentration (mm /kg)
2,500
100 Alumina
2
90
Manganese Oxid
2,000
80
Large Carbide
70
1,500 Small Carbide

60
50 Oxide Films
1,000
40
30
0,500 20
10
0,000 0
Al 99,7 AlMn20 waffle Mn1000 Flakes Mn80flux20 Mn60 Splatters Mn80Al20 Mn80Al10flux10
sample
Figure 4: PoDFA results
285
The curves indicate, that flux containing compacts and low concentrated master alloys (Mn20)
have no or minor negative impact to melt quality compared to those without flux. Mn60 splatters
show an acceptable performance.
Since the isolated Prefil® curves can only indicate a tendency about the grade of impurities, the
Prefil® samples (metal residues) were investigated according to the metallographic PoDFA
analysis method (figure 4).
The following figures show filter residues:
Figure 5: 99.7 % Al Figure 6: after addition of Mn flakes
Figure 7: after addition of Mn80Al20 Figure 8: after addition of Mn80flux20
The results of PoDFA investigations from Prefil® samples in general correspond with the Prefil®
curves itselves.
Highly concentrated flux free products (Mn flakes, powder compacts) can create inclusions like
alumina and Mn-oxide. At the same time the number of oxide films increases. This is a logical
finding, because especially the flux free powder compacts consist of fine Mn and Al powder,
which are oxidized at every surface. The surface area of those particles in total is much bigger
than for cast products like Mn20 and Mn60. In case of flux absence, the inclusions remain in the
melt and require a subsequent melt cleaning, which is a normal treatment step in casthouses.
If flux is present in the formulation, either with 10% or 20%, the inclusions and especially the
oxide films are floated to the surface and can be skimmed off. It is a remarkable finding, that also
286
a significantly decreased amount of flux in the formulation (10% flux and 10 % Al) results in a
very clean melt after finishing the alloying procedure.
Conclusion And Summary
The dissolution characteristics and the impact on melt quality from various alloying additions for
Mn was determined systematically in laboratory scale trials. The findings were as follows:
Dissolution Characteristics
Highly concentrated Mn powder compacts exhibit superior dissolution performance, both with or
without flux content. Lower concentrated master alloys show inferior dissolution performance,
which is due to a significant decrease of the melt temperature arising from higher necessary
amount of cold alloying additions added to the melt.
Pure Mn flakes show a very bad dissolution performance because of the comparably big Mn
particles and the low contact area to the surrounding liquid metal.
Recoveries were found to be > 95% according to AA TP-2 test.
Impact On Hydrogen Content

Hydrogen content can be considered as not affected significantly in any case.
Impact On Inclusion Level

Cast products are beneficial for the melt cleanliness, whereas high concentrated, flux free
compacts require subsequent cleaning of the melt. Flux containing powder compacts instead
contribute significantly to melt cleanliness. In this case, the remainder of the formulation can be
a mixture of flux and aluminium powder. Our investigations point out, that even a smaller
amount of flux (e.g. 10% instead of 20% for Mn80) may result in a clean melt.
Conclusions For Use Of Alloying Additions In Practice
In practice, commercial factors are parameters, which have to be considered as well as quality
requirements. In general, high concentrated alloying additions are commercially beneficial
(lower costs for alloying element, lower storage and transportation costs). Thus, it is desirable to
use high concentrated master alloys, where melt quality is not affected negative.
For the main alloying work, mostly done in melting furnaces, the use of powder compacts is
recommended. The remainder part of the formulation besides of the alloying element can be
either aluminium or flux or a mixture of both. Laboratory scale trials show, that flux containing
compacts contribute significantly to melt cleanliness, so that flux containing compacts should be
considered, if secondary aluminium metal or higher amounts of in house scrap is used, bringing
inclusions to the melt. Powder compacts can be formulated tailor made fitting to the specific
process and to the typical metal mix used in each casthouse operation.
If flux containing additions are applied, the flux requires some settling time before skimming, so
that the flux has time enough to float to the surface, together with the inclusions. In practice,
settling times of 10 – 15 minutes have proven as sufficient.
Flux free compacts show excellent dissolution characteristics as well, if well formulated.
Commercially, if the remainder is consisting of Al powder exclusively, this kind of compact is
more expensive, even if the recovery of the additional aluminium from the compacts is
287
considered. However, if a flux free process has or wants to be maintained or if the process is
based on primary metal, inclusions can be removed by common methods of filtration with
preferably continuous control of inclusion levels.
The commercial disadvantage of lower concentrated master alloys like Mn20 compared to Mn80
powder compact is even more significant, because of the higher amount of “processed” Al.
Additionally, the remelting of the master alloys requires additional energy and, as shown in this
paper, the dissolution rate is, due to the cooling of the melt, lower than powder compacts.
Thus, the application of cast low concentrated master alloys is only recommended at a later stage
of production (e.g. in transfer launder) for fine adjustment of the chemical composition.
References
1. W.S. Miller, C.W.T. Lahaye, “Aluminium on the move: Trends in aluminium applications
from a European perspective”, Aluminium Cast House Technology 2007, 171-178.
2. Gregorio Borge, Paul S. Cooper, and Stuart R. Thistlethewaite, Review of Dissolution Testing
and Alloying Methods in the Casthouse (Frankfurt, Ger: International Conference Continuous
Casting, 2000)
3. Peter Fisher, Paul S. Cooper, and Stuart R. Thistlethwaite, Dissolution mechanisms in
Aluminium alloy additives (San Francisco, USA: Light Metals, 1994)
4. Young E. Lee, and Dana LeMasters, Alloying Kinetics of Mn in Aluminium Melt (New
Orleans, USA: Light Metals 2001)
5. D.J. Bristow et al., Dissolution mechanisms of Compressed Additives in Aluminium (San
Diego, USA: Light Metals 1999)
6. Aluminium Association standard test procedure (TP-2) for measuring the dissolution of
aluminium hardeners (Washington D.C., USA: The Aluminium Association, 1990)
7. Gregorio Borge, and Paul S.Cooper, Recent studies of compacted additives including
industrial scale tests (Seattle, USA: Light Metals, 2002)
8. C.E. Ransley, and H. Neufeld, “The solubility of hydrogen in liquid and solid aluminium”, J.
Inst. Metals, 1959-60, 599, 620, vol.LXXIV, 1945
288
Manufacture and Characterization of Al-3Mg-Nb Alloys

Noe López P.1; Xochitl I. Rodríguez G.1; Sandra D. Domínguez M.1;
Lucio Vázquez B.1; Víctor J. CortésS.1; Marco A. Domínguez2; Gabriel Lara3;
Manuel Vite4, Joel Aguilar4; Silvia Buenavista5;
1
Universidad Autónoma Metropolitana, Av. San Pablo 180, Azcapotzalco 02200 México, D.F.;
2
Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas 152, Gustavo A. Madero, 07730,
México, D.F.;
3
Instituto de Investigación en Materiales, UNAM, Ciudad Universitaria, México D. F.
4
Sección de Posgrado en Ingeniería, ESIME, Unidad Adolfo López Mateos, Edificio 5, Av.
PolitécnicoS/N, Gustavo A. Madero, C.P. 07338;
5
ESIQIE, Unidad Adolfo López Mateos, Edificio 8 Av. Politécnico S/N, Gustavo A. Madero,
C.P. 07338
Keywords: Manufacture, Properties, Al-3Mg-Nb, Alloys
Abstract
Additions of 0.03 % and 0.06 % niobium to an Al-3Mg alloy refined the microstructure,
improved the tensile properties, and decreased the loss of weight due to salt spray corrosion, of
the plain alloy. The effect of niobium on the loss of weight by wearing and by corrosion under
dynamic conditions was negligible. Corrosion in the alloys with Nb was more uniform in both
type of corrosion tests.
Introduction
Lately, Al-Mg alloys with small additions of transition metals of high fusion point have been of
interest in many research labs throughout the World. Some of their properties, such as fine grain
and therefore high mechanical strength, high resistance to corrosion and wear, besides a high
strength/weight ratio make them suitable for automotive, aerospace and ship applications.
Since many years ago B-Ti alloys have been used as grain refiners, it has been reported recently
of the excellent properties of Sc- Al-Mg alloys [1]. Scandium, however, is a very scarce element
and therefore very expensive, the present work is the beginning of an effort to characterize Al-
Mg alloys combined with niobium, a less expensive element.
Aim
The purpose of this work is to determine the effects that small additions of niobium to an alloy
Al-3Mg have on its microstructure, mechanical properties and on its resistance to wear and
corrosion.
Manufacture
Fusion and Thermomechanical Treatment of the Alloys
The chemical composition of the manufactured alloys is given in Table I.
The raw materials to prepare the alloys were electrolytic aluminum and electrolytic magnesium –
with a purity of 99.5 % and niobium powder 99 + % of a particle size of ~ 100 nm. The materials
in the proper amounts were placed in a graphite crucible and fused in an induction heating
furnace. The furnace first was purged to a 10-2 Torr vacuum and then the metals were fused in an
argon atmosphere. The fusion at about 750 ºC was poured in a mould of copper and cooled with
running water. Ingots of a transverse section 50 mm x 50 mm and 300 mm height of three
aluminum alloys were prepared in this way.
289
The alloys received a homogenization heat treatment of 14 h at 450ºC in a box furnace using an
argon atmosphere for protection against oxidation. The microstructure of the alloys after this
treatment is shown in Figure 1.
Table I. of chemical composition of the alloys
Element Alloy 1 Alloy 2 Alloy 3
Al 96.6 96.5 95.8
Mg 3.174 3.216 3.349
Si* 0.0677 0.0622 0.1084
Fe 0.1573 0.1461 0.3664
Mn* 0.0080 0.0079 0.3459
Nb** 0.03 0.06 0.0
Traces of other elements*** 0.0267 0.0265 0.0309
* Alloy 3 was prepared from another Al batch, therefore the higher % of Mn and Si; ** the niobium content is
nominal, because the spectrometer was not conditioned to analyze this element;*** among these elements are Cu,
Zn, Ni, Cr, Pb, Ti, V, Co and Sr.
50 μm 50 μm 50 μm
(a) (b) (c)

Figure 1. Microstructure of the alloys after homogeneization, (a) alloy 1, (b) alloy 2, (c) alloy (3). 100X
The alloys containing niobium are characterized by a predominantly cell substructure with some
dendritic substructure, while the alloy Al-3Mg has mainly a dendritic substructure.
Second phases are visible at higher magnification, as shown by Figure 2. Assuming that at room
temperature the solubility of the impurities in Al is almost cero and that these combine only with
Al, Table II presents the percentage in weight of second phases.
50 μm 50 μm 50 μm
(a) (b) (c)

Figure 2. Microstructure of the alloys after homogeneization, (a) alloy 1, (b) alloy 2, (c) alloy (3).
The ingots were cut longitudinally with a brush then they their ends were cut with a saw to
eliminate shrinkage, finally the pieces of alloy were reamed to obtain prisms of parallel faces
with a transverse section of 40 mm x 21 mm and variable length.
Heat treatment and rolling
The experimental material was preheated in an electrical box furnace during 30 minutes at 100ºC
and rolled, reducing in each pass 0.2 mm until a total reduction of 40 %, for a final thickness of
290
13 mm. After rolling, the plate was annealed for 45 min at 350ºC. An argon flow of 10 feet3/h
was used for preheating and annealing treatments.
Samples of each alloy were prepared for hardness, tension, corrosion, wear and metallographic
examination.
Table II. Weight % of second phases [2]
Second Phase Alloy 1 Alloy 2 Alloy 3
β phase (Al3Mg2), weight % 8.4 8.6 8.9
θ phase (Al3Fe), weight % 0.38 0.36 0.9
β phase (Al3Nb), weight % 0.056 0.112 0.0
Eutectic Al – Si, weight % 0.133 0.122 0.212
β phase (Al6Mn), weight % 0.03 0.03 1.36
Testing and results

Hardness Test
Pieces of each alloy with parallel polished faces 13 mm thickness were indented with a Brinell
hardness tester, using a 250 kg load and a 2.5 mm diameter steel ball, the results are shown in
table III.
Tensile Test
Five tests were carried out in an Instron machine for each alloy, according to ASTM E-8 [3], at a
head machine speed of 0.75 mm/min, the diameter and gage length were 6.25 mm and 25.4 mm,
respectively. The fracture surfaces of the tensile specimens are shown in Figure 3, while the
average of the five results is shown in table III.
(a)
(b) (c)
Figure 3. Reduction of area: (a) alloy 1, (b) alloy 2, (c) alloy 3.
291
Wearing Test
Three samples for each alloy were tested according to ASTM G-65 [4], in dry conditions. In this
test a 25.4 mm wide x 75 mm length x 12 mm thickness specimen of each alloy was fixed to the
arm of a balance, the other arm was loaded with 400 g load. The length of the balance allows that
a 228.6 mm diameter, metallic disc rotating at 200 rpm applies a force of 1 kg on the surface of
the sample, as a 400 g/min sand flow drops of a hopper. The fineness of the sand was 50 to 70
meshes.
TABLE III. Mechanical Properties
Mechanical Properties Alloy 1 Alloy 2 Alloy 3
Yield Stress
0.2 % offset (MPa 98.9 187 158.5
Tensile Strength (MPa) 243.3 278.8 201.4
Fracture Stress 236.2 247.7 152.3
Reduction of Area (%)
Resilience (J/m3) 27.4 36.6 25.9
Toughness (J/m3) 46.7 74.1 38.6
Brinell Hardness 230 28.5 315
Each sample was exposed to 5 runs, each run had a duration of 5 minutes to render a total of 5
000 revolutions. The distance traveled by the disc is its perimeter times number of turns or
3590.8 m. Table IV displays the average wearing rates for the five tested samples of each alloy.
Corrosion Tests
The alloys were subjected to two kinds of test: a dynamic corrosion test, known as the wheel
method and a static corrosion test or salt spray box method. Coupons of 25.4 x 25.4 x 5 mm,
with a grid 600 sandpaper finished surface, were used for both types of test.
Table IV. Wearing Rate.
Alloy Loss Rate (mg/m)
1 0.02426
2 0.02345
3 0.02544
Dynamic Corrosion Test (The Wheel Method)

Two coupons of each alloy were tested according to the method NACE 1D 182 [5] and weighed
before and after testing. The specimens were submerged in a glass bottle containing synthetic
water see [6], during 46 h at 70 ºC. The wheel is a carrousel where the bottles are located which
rotates at a 30 rpm speed. Table V shows the loss of weight for the three alloys and Figure 4
exhibits the microstructures after the test.
Table V. Loss of Weight %
Alloy Average Loss of Weight % Average Loss of Weight %
Dynamic Test Salt Spray Box
1 0.056 0.027
2 0.056 0.013
3 0.061 0.051
Static Corrosion Test (Salt Spray Box)

Two coupons of each alloy were tested according to the method ASTM B-117 [7], and weighed
before and after testing. The coupons are located on a table which forma a 75º angle with the
horizontal plane, the temperature in the interior of the box was 35 ºC, and the exposition to the
salt spray fog had duration of 800 h. Table V shows the loss of weight for the three alloys and
Figure 5 displays the microstructures after the test.
292
Analysis of Results
- Hardness. The higher hardness of alloy 3 is due to its higher contents of impurities, Fe, Si and
Mn and therefore to the higher percentage of second phases.
- Tensile Testing.The higher values of yield strength and tensile strength, resilience, toughness
and elongation displayed by alloy 2 are due to its finer microstructure produced by niobium. This
alloy 2 presents narrower Lüder bands because the dislocation distribution is more uniform in a
fine cell microstructure. The fracture surfaces of all the samples exhibit chisel shape, a feature of
ductile metals.
-Wearing Test. The wearing rate for the alloys containing niobium is slightly less than for the
alloy 3. In the three alloys the loss of weight varies linearly with the run distance.
Wheel Corrosion Test. Corrosion occurred over all the surface and along grain boundaries as
pinning points. The points are connected in the case of alloy 3 and formed crevices. The loss of
weight due to corrosion for the three alloys is the same.
Salt Spray Corrosion Test. Corrosion occurred evenly distributed over the surface as fine pinning
points. Some of the points, in the case of alloy 3, enlarged until one touched with another and
formed a crevice. The loss of weight of alloy 1 is twice that for alloy 2 and this loss of alloy 3 is
four times that for alloy 1. The corrosion which undergone the alloys in this test was milder than
for the wheel corrosion.
50 μm 50 μm 50 μm
(a) (b) (c)

Figure 4. Microstructure at the end of the wheel corrosion test (a) alloy 1, (b) alloy 2, (c) alloy 3, 200X.
50 μm 50 μm 50 μm
(a) (b) (c)

Figure 5. Microstructure at the end of the salt spray corrosion test (a) alloy 1, (b) alloy 2, (c) alloy 3, 200X.
Conclusions
• Niobium refined the microstructure of the alloys Al-3Mg.
• The hardness of alloy 3 is higher because its higher content of impurities, particularly, Fe,
Mn and Si.
• The tensile properties improved with increasing niobium content.
• The wearing resistance increased slightly with niobium additions.
293
• The effect of niobium on the corrosion resistance under dynamic conditions (wheel method)
is negligible.
• Niobium appreciably enhanced the corrosion resistance under static conditions (salt spray
box).
References
1. Ahmad Zaki, The Properties and Applications of Scandium –Reinforced Aluminum, Journal
of Metals, February 2003.
2. Metals Handbook, V. 8, Metallographic Structure and Phase Diagrams, 8 ed. ASM, 1973.
3. Standard Test Methods for Tension Testing of Metallic Materials, ASTM E-8.
4. Standard Test Methods for Wearing Testing of Metallic Materials ASTM G-5.
5. Wheel Test Method Used for Evaluation of Film Persistent Inhibitors for Oilfield
Applications, December 1982.
6. Standard Practice for the Preparation of Substitute Ocean Water, ASTM D.1141.
7. Standard Practice for Operating Salt Spray (Fog) Apparatus, ASTM B-117.
8. Standard Practice for the Preparation of Salt Solution for Salt Spray Apparatus, ASTM D-
1197.
294
An Investigation of Hexavalent-Free Chromate Conversion Coatings

for Test and Measurement Instrumentation
Mike Powers
Agilent Technologies
1400 Fountaingrove Parkway, Santa Rosa, CA, 95403, USA
Keywords: Chromate Conversion Coating, Aluminum Alloy, Contact Resistance
Abstract
Test and Measurement (T&M) products represent a very high performance subset of the
monitoring and control product category. These products are characterized by highly sensitive
electrical systems that must perform at levels well beyond the conventional products they test.
This is an investigation to define and develop a cost effective production process for application
of a trivalent (Cr3+) chromate conversion coating to replace the hexavalent (Cr6+) chromate
conversion coating that has traditionally been employed for aluminum alloy shields, waveguides
and other aluminum components used in high frequency T&M instruments. Testing and
characterization included surface contact resistance, corrosion resistance, paint adhesion and X-
Ray Photoelectron Spectroscopy. It was found that several trivalent chromate conversion coating
products demonstrate electrical performance and corrosion resistance that is essentially equivalent
to the traditional Cr6+ chromate conversion coating, while mitigating the toxicological and
environmental concerns associated with the use of hexavalent chromium.
Introduction
First introduced in the aerospace industry as an alternative to anodizing, hexavalent Cr6+-based
chromate conversion coatings (CCC) have increasingly been used in other industries; primarily
for their excellent corrosion resistance, but also for their low contact resistance, self healing
properties and outstanding overcoat paint adhesion [1,2]. Despite these ideal properties,
hexavalent CCC have recently faced regulatory obstacles in several dynamic markets (Europe,
China). This is the result of research that proved Cr6+ to be genotoxic and a human carcinogen
[3]. These negative health effects have also been identified in the United States under the
Occupational Safety & Health Administration (OSHA) [4]. The European Union’s Restriction on
Hazardous Substances (RoHS) Directive (2002/95/EC) states that “Member States shall ensure
that, from 1 July 2006, new electrical and electronic equipment put on the market does not
contain lead, mercury, cadmium, hexavalent chromium, polybrominated biphenyls (PBB) or
polybrominated diphenyl ethers (PBDE).” [5]. Similar directives restricting the use of hexavalent
chromium are pending in other countries such as China and Korea.
In the spring of 2002 the U.S. Navy patented a trivalent (Cr3+) chromate conversion coating
chemistry that was developed by researchers at the Naval Air Systems Command (NAVAIR)
headquartered in Patuxent River, Maryland [6]. The NAVAIR patent represented a breakthrough
for chromate conversion coating chemistry because it displayed excellent corrosion resistance
coupled with low surface contact resistance, while circumventing the use of hexavalent
chromium. The technology was subsequently licensed under a partially exclusive agreement [7]
to several manufacturers including SurTec International GmbH, Metalast® International, Inc. and
Henkel Surface Technologies.
This investigation reports the results of a comparative characterization study of the surface
contact resistance, corrosion resistance and paint adhesion between three trivalent (Cr3+)
295
chromate conversion coating products and a benchmark hexavalent (Cr6+) chromate conversion
coating product on aluminum alloy test coupons. Comparison of these properties was employed
to evaluate the viability of using trivalent CCC coatings on components used in high frequency
test and measurement instruments.
Sample Preparation
Test coupons were prepared using two different aluminum alloys, 6061 T-6 wrought aluminum
(to represent instrument cages and sheet metal applications) and AA383 cast aluminum (to
represent electromagnetic containment shields and casting applications). The coupons were
fabricated with nominal dimensions of 76 mm x 76 mm x 1 mm. The coupons were first cleaned
and then conversion coated. The cleaning sequence involved first degreasing the coupons in a
terpene based solvent at 52° C with ultrasonic agitation for five minutes, followed by immersion
is a non-etching, non-silicated alkaline cleaner at 50° C for three minutes and culminated by a
light acid etch in dilute H2SO4/HNO3/NH4HF2 for thirty seconds. All cleaning and conversion
coating process steps were followed by a two stage rinse in deionized water with a minimum
resistivity of 1 MΩ·cm. After the conversion coating step, the coupons were rinsed in deionized
water followed by a methanol rinse and then they were dried in a low temperature oven at 38° C
for two hours. Sets of coupons were chemical conversion coated using each of three trivalent
CCC products; SurTec® 650 chromitAl® TCP, Metalast® TCP-HF and Henkel Alodine® T 5900.
Another set of coupons was prepared using a benchmark hexavalent CCC, Henkel Alodine®
1500. The specific conversion coating process parameters for each of the CCC products tested,
including bath concentration, pH, temperature and immersion time, are shown in Table I.
Table I. Conversion Coating Process Parameters
Contact Resistance Measurements

Contact resistance measurements were conducted using an Agilent 34420A NanoVolt/Micro-
Ohm meter in four wire ohm mode. This high sensitivity multimeter is optimized for performing
low-level measurements with a resolution of 7.5 digits and sensitivity in resistance mode of 100
nΩ. Offset compensation was employed to minimize errors associated with thermal EMFs. A
concentric ring probe, designed and fabricated by engineering students at the University of
California Davis, was used for the contact resistance electrode [8]. An annular probe geometry
was utilized to take an infinite average of the surface resistance to account for any non-uniform
areas of the conversion coating. An applied weight of 7.4 kg was placed on top of the electrode-
coupon stack to insure consistent pressure and mitigate the effect of surface asperities in the
coatings. Resistance measurements were performed on sets of coupons representing each of the
conversion coating chemistries. Each set contained five coupons and four resistance
measurements were taken on each coupon, two per side. The resistance measurements for each
set of coupons were averaged and the standard deviation for the measurements was calculated.
The contact resistance of the test coupons was measured as conversion coated and then
periodically after exposure to moisture at elevated temperature (85% relative humidity and 85°
C, see section on Corrosion Testing). Figure 1 shows the experimental setup for contact
resistance measurements.
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Figure1. Contact resistance measurement experimental setup.
Corrosion Testing
The corrosion resistance of the test samples was evaluated by a vapor phase moisture resistance
test, similar to the JEDEC Std. 22-A110 Highly Accelerated Temperature and Humidity Stress
Test. This is an accelerated test for aluminum corrosion failures widely used in the electronics
industry. It involves placing the test coupons in an environmental chamber at 85° C and with a
relative humidity of 85% (85/85) for at least ten days, followed by visual inspection for any signs
of corrosion (e.g. discoloration, appearance of corrosion products, etc.) using an optical
microscope at 10x magnification. The test coupons were inspected as conversion coated, then
after 256, 496, 760 and 1066 hours of exposure in the 85/85 chamber.
Paint Adhesion Testing
Overcoat paint adhesion testing was performed using a tape test per ASTM D3359, Test Method
B (cross-cut tape test) [9]. As conversion coated test coupons were spray painted with Agilent’s
standard water based instrument enclosure paint. The coupons were then scribe cut, tape tested in
three different locations, inspected and graded according to the scale provided in the ASTM
standard. The grading scale goes from 0 to 5, where 0 indicates that most of the paint was
removed by the tape and 5 indicates that none of the paint was removed by the tape. For this
evaluation, a grade of 4 or 5 was considered acceptable and a grade of 3 or less was considered
unacceptable.
X-ray Photoelectron Spectroscopy
X-ray photoelectron spectroscopy (XPS) was performed by an external analytical laboratory
(Rocky Mountain Laboratories, Inc.) on one test sample each of Alodine® 1500 (hexavalent
CCC) and SurTec® 650 (trivalent CCC) using a Kratos Axis HSi instrument at a nominal
operating pressure of 2 x 10-10 torr. Samples were measured at a 90° take-off-angle yielding a
sampling depth of ~10 nm. The analysis area was ~500 µm in diameter. Analyses were
performed with a monochromatic Al kα x-ray source. Energy scales of the spectra were
referenced to the C 1s C-C/C-H signal at 284.5 eV. High energy resolution XPS analysis was
performed on the Cr 2p3/2 region of the spectra.
297
The results of contact resistance measurements for test coupon sets with fresh chromate
conversion coatings and then after 256, 496, 760 and 1066 hours of vapor phase moisture
resistance testing are complied in the graphs of Figure 2. It will be appreciated that the ordinate
scales for each graph are not necessarily equivalent. The error bars represent the standard
deviation of all measurements used to calculate the average contact resistance for a particular
coupon set. The second letter in the specimen code indicated on the abscissa of each graph
corresponds to W for wrought material and C for cast material.
Figure 2. Contact resistance values before and after vapor phase moisture resistance testing.
It is clear from these results that the initial contact resistance of the Cr3+ samples compares
favorably with that of the Cr6+ specimens, with average contact resistance values in the 1 - 2 mΩ
range. After progressive exposure to 85% relative humidity at 85° C through 1066 hours of
accelerated testing, the measured contact resistance for the trivalent CCC specimens remained
relatively stable, with values in the 1 – 4 mΩ range. By contrast, the hexavalent CCC specimens
displayed a step function increase in contact resistance around 760 hours, in some cases nearly
an order of magnitude higher. This could be due to the fact that hexavalent chromate conversion
coatings are known to degrade over time when exposed to temperatures over 60° C [10].
However, it will be noted that the contact resistance of the Cr6+ specimens did not degrade
further after an additional 306 hours of 85/85 (1066 hours total).
All of the test coupons were inspected for evidence of corrosion after each of the four times they
were removed from the 85/85 chamber for contact resistance testing. None of the coupons
showed any evidence of discoloration or corrosion at any time during the testing. This result
298
indicates that the trivalent CCC specimens are equivalent to the hexavalent CCC benchmark with
regard to corrosion resistance as evaluated using the vapor phase moisture resistance test.
Wrought and cast aluminum test coupons representative of each of the test groups were
evaluated for paint adhesion. Figure 3 shows an example of a trivalent conversion coated test
coupon (Metalast® TCP-HF on cast aluminum) that was scribed and tape tested. This sample was
given a grade of 5 according to the ASTM D3359 grading scale criteria.
Figure 3. Micrograph (10x) of paint adhesion test coupon before (left) and after (right) tape test.
The paint adhesion results for all of the test groups are shown in Table II. Since all of the
coupons tested received a grade of 4 or 5, the associated chromate conversion coatings are
considered to display good paint adhesion characteristics.
Table II. Paint Adhesion Tape Test Results
High energy resolution XPS spectra for a wrought aluminum test specimen with a trivalent
chromate conversion coating (SurTec® 650, specimen code ST-1) and the benchmark hexavalent
chromate conversion coating (Henkel® Alodine 1500, specimen code AL-1) are shown in Figure
4. It is clear from these XPS spectra that the surface region of the hexavalent CCC has a
significant concentration of Cr6+, as compared with the trivalent CCC specimen where the Cr6+ is
below the nominal instrumental detection limit of ~0.1 atom %. This result indicates that the
trivalent chromate conversion coating does not contain any hexavalent Cr, as expected.
299
Figure 4. High energy resolution XPS spectra for Cr3+ (left) and Cr6+ (right) specimens.
Conclusions
Electrical contact resistance testing performed on wrought aluminum and cast aluminum test
specimens coated with three different Cr3+ chromate conversion coating products resulted in
measured values that are comparable to those achieved using a benchmark Cr6+ chromate
conversion coating. In conjunction with acceptable paint adhesion and accelerated corrosion
testing, these results support the viability of using trivalent chromate conversion coatings on
aluminum components employed in high reliability test and measurement instrumentation.
References
1. S. Wernick and R. Pinner, The Surface Treatment and Finishing of Aluminium and its Alloys, 5th ed.,
Finishing Publications, Teddington, U.K. (1986).
2. L. Xia and R. McCreery, “Storage and Release of Hexavalent Chromium from Chromate Conversion
Coatings,” Journal of the Electrochemical Society, 147 (2000), p. 2556.
3. L. Friberg, G.F. Nordberg and V.B. Vouk, Handbook of Toxicology of Metals, Vol. II, Elsevier,
Amsterdam (1986).
4. U.S. Department of Labor - Occupational Safety & Health Administration, “Chromium (VI)
(Hexavalent Chromium),” <http://www.osha.gov/dts/chemicalsampling/data/CH_228697.html>,
2007.
5. “Directive 2002/95/EC of the European Parliament and of the Council,” Official Journal of the
European Union, 27 January 2003.
6. C. Matzodorf, M. Kane and J. Green, “Corrosion Resistant Coatings for Aluminum and Aluminum
Alloys,” U.S. Patent 6,375,726 B1, April 23, 2002.
7. Federal Register, Vol. 68, No. 204, Wednesday, October 22, 2003, Notices. p. 60339-60341.
8. M. Powers et al., “Comparative Characterization of Cr3+- and Cr6+-based Chromate Conversion
Coatings on Al Substrates for Test and Measurement Applications,” Proceedings of the 2007
Materials Science and Technology Conference, American Society for Metals International, Materials
Park, OH (2007).
9. ASTM D3350-02, Standard Test Methods for Measuring Adhesion by Tape Test, American Society
for Testing and Materials International, West Conshohocken, PA (2002).
10. V. Laget et al., “Dehydration-Induced Loss of Corrosion Protection Properties in Chromate
Conversion Coatings on Aluminum Alloy 2024-T3,” Journal of the Electrochemical Society, 150, 9
(2003), p. B425-B432.
300
FABRICATION OF AA2024-SiC NANOCRYSTALLINE METAL MATRIX

COMPOSITE
Timothy Zhigang Lin1, Chunhu Tan1, Bob Liu1, Quan Yang1, and Adolphus McDonald2
1
Aegis Technology Inc.
3300 A Westminster Ave., Santa Ana, CA 92703, USA
2
U.S. Army Research, Development & Engineering Command
Aviation & Missile Development Engineering Center
Bldg. 5400, Redstone Arsenal, Al 35898, USA
Keywords: Nanocrystalline Metal Matrix Composite, AA2024-SiC, Hot Isostatic Pressing
(HIPing)
Abstract
Consolidation of nanometer-sized AA2024-25 wt.% SiC powders produced by mechanical
milling at cryogenic temperature (cryomilling) was performed using Hot Isostatic Pressing
(HIPing) at various temperatures. Microstructure and mechanical properties of consolidated bulk
specimens were characterized to understand the densification behavior. The correlation between
the HIPing temperature and the densification behavior was obtained. The bulk composite was
found to consist of nanometer-sized (<100 nm) to sub-μm-sized α-Al grains. On the basis of the
optimized HIPing process, AA2024-SiC nanocrystalline metal matrix composite in large
dimension billet was fabricated for lightweight armor applications.
Introduction
Metal matrix composites (MMCs) typically based on Al alloys are currently the materials of
choice for many lightweight structural applications. Recent development in nanocrystalline (NC)
metals and alloys, with average and range of grain sizes typically smaller than 100 nm, has
attracted considerable research interest seeking a new opportunity for substantial strength
enhancement of materials. This is primarily due to superior mechanical properties found in this
class of materials, including high strength and high toughness [1]. For lightweight structure
applications such as lightweight ballistic armors requiring high strength, an increase in material
strength consequently leads to a reduction of structure weight. However, the major roadblock to
NC’s structural applications is the difficulty in fabricating them into a bulk form. Toward this
end, much research has so far focused on the synthesis of bulk NC metals and alloys using a
variety of techniques [2-4].
This study is devoted to fabrication of Al-SiC Nanocrystalline MMC (NMMC) in bulk form
applicable for high-strength lightweight structures, particularly aimed for large-dimension
lightweight armors that can provide enhanced ballistic protections yet with reduced weight. With
respect to cost effectiveness and ease of scale up for mass production, a low-cost, scalable
consolidation process of AA2024-SiC NMMC powders produced by mechanical milling was
employed. AA2024 Al alloy was selected for the matrix and SiC particles for the reinforcement
of MMC. Consolidation was performed using Hot Isostatic Pressing (HIPing) at different
temperatures to optimize the processing condition. Microstructure and mechanical properties of
consolidated specimens were characterized to understand the densification behaviors.
Materials and Experiments
Commercial AA2024 Al alloy powders from Valimet Inc. (Stockton, CA) and SiC powders from
Atlantic Equipment Engineering (Bergenfield, NJ) were used as the starting materials for
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mechanical milling at cryogenic temperature (cryomilling [5]). The diameters of SiC particles
vary from sub-μm to several μm. The blend of 75 wt.% Al alloy and 25 wt. % SiC powders was
milled in liquid nitrogen for 9 hrs. To produce bulk materials, the cryomilled AA2024-SiC
powders were consolidated using Hot Isostatic Pressing (HIPing) at various temperatures from
390 to 510°C with a pressure of 200 MPa for 1 h. Prior to HIPing, the cryomilled powders were
degassed at temperatures up to 350°C until the canned powder reaches a vacuum of 10-6 torr.
Scanning electron microscopy (SEM) observation was performed on a Philips XL 30 microscope
with a field emission gun. X-ray diffraction (XRD) measurements were carried out with a
Siemens D5000 diffractometer equipped with a graphite monochromator using Cu Kα radiation.
Transmission electron microscopy (TEM) observations were carried out with a Philips CM20
microscope operated at 200 kV. Compression test was conducted at room temperature at a cross-
head speed of 0.1 mm/min with specimen dimension of 4 mm x 4 mm x 8 mm.
1. Formation of AA2024 -SiC composite structure with nanometer-sized grains
Figure 1 presents representative SEM images of cryomilled AA2024-SiC powders. The milled
particles were about 10 μm to 120 μm, and were agglomerated with irregular-shaped feature
indicative of severe deformation caused by the ball milling process.
a) b)
Figure 1: SEM images of cryomilled AA2024-25%SiC powders used for HIPing.
XRD measurements of the cryomilled powders revealed the formation of composite structure
with nanometer-sized grains. The XRD peaks were found to consist of the reflection peaks from
both AA2024 Al alloy (i.e., α-Al) and SiC. The α-Al peaks of the milled mixture are much
broadening, indicating the refinement of microstructure in the sample. The average grain size of
α-Al phase estimated using the Scherror formula based on the peak broadening was about 25
nm. The grain size results are consistent with those reported for milled Al metal and alloys [2, 6].
TEM observations confirmed the formation of nanostructured composite in the cryomilled
powders. Representative images are displayed in Figure 3. The typical grain sizes were in the
range from ~ 10 to 50 nm. The nanometer-sized Al grains were found to be uniform, as shown
by the dark field images (Figure 2). The bright particles in the dark field image were
corresponding to α-Al. It is clear that the nanometer-sized grain microstructure formed.
302
a) b)
Figure 2. TEM images of cryomilled AA2024-25%SiC powder sample.
XRD results of three HIPed samples are shown in Figure 3. The reflection peaks from AA2024
alloy (i.e., α-Al and Al-Cu compound) and SiC were found. The average grain sizes estimated
from α-Al peak broadening using the Scherror formula were about 50 nm, implying the retaining
of nanostructure despite of grain coarsening during the consolidation process. Similar grain
growth behavior was also reported for milled Al metal and alloys [4, 6,7].
TEM observation revealed that non-uniform grain structure in the consolidated samples, as
shown by representative images in Figure 4. Compared to the as-cryomilled state, the bulk
samples have much larger grain sizes, typically in the range of 100 to 200 nm, as revealed by the
dark field images. Grains ≤ 50 nm were also frequently present. In some area, much large grains,
in the range of 1 μm, were also observed. The increase of grain size is due to the recrystallization
and grain coarsening at elevated temperatures [6,7] during the degassing and HIPing processes.
Among different bulk samples, no significant difference in the grain size and morphology feature
was detected.
062906_450 C_1h
062906_480 C_1h
062806_510 C_1h
Intensity (Counts)
30 40 50 60 70 80 90
2 Theta (Degree)
Figure 3: X-ray diffraction patterns of 3 bulk AA2024-25%SiC samples.
303
a) b)
c) d)
Figure 4. TEM images showing the grain size in consolidated bulk AA2024-25%SiC sample consolidated by
HIPing at 450°C.
2. Densification behavior of AA2024 -SiC NMMCs

The densification behavior can be reflected by microstructure and mechanical performance of the
consolidated AA2024-SiC samples. Figure 5 displays representative optical microscope images
taken from mechanically polished surface of the HIPed samples. It is found that sample
consolidated at 400°C exhibited the highest density of voids/pores, suggesting the bulk sample
was not fully dense. With an increase of HIPing temperature, the number of voids/pores
decreases. In sample consolidated at 420°C, voids/pores were much less frequently observed.
a) b)
c) d)
Figure 5. Representative optical microscopy image of the surface microstructure in bulk AA2024-SiC samples: a)
sample HIPed at 400°C showing a large number of voids/pores; b) sample HIPed at 420°C showing a small
number of voids/pores; c) sample HIPed at 450°C and d) sample HIPed at 510°C showing no voids/pores.
304
HIPing at temperature 420°C, voids were rarely found, indicating fully dense was obtained.
The high HIPing temperatures (500 and 480°C) produced fully dense bulk NMMCs, but softened
the strength, as shown in Figure 6a. The microhardness data are used to study the densification
behavior. It is found that sample HIPed at 450°C exhibited the highest mean value. For HIPing at
420 and 410°C, the mean value is slightly lower. But no significant difference was found among
these three specimens. At temperatures below 450°C, the general tendency is that the hardness
appears to be stable in high hardness value range. The abnormally low hardness for sample
HIPed at 400°C was noted. The cause is not clear. It is assumed that this may be attributed to
many pores/voids observed in the specimen, as shown in Figure 5a. It is therefore concluded that
a moderate HIPing temperature would achieve the best hardness property.
2500
2000
1500
Hv (MPa)
1000
500
0
350 400 450 500 550
o
HIPing Temperature ( C)
a)
700
650
600
Ultim ate Strength (M Pa)
550
500
450
400
350
300
350 400 450 500 550
HIPing Temperature (0C)
b)
Figure 6. Variation of a) microhardness; and b) ultimate strength with HIPing temperature
for bulk AA2024-SiC specimens.
Moreover, the compressive ultimate strength data are presented in Figure 6b for the HIPed
specimens. It is found that bulk specimens HIPed at moderate temperatures exhibit the best
strength, with ultimate strength over 650 MPa. One can see that the strength decreases for the
specimens HIPed at high temperatures. As the HIPing temperature decreases below 410 °C, the
compressive strength drops significant, being consistent with the hardness data. As discussed in
previous section, this may be attributed to many pores/voids observed in the specimen.
The above process optimization results were used to scale-up for prototype fabrication of
AA2024-SiC NMMC at large-dimension billets. The large amount of cryomilled AA2024-25
305
wt.% SiC powder composite was HIPed at 410°C to produce a prototype billet with diameter of
8 inch and thickness of 1 inch, as shown in Figure 7. SEM observation indicated good
consolidation and uniformity in the prototype. The grain structure revealed by TEM was found to
be similar to those shown in Figure 4. Preliminary results indicated compressive ultimate
strength as high as 700 MPa for the large dimension billet.
a) b)
Figure 7. a) Photo of AA2024-SiC prototype billets; b) SEM image showing typical microstructure in
the prototype fabricated by HIPing. The bright particles were Al-Cu and the dark ones were SiC.
Summary
A large amount of AA2024-25wt.%SiC powder composite consisting of α-Al phase with the
grain size about 25 nm and micrometer-sized SiC particle were produced via cryomilling. In the
bulk samples consolidated by HIPing, the growth of nanometer-sized grains was found to be
limited resulting in α-Al grains with non-uniform sizes typically in the range from about 50 nm
to 200 nm. A moderate HIPing temperature would be used to achieve the best tensile strength
property. For AA2024-25wt.% SiC, HIPing at 410°C appears to be optimal with respect to the
mechanical property. The strength performance was found to be degraded at temperatures above
450°C or below 400°C. The optimized laboratory process was successfully scaled up for mass
production yielding large-dimension NMMC billets with high strength above 700 MPa.
Acknowledgement: This work was supported by US Army Research and Engineering Command
under a SBIR fund covering Phase I and II (Phase II Contract no.: W911W6-06-C-0032).
Reference
1. K.S. Kumar, H. Van Swygenhoven, and S. Suresh: Acta Materialia, 2003, 51, pp.5743-5774.
2. C. C. Koch: Nanostruct. Mater., 1997, vol. 9, pp. 13-22.
3. R.Z. Valiev, R.K. Islamgaliev, and I.V. Alexandrov: Prog. Mater. Sci., 2000, 45, pp.103-189.
4. D. Witkin, B.Q. Han, and E. J. Lavernia, Metall. Mater. Trans., 2006, A37, pp.185-194.
5. M. J. Luton, C.S. Jayanth, M.M. Disko, S. Matras, and J. Vallone: Mat. Res. Soc. Symp.
Proc., 1989, 132, pp. 79-86.
6. F. Zhou, X.Z. Liao, Y.T. Zhu, S. Dallek, E. J. Lavernia, Acta Materialia 51 (2003) 2777-
2791.
7. F. Zhou, J. Lee, S. Dallek, and E. J. Lavernia, J. Mater. Res., 2001, 16, pp. 3451-3458.
306
COMPARATIVE ANALYSIS OF THE INFLUENCE OF INHIBITOR

CONCENTRATIONS ON THE CORROSION SUSCEPTIBILITY OF AL -
1.0%ZN ALLOY IN ACIDIFIED VERNONIA AMEGDALINA,
PIPERNIGRUM AND TELFERIA OCCIDENTALIS.
Ndubuisi Idenyi1, Chinedu Ekuma1, Simeon Neife2
1. Department of Industrial Physics, Ebonyi State University, P.M.B. 053, Abakaliki, Nigeria.
2. Department of Material & Metallurgical Engineering, Enugu State University of Science and
Technology, P.M.B. 01160, Enugu, Nigeria.
Keywords: Corrosion, Aluminium-Zinc, Vernonia Amegdalina, Pipernigrum, Telfera
Occidentalis
Abstract
The influence of varying concentrations of extracts of vernonia amegdalina, pipernigrum and
telferia occidentalis on the corrosion behaviour of Al - 1.0%Zn alloy in varying molarities of
HCl has been investigated. Pre-weighed samples of the alloy were subjected to 0.5M and 1.0M
HCl, each containing 50 cm3and 100 cm3of the extracts separately. The set-ups were allowed to
stand for 28 days with a set of samples withdrawn weekly for corrosion rate characterization.
The results obtained showed the usual corrosion behaviour of initial steep increase in corrosion
rate followed by a gradual decline over exposure time, characteristic of most passivating metals.
Expectedly, the vegetable extracts showed inhibition traits with pronounced effects at lower acid
molarities with higher extract concentrations. When compared, telferia occidentalis showed the
best manifestations, vernonia amegdalina the worst and pipernigrum in-between.
Introduction
The service life of most engineering materials depends on their ability to resist degradation.
Comparatively, some metals are more intrinsically resistant to corrosion than others, either due
to the fundamental nature of the electrochemical processes involved or due to the details of how
reaction products form [1].
The complexity of the corrosion process may be better appreciated by recognizing that many
variables are involved, including environmental, electrochemical and metallurgical aspects. For
example, anodic reactions and rate of oxidation, cathodic reaction and rate of reduction,
corrosion inhibition, polarization or retardation; passivity, effect of oxidizers, effect of velocity,
temperature, corrosive concentration, galvanic coupling and metallurgical structure all influence
the type and rate of the corrosion process [2].
Amongst the various corrosion control and prevention techniques, certain types of chemicals
known as inhibitors may be added to the environment to reduce the aggressiveness of the
environment or to slow down the corrosion process. Inhibitors function by ion- or molecule-
adsorption onto a metal surface. The corrosion rate is reduced by: increasing or decreasing the
anodic and/or cathodic reaction; decreasing the diffusion rate for reactants to the surface of the
metal; or increasing the electrical resistance of the metal surface [3]. However, the types of
environment that can be modified include aqueous, partly aqueous (often found in at near neutral
pH range such as natural waters, cooling water systems and in acidic range such as acid pickling
to remove rolling scale as well as in the production and refinery of oil and gas) and gaseous.
The permanence of metals or alloys in an aggressive environment depends on the protective
properties of organic or inorganic films as well as on the layer of corrosion products. Some film
characteristics, such as chemical composition, conductivity, adhesion, solubility, hygroscopy,
307
and morphology, determine its ability as controlling barrier to different kinds of attack and
corrosion rates [4]. On the other hand, these characteristics depend, in turn, on chemical
composition and metallurgical history of the metal, on physicochemical properties of coating,
and on environmental variables such as atmospheric conditions, type and amount of pollutants,
wet-dry cycles, etc. [4, 5, 6].
Corrosion measurement involves the application of various techniques to determine the
corrosiveness of the environment and the rate of metal loss. It is usually a quantitative method of
evaluating the performance and effectiveness of corrosion control and prevention techniques.
After evaluation is completed, the result obtained is used to improve and enhance the techniques.
These methods for corrosion measurement can be broadly divided into five categories namely:
non-destructive testing, analytical chemistry; fluid electrochemistry; operational data and
corrosion monitoring [3]. The corrosion penetration rate (CPR) as the result of the
physiochemical interactions mostly expressed in mils/year or mm/yr is an important corrosion-
monitoring index that gives reliable information to corrosion experts on the extent of corrosion
advancement in a certain material in service. The mathematical computation of CPR is based on
the formula
k Δ w
C P R = (1)
ρ A t
where Δw is the weight loss after exposure time t, ρ and A are density and exposed specimen
area respectively, and k is a constant whose magnitude depends on the system of units used. For
instance, in this work, k = 87.6. Then, CPR is in mm/yr, and ΔW , t, ρ and A are expressed in mg,
hrs, g/cm3 and cm2 respectively [7]. It must be noted that this estimation is suitable only for
uniform corrosion and becomes somewhat erratic with local instability [8].
The present research is aimed principally on investigating the effect of introducing varying
volumes of different vegetable extracts: vernonia amegdalina, pipernigrum and telferia
occidentalis on the corrosion behaviour of Al - 1.0% Zn alloy haboured in 0.5M and 1.0M
concentrations of hydrochloric acid environments. This study is also necessitated by the
increasing concern about the toxic nature of corrosion inhibitors in industry, which may not only
affect living organisms but also be poison to the earth.
Experimental Techniques
Study Area:
The research “Comparative Analysis of the Influence of Inhibitor Concentrations on the
Corrosion Susceptibility of Al - 1.0%Zn Alloy in Acidified Vernonia Amegdalina, Pipernigrum
and Telferia Occidentalis” was carried out in Abakaliki, Ebonyi State, Southeastern part of
Nigeria in the month of July 2007.
Materials/Equipment:
The materials used for this work were scraps of aluminium (99% pure Al) procured from
aluminum stockist and pure granulated zinc metal procured also from metal stockist. The other
materials used were: vernonia amegdalina, pipernigrum and telferia occidentalis, acetone,
hydrochloric acid, distilled water, laboratory beakers, measuring cylinders, etc.
The equipment used were: lathe machine, drilling machine, a surface crucible furnace and
analytic digital weighing machine which measures to an accuracy of 0.0001g which was used to
weigh the test coupons before and after immersion to know the exact weight loss.
Preparation of Test Samples:
The aluminium scraps and zinc ingot were thoroughly cleaned and the composition carefully
worked out and charged into the surface crucible furnace. The molten alloys were cast into rods
after melt down, machined to considerable dimensions and subsequently, cut into coupon
308
samples of dimension range of 15mm x 14mm x 13.5mm and initial specific surface area of
about 11.6373cm2. Each sample coupon was drilled with a 10mm drill bit to provide hole for the
suspension of the strings and the surface of each thoroughly polished according to ASTM
standard.
Preparation of Test Environment:
The environments for this work were acidic environments of two concentrations (0.5M and
1.0M) made from the stock solution of hydrochloric acid (36.5% purity assay) using normal
procedure.
Experimentation:
To 1 dm3 of concentrations of the hydrochloric acid (0.5M and 1.0M) were respectively added
50cm3 and 100cm3 of the vernonia amegdalina, pipernigrum and telferia occidentalis extracts,
which were found to be totally soluble in the acid. These media were measured out into twelve
(12) beakers and in each of the beakers were suspended four (4) sample coupons of the alloy
after which the set up allowed to stand for 28 days (672 hours). A sample coupon was then
withdrawn from each beaker every 7 days (168 hourly), washed with distilled water, cleaned
with acetone and dried in an open air. The final weight of each of the test sample was determined
using the digital analytic weighing balance.
Results And Discussion
Results:
Tables 1 – 2 represent the corrosion rate data for the Al – 1.0% Zn alloy in the various volume
concentrations of the extracts in 0.5M and 1.0M HCl concentrations.
Discussion of Results:
From the tables, there is apparent indication that normal corrosion trends for passivating metals
were followed in each of the media studied. There was an initial steep rise in corrosion rate
which progressively declined as the exposure time increased. That being the case however, the
degree of passivity varied significantly as the concentrations of the vegetable extracts changed.
Again the chemical nature of the extracts affected their inhibitive characteristics even under the
same acid molarity.
A cursory look at the passivation trends shows that increasing the volume of the extracts at a
constant acid molarity showed an increasing passivity, while at a constant extract volume the
corrosion rates increased as the molarity of the acid increased. This latter case means that at
constant extract volumes the molarity of acid becomes a determining factor in corrosion
behaviour in such a manner that higher acid molarities raise corrosion penetration rates.
In effect, the quantitative and chemical characteristics of the vegetable extracts influenced their
inhibition potentials such that telferia occidentalis proved to be the best inhibitor of the three
studied, followed by pipernigrum, while vernonia amegdalina exhibited the weakest inhibitor
potentials among them.
Consequently, a conclusion is drawn to the effect that the varying degree of inhibition
potentialities of the vegetable extracts is a function of their individual chemical constituents as
opposed to their volumetric characteristics in the acid media.
Acknowledgement
The authors are grateful to the Management of Standards Organization of Nigeria, Delta State
Laboratory for permission to use their facilities and to Ene Esther for her contributions in this
work.
309
References
1. Chinedu E. Ekuma, Ndubuisi E. Idenyi and Anoke E. Umahi, “The Effects of Zinc
Additions on the Corrosion Susceptibility of Aluminium Alloys in Various
Tetraoxosulphate (vi) Acid Environments”. J. of Appl. Sci., 7 (2) (2007), 237-241.
2. Ndubuisi E. Idenyi, Chinedu E. Ekuma and Israel O. Owate, “The Influence of Alloy
Compositions on the Passivation Layer Characteristics of Al – Zn Alloys Systems”. The
Impact of Design on Corrosion Performance, Material Science and Technology (MS&T),
(2006), 613-617.
3. M.N.C. Ijomah, Elements of Corrosion and Prevention Theory, (Enugu, NIG: Auto-
Century Publishing Co. Ltd., 1991), 50-75.
4. M. Stratmann, K. Bohnenkamp, and W. Engell, “An electrochemical study of phase-
transition in rust layers”. Corrosion Science, 23 (1983), 969 – 985.
5. Chinedu E. Ekuma and Ndubuisi E. Idenyi, “Statistical Analysis of the Influence of
Environment on Prediction of Corrosion from its Parameters”. Res. J. Phy., 1 (1) (2007),
27-34.
6. S.G. Stratmann and H. Streckel, "On the Atmospheric Corrosion of Metals which are
covered with thin Electrolyte Layers II - Experimental Results", Corros. Sci., 30 (1990),
697 – 714.
7. William D. Callister, Materials Science and Engineering – An Introduction, (New York,
NY: John Wiley and Sons Inc., 1997), 549-590.
310
Table I: Corrosion characteristics of Al – 1.0% Zn immersed in 50cm3 of the vegetable extracts
in molar concentrations of HCl.
Code Time Initial Final Weight Weight Loss Corrosion
(Hours) Weight (g) (g) rate (mm/yr)
(g)
0.5M HCl + 50cm3 UGU LEAF EXTRACT (telferia occidentalis)
A1 168 10.1250 9.8012 0.3238 5.3537
A2 336 9.9876 9.5287 0.4589 3.7937
A3 504 10.3326 10.1988 0.1338 0.7374
A4 672 10.8790 10.8685 0.0105 0.0434
3
0.5M HCl + 50cm BITTER LEAF EXTRACT (vernonia amegdalina)
A5 168 11.1016 10.5498 0.5518 9.1234
A6 336 10.9760 10.3419 0.6341 5.2420
A7 504 10.5439 10.0609 0.4830 2.6619
A8 672 10.9987 10.6148 0.3839 1.5868
3
0.5M HCl + 50cm UZIZA LEAF EXTRACT (pipernigrum)
A9 168 10.1187 9.0422 1.0765 17.7987
A10 336 10.8764 9.4274 1.4490 11.9788
A11 504 10.5420 9.7456 0.7964 4.3892
A12 672 10.8713 10.3181 0.5532 2.2866
3
1.0M HCl + 50cm UGU LEAF EXTRACT (telferia occidentalis)
A13 168 11.3217 10.6826 0.6391 10.5668
A14 336 11.0875 10.3927 0.6948 5.7439
A15 504 10.9856 10.4126 0.5730 3.1580
A16 672 10.7632 10.3201 0.4431 1.8315
3
A17 168 10.1879 8.1992 1.9887 32.8808
A18 336 10.0549 7.9404 2.1145 17.4804
A19 504 10.9812 9.2167 1.7645 9.7246
A20 672 10.1769 8.8321 1.3448 5.5587
1.0M HCl + 50cm3 UZIZA LEAF EXTRACT (pipernigrum)
A21 168 11.1087 9.9767 1.1320 18.7163
A22 336 11.4198 9.8262 1.5936 13.1742
A23 504 10.8753 9.6359 1.2394 6.8307
A24 672 10.9632 10.2983 0.6649 2.7483
311
Table 2: Corrosion characteristics of Al – 1.0% Zn immersed in 100cm3 of the vegetable extracts
in molar concentrations of HCl.
Code Time Initial Final Weight Weight Loss Corrosion
(Hours) Weight (g) (g) rate (mm/yr)
(g)
0.5M HCl + 100cm3 UGU LEAF EXTRACT (telferia occidentalis)
A25 168 10.1879 9.9010 0.2869 4.7436
A26 336 10.6532 10.2700 0.3832 3.1679
A27 504 10.7653 10.5222 0.2431 1.3398
A28 672 10.7301 10.5394 0.1907 0.7883
3
A29 168 11.2396 10.7478 0.4918 8.1313
A30 336 11.0952 10.5742 0.5210 4.3071
A31 504 10.8959 10.4978 0.3981 2.1940
A32 672 10.1198 9.8720 0.2478 1.0243
3
0.5M HCl + 100cm UZIZA LEAF EXTRACT (pipernigrum)
A33 168 10.7620 10.2961 0.4659 7.7031
A34 336 11.0988 10.5597 0.5391 4.4567
A35 504 11.4322 11.0402 0.3920 2.1604
A36 672 10.9539 10.7100 0.2439 1.0081
3
1.0M HCl + 100cm UGU LEAF EXTRACT (telferia occidentalis)
A37 168 10.1542 9.6103 0.5439 8.9927
A38 336 10.9759 10.3639 0.6120 5.0594
A39 504 10.6523 10.2213 0.4310 2.3754
A40 672 11.0958 10.6660 0.4298 1.7766
3
A41 168 10.1173 8.3741 1.7432 28.8218
A42 336 10.1576 8.3600 1.7976 14.8606
A43 504 10.9016 9.2484 1.6532 9.1112
A44 672 10.6217 9.5719 1.0498 4.3393
1.0M HCl + 100cm3 UZIZA LEAF EXTRACT (pipernigrum)
A45 168 10.2301 8.7547 1.4754 24.3940
A46 336 10.2319 8.8515 1.3804 11.4116
A47 504 10.4309 9.3241 1.1068 6.0999
A48 672 10.4386 9.4312 1.0074 4.1640
312
THE IMPACT OF CORROSION ON THE DEFORMATION BEHAVIOUR

OF Al - Zn ALLOYS IN 0.1M HCl AND SEAWATER.
Ndubuisi Idenyi1, Israel Owate2, Cajethan Okeke3, Simeon Neife4.
1. Department of Industrial Physics, Ebonyi State University, P.M.B. 053, Abakaliki, Nigeria.
2. Department of Physics, University of Port Harcourt, Cboba, Nigeria.
3. Department of Physics and Astronomy, University of Nigeria, Nsukka.
4. Department of Material & Metallurgical Engineering, Enugu State University of Science and
Technology, P.M.B. 01160, Enugu, Nigeria.
Keywords: Deformation, Corrosion, Embrittlement And Aluminium-Zinc Alloy.
Abstract
An investigation into the deformation characteristics of Al - Zn alloys exposed to corrosion
environments has been carried out. Tensile specimen samples of four (4) different grades of
aluminium alloys with varying percentages of zinc were prepared and immersed in baths
containing 0.1M HCl and seawater separately and allowed to stand for 30 days. At expiration of
the exposure time, the samples were withdrawn and rinsed with distilled water and acetone
before being subjected to tensile loading until fracture occurred. The results showed that all the
samples obeyed the stress - strain relationship for a relatively ductile material with those exposed
to acid showing more brittle fracture than those exposed to seawater, a behaviour that is possibly
attributable to hydrogen embrittlement necessitated by the diffusion of hydrogen into the alloy
samples from the acidic media.
Introduction
The development of many technologies that make our existence so comfortable has been
intimately associated with the accessibility of suitable materials. For example, automobiles
would not have been possible without the availability of inexpensive steel or some other
comparable substitute. In our contemporary era, sophisticated electronic devices rely on
components that are made from what are called semi-conducting materials [1]. However, in spite
of the tremendous progress that has been made in the discipline of materials science and
engineering within the past few years, there still remain technological challenges, including the
development of even more sophisticated and specialized materials as well as consideration of the
environmental impact of materials production [2].
Many times, a materials problem is one of selecting the right material from the many thousands
that are available. There are several criteria on which the final decision is normally based. First
of all, the in-service conditions must be characterized, for these will dictate the properties
required of the material. On only rare occasions does a material possess the maximum or ideal
combination of properties. Thus, it may be necessary to trade off one characteristic property for
another. A second selection consideration is any deterioration of material properties that may
occur during service operation. For example, significant reductions in mechanical strength may
result from exposure to elevated temperatures or corrosive environments. Finally, probably the
overriding consideration is that of economics: What will the finished product cost? A material
may be found that has the ideal set of properties but is prohibitively expensive [3].
Corrosion, a term derived from the Latin word corrosus meaning “gnawed away”, occurs as a
result of a physiochemical interaction between the material, mostly a metal and its environment.
As a result, the mechanical properties of metals may be greatly impaired even when no visible
change is observed on the surface of the metal [4].
313
The main factor that causes corrosion of metals is the consequence of their temporal existence in
a state of higher energy level due to the absorbed energy during extraction from their ores. This
makes them unstable and certain environments enhance their combination chemically with
elements in their environment to form compounds and return to their natural stable ore state with
accompanying reduction in the free energy of the system [5].
Aluminum alloys of the 1xxx, 3xxx, 5xxx and 6xxx series are resistant to corrosion in many
natural waters. The major determining factor to the corrosivity of natural waters in aluminum
alloys includes temperature, pH and conductivity, availability of cathodic reactant, presence or
absence of heavy metals, and the corrosion potentials and pitting potentials of the specific alloys.
Wet corrosion comprises the degradation effect of engineering materials in soil, seawater,
oceans, steam plants etc. Basically, corrosion in wet environment can be minimized by:
eliminating contact of dissimilar metals by using insulating couplings or joints; the removal of
dissolved oxygen; and the use of protective coatings or oxide coatings, which provides a barrier
between the corroding metal and its environment [6].
Metals deform principally due to the motion of existing dislocations coupled with the interaction
of many additional dislocations in a crystallographic unit cell. But in a polycrystalline specimen,
mutual interface of adjacent grains results in slip occurance accompanied with strain hardening
of the metal. Depending on whether the dislocation that cut across one another are of edge or
screw, a consequence of the Burger’s vector, the result may be the creation of a line of vacancies
or interstitialcies in the crystal lattice or displacement of part of the dislocation into a slip plane
parallel to the original slip plane. These structural defects could to a large extent be a major
determinant of the degree of resistance of metal components to the effects of media-driven
corrosion [7].
Experimental Techniques
Materials/Equipment:
The materials used for this work were sheets of Al – Zn alloys of known compositions produced
by FIRST ALUMINIUM PLC., Port Harcourt, Nigeria, acetone, 0.1Mhydrochloric acid,
seawater, distilled water, laboratory bowls, strings, etc.
The equipment used were metal shearer and tensile testing machine.
Preparation of Test Samples:
The sheets were sheared to standard tensile test specimen sizes using the metal shearer in the
factory laboratory.
Preparation of Test Environment:
The environments for this work were 0.1M hydrochloric acidic prepared in the Industrial
Chemistry Laboratory of Ebonyi State University, Abakaliki and seawater sourced from Port
Harcourt, a river-rine city in Nigeria.
Experimentation:
Both environments were each poured into large plastic bowls. The test coupons were suspended
with nylon strings into the bowls. The setup were allowed to stand for 30 days, after which they
were withdrawn, soaked in acetone for 5 minutes and then rinsed with distilled water. They were
then subjected through the normal procedures for tensile test determination and the required
parameters measured. Graphs of force against extension for each sample in each media were
plotted and compared against those of the control samples which were not immersed into any
environment.
314
Results And Discussion
Results:
Figures 1 – 3 represent the force against extension curves for each of the four samples in the
various corrosion environments.
1600
1400
1200
1000
Force (N)
A
B
800
C
D
600
400
200
0
0 0.4 0.8 1.2 1.6 2 2.4 2.8 3.2 3.6 4
Extension (mm)
Fig. 1 Force against extension graph for the control samples.
1600
1400
1200
1000
A
Force (N)
B
800
C
D
600
400
200
0
0 0.4 0.8 1.2 1.6 2 2.4 2.8 3.2 3.6 4
Extension (mm)
Fig. 2 Force against extension graph for the samples in seawater.
315
1400
1200
1000
800 A
Force (N)
B
C
600 D
400
200
0
0 0.4 0.8 1.2 1.6 2 2.4 2.8 3.2 3.6 4
Extension (mm)
Fig. 3 Force against extension graph for the samples in 0.1M HCl.
Discussion of Results
From the figures, it could be seen that the normal stress – strain curves for relatively ductile
materials, to which aluminium belongs, were followed by all the samples in each of the media
studied.
Strain Behavior: A critical look at the curves shows that for the controls (fig. 1), apart from
sample A which fractured at an extension of 3.60mm and C fracturing at an extension of
2.80mm, the other samples could only extend up to 2.40mm before fracture. In seawater (fig. 2),
sample A extended up to a maximum of 2.40mm, B and C extended up to 2.00mm maximum
and D extended to only 1.60mm maximum before ultimately fracturing. In acid (fig. 3), there
was no serious departure from the strain values observed in seawater except for sample A that
could only extend up to 2.00mm and C that was indeterminate due to excessive reduction in
thickness beyond the limit that could be gripped unto the tensile testing machine. These
behaviours suggest that there is a relationship between corrosion media and strain such that the
presence of embrittling species in a corrosion medium reduces the ductility of the material.
Stress Behavior: Of important consideration is the maximum force to failure of each sample in
the various media. Sample A failed at 1395.00N, 1410.00N and 1081.25N for the control,
seawater and acid respectively. B failed at 1275.00N, 1237.50N and 1062.50N in the same order;
C, at 980.00N and 987.50N for the control and seawater, the acid being indeterminate; and D
failed at 1470.00N, 1350.00N and 1215.00N respectively.
In comparative terms, sample A appear to be more ductile and relatively easy to be drawn with
minimal force followed by D, while B and C are apparently brittle with C showing more
brittleness than D. The import of this is that strain hardening set in and progressively increased
as the samples were drawn in the order A, D, B and C, which may have resulted from the
percentage of zinc in the samples where chemical analysis showed the Zn values as 0.29370,
0.24036, 0.18574 and 0.10103 for A, D, B, and C respectively. This is reasoned from the point
316
of view that zinc would settle along the grain boundaries and interfere with dislocation
movements thereby causing strain hardening.
Conclusion
Based on the foregoing discussions, a conclusion is drawn to the effect that the presence of zinc
indeed improved the deformation characteristics of aluminium even in harsh corrosion
environments especially its ductility and strength the indeterminate value of sample B in acid not
withstanding, since there must have been other extraneous factors that may have led to the rather
faster corrosion rate observed in this particular case.
Acknowledgement
The authors are grateful to the Staff and Management of First Aluminium Plc, Port Harcourt,
Nigeria for permission to use their facilities for this work.
References
1. D.R. Askeland, The science and engineering of materials, (Boston, MA: Wardsworth
Inc., Boston, Massachusetts, 1985), 521-551.
2. Chinedu E. Ekuma, and Ndubuisi E. Idenyi, “The analysis of the corrosion susceptibility
of Al – Zn alloys in tetreoxosulphate (vi) acid environments”. Trends in Applied
Scientific Research, USA, 2 (1) (2007), 66 – 70.
3. Myer Kutz, (ed), A handbook of materials selection. (New York, NY: John Wiley and
Sons Inc., 2002), 89-134.
4. G. Wranglen, An introduction to corrosion and protection of metals. (New York, NY:
Champan and Hall Inc., 1985), 421-433.
5. Milton Ohring, Engineering materials science, (California, CA: Academic Press Inc.,
California, 1995), 501-553.
6. Ndubuisi E. Idenyi, Chinedu E. Ekuma, and Israel O. Owate, “The influence of alloy
compositions on the passivation layer characteristics of Al – Zn alloys systems”.
Proceedings of Materials Science and Technology 2006 Meeting and Exhibition,
Cincinnati, Ohio, USA, (October 15th – 19th), 613 – 617.
7. Ndubuisi E. Idenyi, Simeon I. Neife, and Anyasi, U. Uzor, “The corrosion behaviour of
recrystalized mild steel in various tetraoxosulphate (vi) acid [H2SO4] concentrations”,
Journal of Corrosion Sc. and Tech. 1 (1) (2004), 54 – 55.
317
EFFECTS OF DIFFERENT ANNEALING PROCESSES ON

MICROSTRUCTURAL FEATURES OF TWIN ROLL CAST 3003 AND
8006 ALUMINUM ALLOYS
B. Çorlu1, A. Dursun1, M. Dündar1, C. Inel1
1
Assan Aluminyum A.Ş. D-100 Karayolu Uzerı 32.km Tuzla, Istanbul, 34940, Turkey
Keywords: Twin Roll Casting, 3003, 8006, Salt Bath, Continuous Hot Annealing.
Abstract
Twin roll casting (TRC) can be used to produce aluminum sheets by direct solidification from
the melt. Rapidly solidified (upto 800 0C/sec) outer skin has a supersaturated microstructure with
very fine grains. Application of prescribed processing routes of TRC cast material, like soft
annealing to produce H1X tempers, to the TRC 3003 and 8006 alloys, results in the formation of
very large surface grains after recrystallization which causes unwanted surface features called
“orange peel” after bending or deep drawing processes. In the present work, annealing processes
were carried out in a salt bath in order to see the effect of high heating rate on recrystallized
grain size. In addition, the effect of high temperature rapid annealing process prior to the rolling
operation on microstructural features were also demonstrated. Surfaces and through-thickness
microstructures of the specimens were investigated under optical microscope and the mechanical
properties have been discussed accordingly.
Introduction
TRC aluminum has different microstructure than that of DC cast materials [1,2]. Water cooled
caster rolls provide very high solidification rates (upto 800°C/sec). Rapidly solidified outer skin,
can be called featureless zone, has a supersaturated microstructure with very fine grains
decorating this limited volume. In addition to this characteristic microstructure, when big TRC
3003 and TRC 8006 aluminum coils are subjected to homogenization treatment in batch type
annealing furnaces, the heating regimes delays the time required to reach the desired annealing
temperature at every point of the coil. The combination of the metallurgical transformations due
to the heating regime and the supersatured zone on surfaces of TRC 3003 and TRC 8006 alloys
leads to some unwanted microstructural features like grain coarsening.
Some studies revealed that high heating rates has a great influence on microstructural
characteristics [3,4]. In addition to that, Somerday, et.al [5] investigated the effects of heating
rates and precipitate formation on the grain size of Al-Mn alloys.
In this study, annealing processes have been carried out in a salt bath in order to see the effect of
high heating rate on recrystallized grain size. In addition, the effect of high temperature rapid
annealing process prior to the rolling operation on microstructural features have also been
demonstrated. Chemical compositions (wt.%) of 3003 and 8006 aluminum alloys that were used
in this study are given in Table I. 6mm 3003 and 8006 sheets were produced by TRC technology
and further processed according to the sequences given in Tables II and III.
Table I. Chemical compositions of 3003 and 8006 aluminum alloys (wt.%).
Si Fe Cu Mn Mg Cr Zn Pb Al
3003 0.11 0.424 0.06 1.059 0.006 0.001 0.008 0.0007 98.29
8006 0.098 1.412 0.006 0.644 0.002 0.004 0.006 0.0008 97.79
319
Salt Bath Annealing
In Table II, „SB“ abbreviation represents that the annealing process was carried out in salt bath
according to the given process parameters and that the samples were air cooled after SB
annealing. Five main process sequences were followed in this section; three for 3003 samples
and two for 8006 samples. Process number „1“ includes final annealing (FA). Process number
„2“ includes a high temperature homogenization treatment (HTH) at as-cast thickness (6mm),
cold rolling down to 1.5mm and then a FA. Regarding process number „3“, the samples were
cold rolled to 2.5mm at which an intermediate thickness high temperature homogenization
treatment (IHTH) was carried out; then the samples were cold rolled to 100µ and subjected to a
FA. “4” and “5” coded processes include a HTH at 6mm, cold rolling down to 250µ and 250µ,
respectively, and a FA. The corresponding process details conducted in SB and their locations in
the process sequence are given in Table II.
Table II. The applied process details.
Process
Alloy Process Details
No
1 6.0mm→1.5mm→FA
2 6.0mm→HTH→1.5mm→FA
3 6.0mm→2.5mm→IHTH→100µ→FA
3003
1-SB 6.0mm→1.5mm→520°C /20min (SB)
2-SB 6.0mm→520°C /20min (SB)→1.5mm→FA
3-SB 6.0mm→2.5mm→520°C /20min (SB)→100µ→FA
4 6.0mm→HTH→250µ→FA
8006 5 6.0mm→HTH→120µ→FA
4-SB 6.0mm→520°C /20min (SB)→250µ→FA
5-SB 6.0mm→520°C /20min (SB)→120µ→FA
High Temperature Rapid Annealing Prior to Rolling

The schematic view of the process conducted in this part of the study includes a 3m length
continuous annealing furnace prior to the rolling process (CAF1), a roller and a 3m long CAF2
after the roller (Figure 1).
Rolling
Al-Coil CAF1 CAF2

Cut-to-length sample
3m 3m
Figure 1. Schematic view of “High Temperature Rapid Annealing Prior to Rolling” Process
Only 3003 samples were employed in this study. Applied changes in the process parameters
resulted in the surface temperatures given in Table III. Only CAF1 was run for the first 8
samples. On the other hand, for the samples “9-16”, both CAF1 and CAF2 were operated.
320
Table III. The “sample codes” and corresponding applied process parameters
Sample Sheet Surface Temperature Sheet Surface Temperature Line Speed Final Thickness
Code Measured After CAF1 (°C) Measured After CAF2 (°C) (m/dk) (mm)
1 295 - 5.34 1.25
2 325 - 5.34 1.25
3 350 - 5.34 1.25
4 375 - 5.34 1.235
5 400 - 5.34 1.22
6 425 - 5.34 1.195
7 455 - 5 1.135
8 477 - 5 1.13
9 295 510 5.3 1.27
10 325 520 5.3 1.25
11 350 518 5.3 1.235
12 375 525 5.3 1.225
13 400 520 5.3 1.2
14 425 510 5.3 1.18
15 455 515 5 1.14
16 477 477 5 1.15
Specimen cross-sections were examined metallographically by utilizing Zeiss AxioCam MRc5

optical microscope. Samples were ground with SiC paper, polished with 3 μm diamond and
finished with colloidal silica. After electropolishing with Barker’s solution, grain structures were
observed under cross polarized light. In addition, the mechanical tests were preformed on the
specimens by utilizing Zwick Roell 1478 tensile testing equipment and Zwick Z10 hardness
equipment.

Salt Bath Annealing
Mechanical Properties. Standard mechanical properties (1-5) and their counterparts after SB
annealing are given in Table IV. “1” and “1-SB” exhibit similar mechanical properties which
could be considered as the success of SB annealing treatment at 1.5 mm thickness. As comparing
the mechanical properties of the samples obtained from processes “2 “ and “2-SB”, it should be
noted that FA of the latter was conducted at a higher temperature than that of the former. Despite
higher FA temperature, standard mechanical properties could not be reached when SB heat
treatment was carried out instead of HTH treatment. As SB annealing is applied instead of IHTH
treatment as in the case of “3-SB”, although the yield and tensile strengths are very close to the
standard values, elongations are much lower. Regarding 8006 samples, standard HTH treatment
were replaced by SB annealing; hence desired mechanical properties could not be obtained after
“4-SB” and “5-SB” coded processes.
321
Table IV. Mechanical properties obtained after specified processes.
Direction
wrt. Yield Tensile
Thickness Elongation
Alloy Process No Rolling Strength Strength n r
(mm) (%)
Direction (MPa) (MPa)
(°)
0 64.9 119 32.8 0.13 0.89
1 1.5 45 63.5 114.2 28 0.13 0.72
90 61.4 114.3 27.7 0.14 0.45
0 52.2 108.3 31.6 0.19 0.95
2 1.5 45 53.3 106.6 26.9 0.19 0.87
90 52.5 103.4 32.7 0.19 0.71
3003 3 0.1 0 151.4 162.3 14.1 - -
0 64.5 118.5 29.9 0.13 0.84
1-SB 1.5 45 64.7 116.9 24.8 0.13 0.77
90 62.3 115.1 25.7 0.14 0.43
0 61.7 116.4 25.1 0.15 -
2-SB 1.5
0 62 117.1 27 0.15 -
3-SB 0.1 0 146.4 165.1 5 - -
4 0 90.8 127 30.1 - -
5 0 94.7 128.4 23.2 - -
8006
4-SB 0 112.9 162.5 14.5 - -
5-SB 0 141.4 161.7 15.2 141.4 161.7
Microstructural Investigation. Longitudinal and transversal cross sectional microstructures of

3003 samples cold rolled down to 1.5 mm and those subjected to process “1” and “1-SB” are
given in Figure 2. Standard samples exhibit very large grains on the surface. However, surface
grain size of SB treated counterparts are much smaller and distributed much more uniformly
through the thickness. Small photographs placed on Figure 2.b and c are the surface
macrostructure of the samples. (It should be noted that these macrographs should be compared to
each other only.)
1.5mm 1.5mm-FA 1.5mm-520°C/20min-SB
a b c
1.5mm 1.5mm-FA 1.5mm-520°C/20min-SB
d e f
Figure 2. a,b,c. Longitudinal and d,e,f. transversal cross sectional microstructures of the specimens cold
rolled to 1.5 mm and annealed under specified conditions.
HTH treatment applied in “2” and its counterpart “2-SB” resulted in completely different
microstructures and intermetallic distribution (Figure 3 and 4). Although HTH treated 6mm thick
specimen exhibits very large grains, grain structure obtained as a result of “2-SB” is very similar
to that of as-cast specimen. However, it should be kept in mind that these results are depicted
from optical microscopy which has a limited magnification and resolution ability. It could be
322
stated that intermetallic distribution of SB treated specimen remained unchanged, whereas HTH
treatment allowed the diffusion of the intermetallic constituents resulting in different particle
distribution. Therefore, the intermetallic “channels” of the as-cast specimen transformed into
“spherical” intermetallics after HTH. On the top of each image in Figure 4, surface hardnesses of
each specimen in HB are shown. As expected, as-cast specimen has the highest hardness (44,5
HB). Although there were no indications of recrystallization in SB treated samples, the hardness
value decreased to 40 HB, which could be interpreted as an amount of recovery taking place
during SB treatment. On the other hand, samples subjected to HTH treatment have undergone
recrystallization and grain growth leading to 32 HB hardness values.
6mm 6mm-HTH 6mm-520°C /20min (SB)
a b c
Figure 3. Longitudinal microstructures of 6mm thick 3003 aluminum alloy specimens a. without
annealing b. HTH treated c. 520°C/20min SB annealed.
323
6mm (44.5HB) 6mm-HTH (32HB) 6mm-520°C/20min(39HB)
a b c
Figure 4. Longitudinal intermetallic distribution of 6mm thick 3003 aluminum alloy specimens a.
without annealing b. HTH treated c. 520°C/20min SB annealed.
After HTH and SB treatment at 6mm, specimens were cold rolled down to 1.5mm followed by
FA. As a result, SB treated specimen exhibited larger surface grains than HTH treated ones did.
Photographs placed on Figure 5.a and b reveal this difference clearly. Through thickness grain
size distribution is more homogeneous in SB treated sample.
6mm-HTH-1.5mm-FA 6mm-520°C/20min-SB-1.5mm-FA
a b
6mm-HTH-1.5mm-FA 6mm-520°C/20min-SB-1.5mm-FA
c d
Figure 5. a,b. Longitudinal and c,d. transversal cross sectional microstructures of the specimens annealed
under specified conditions
As the samples colled rolled to 2.5 mm and subjected to IHTH and SB treatments were
investigated, it was observed that the surface grains of the former were much larger than those of
the latter (Figure 6). SB treated specimen’s surface grains are larger than the central ones, but
still more homogeneously distributed through thickness.
324
2.5mm 2.5mm-IHTH 2.5mm-520°C/20min-SB
a b c
2.5mm 2.5mm-IHTH 2.5mm-520°C/20min-SB
d e f
Figure 6. a,b,c. Longitudinal and d,e,f. transversal cross sectional microstructures of the specimens cold
rolled to 2.5 mm and annealed under specified conditions.
Regarding 8006 samples, it is possible to do the same comments for 3003 samples on the grain
appearance and intermetallic distribution (Figure 7 and 8). Again, as-cast specimen has the
highest hardness (44.8 HB). The hardnesses of the HTH and SB treated samples are 31.7 HB and
37.5 HB, respectively pointing out recovery taking place after SB treatment.
325
6mm 6mm -HTH 6mm-520°C/20min-SB
a b c
,
Figure 7. Longitudinal microstructures of 6mm thick 8006 aluminum alloy specimens a. without
annealing b. High temperature homogenized c. 520°C/20min SB annealed.
6mm (44.8HB) 6mm-HTH (31.7HB) 6mm-520°C/20min SB (37.3HB)
a b c
Figure 8. Longitudinal intermetallic distribution of 6mm thick 8006 aluminum alloy specimens
a. without annealing b. HTH treated c. 520°C/20min SB annealed.
326
As briefly mentioned in the introduction part, effect of heating rate is expected to have a great
influence on the microstructural features [3,4]. When an annealing process is conducted
following a certain amount of cold rolling, recovery, recrystallization and grain growth processes
takes place. During recovery, some of the stored internal energy is relieved by dislocation motion
as a result of atomic diffusion at elevated temperatures. There is some reduction in the number of
dislocations, and dislocation configurations are produced having low energies. After recovery is
completed, the grains are still relatively in high energy state which is the driving force for
recrystallization. In these studies, it was proposed that high heating rates could decrease the
amount of recovery and therefore, increase the driving force for recrystallization. Hence, that
would result in the formation of more nucleation sites and finer grain size.
In addition to that, according to studies about Al-Mn alloys conducted by Somerday, et.al. [5], at
low heating rates, quite large number of precipitates are formed on grain boundaries before
recrystallization. It was also shown that at high heating rates (e.g. 500°K/h), precipitation takes
place mostly on high angle grain boundaries (HAGB). At intermediate heating rates (e.g.
100°K/h), probability of precipitation on medium angle and low angle grain boundaries (MAGB,
LAGB) increases. And finally at low heating rates (e.g. 10°K/h), this probability of precipitation
on MAGB and LAGB increases further. Therefore, depending on the type of the grain boundary
in the microstructure, the amount of precipitation taking place before recrystallization, therefore
the final microstructure of the material changes. Due to these different precipitation trends as a
function of heating rate, the precipitate distribution obtained from high heating rates is not as
well distributed as those obtained from low heating rates. Independent of heating rates, these
precipitates tend to align in the rolling direction and during recrystallization and grain growth
they impede the grain boundary movement perpendicular to the rolling direction. Owing to more
homogeneous precipitation, the specimens annealed with slower heating rates exhibit narrower
and larger recrystallized grains [5].
High Temperature Rapid Annealing Prior to Rolling

The first 6 specimens in the present study did not show any signs of recrystallization (Figure 9
and 10). “7” and “8” coded samples exhibit partial recrystallization which could be deduced both
from microstructural examination and mechanical properties (Table 5). “9-16” coded samples
were fully recrystallized and the grains were distributed homogenously through the thickness.
327
Table 5. Mechanical properties at the end of “high temperature rapid annealing prior to rolling”.
Sheet Sheet
Surface Surface Thickness
Line Yield Tensile
Sample Temperature Temperature After Elongation
Speed Strength Strength
Code Measured Measured Rolling (%)
(m/dk) (MPa) (MPa)
After CAF1 After CAF2 (mm)
(°C) (°C)
0 - - - 2.035 180 192 6.4
1 295 - 5.34 1.25 205 209 4.3
2 325 - 5.34 1.25 203 208 4
3 350 - 5.34 1.25 201 205 3.2
4 375 - 5.34 1.235 199 202 4.7
5 400 - 5.34 1.22 196 202 5.1
6 425 - 5.34 1.195 192 197 5.9
7 455 - 5 1.135 170 178 5.6
8 477 - 5 1.13 173 178 6.6
9 295 510 5.3 1.27 75 119 33.9
10 325 520 5.3 1.25 76 119 28.9
11 350 518 5.3 1.235 75 118 28.6
12 375 525 5.3 1.225 78 118 31.2
13 400 520 5.3 1.2 78 116 32.9
14 425 510 5.3 1.18 75 114 27.9
15 455 515 5 1.14 84 117 29.1
16 477 477 5 1.15 81 117 26.4
328
0 1 2 3
4 5 6 7
8 9 10 11
12 13 14 15
16
Figure 9. Surface macrostructures of the high temperature rapid annealed specimens prior to
cold rolling.
329
0
1 2 3
4 5 6 7
8 9 10 11
12 13 14 15
16
Figure 10. Surface microstructures of the high temperature rapid annealed specimens prior to
cold rolling.
In “continuous annealing prior to rolling” process, although the applied annealing temperatures
were relatively high, the time period in the furnace was not adequate in order for recrystallization
takes place. It should be noted that the “7 and 8” coded samples experienced a small amount of
recrystallization owing to a higher annealing temperature. The samples were produced by TRC
and cold rolled down to 2mm have a high amount of stored energy. In this high energy state, if
the material is annealed for 30 seconds, during recovery amount of dislocations decrease due to
dislocation annihilation resulting from enhanced atomic diffusion. Therefore, it should be
expected that microstructural features of the material will be quite different after first continuous
annealing. In addition, hot rolling could induce some amount of dynamic recovery. After this
process, the remaining amount of stored energy is left for driving force for recrystallization.
Hence, after second continuous annealing, an increased number of nucleation sites, that is, fine
grained microstructure are expected.
330
Conclusion
“1” and “1-SB” exhibit similar mechanical properties which could be considered as the success
of SB annealing treatment at 1.5 mm thickness. Standard samples exhibit very large grains on the
surface. However, surface grain size of SB treated counterparts are much smaller and distributed
much more uniformly through the thickness.
Despite higher FA temperature, standard mechanical properties could not be reached when SB
heat treatment was carried out instead of HTH treatment. HTH treatment applied in “2” and its
counterpart “2-SB” led to different microstructures and intermetallic distribution. As-cast
specimen has the highest hardness (44,5 HB). SB treated samples, has the hardness value of 40
HB, which indicates recovery taking place during SB treatment. On the other hand, samples
subjected to HTH treatment have undergone recrystallization and grain growth leading to 32 HB
hardness values.
After HTH and SB treatment at 6mm, specimens were cold rolled down to 1.5mm followed by
FA. As a result, SB treated specimen exhibited larger surface grains than HTH treated ones did.
When SB annealing is applied instead of IHTH treatment as in the case of “3-SB”, although the
yield and tensile strengths are very close to the standard values, elongations are much lower. It
was observed that the surface grains of 2.5mm IHTH were much larger than those of 2.5mm SB.
Regarding 8006 samples, standard HTH treatments were replaced by SB annealing; desired
mechanical properties could not be obtained after “4-SB” and “5-SB” coded processes.
References
1. E. Nes, S. Slevolden, Jahrg., 55 (1979), 319-324

2. H.Westengen, K. Nes, J. Metals, 35 (1983), No 12, 1111-1127
3. X.F. Yu, Y.M. Zhao, X.Y.Wen, T.Zhai, Mater. Sci. Eng. A, 394 (2005) 376-384
4. S. Sarkar, M.A. Wells, W.J. Probe, Mater. Sci. Eng. A, xxx (2006) xxx-xxx (article in press)
5. M. Somerday, F.J. Humhreys, Mater. Sci Tech., 19 (2003) 20-29
331
PREFABRICATED MATERIALS PREFORMS IN TITANIUM ALLOYS

USING STATIONARY SHOULDER FRICTION STIR WELDING
Philip Threadgill1, Bradley Wynne2, Michael Russell1 and Peter Davies2
1
TWI Ltd, Granta Park, Great Abington, Cambridge CB21 6AL, UK
2
Institute for Microstructural and Mechanical Processing Engineering: The University of
Sheffield (IMMPETUS), Mappin Street, Sheffield S1 3JD, UK.
Keywords: Friction Stir Welding, Titanium, Additive Manufacture, Microstructure
Abstract
Many complex aerospace components are machined from expensive large blocks of materials
which often have long lead times. Many of these materials, especially titanium alloys, are
difficult to machine, and since the fly/buy ratios can be below 10%, this is a financially and
environmentally unattractive approach. Many machining preforms can be easily manufactured
from smaller pieces of materials for relatively low cost. Several approaches are available, but this
paper will consider the benefits of stationary shoulder friction stir welding. Examples are given
of recent work which highlight the possibilities for titanium alloys. The paper includes detailed
microstructural analyses of welded samples via optical and scanning electron microscopy, which
demonstrate the excellent microstructures and properties which can be obtained.
Introduction
The high cost of raw materials for aerospace manufacture together with their often limited
availability has awakened interest in the aerospace industry in the use of additive manufacture to
build up complex components from small sub-parts, instead of machining down large blocks,
often removing 90% of the material. The economics of high buy-to-fly ratios are becoming more
difficult to sustain. Although detailed studies are not available, it is also likely that additive
manufacture will also significantly reduce the energy required to manufacture the final
component.
A number of approaches have been proposed to enable additive manufacturing, but the processes
described in this paper will concentrate on the use of the newly developed stationary shoulder
friction stir welding. This approach is suitable for coarse manufacture of pre-forms in titanium,
and the approach has the advantage that fairly high build–up rates are possible. Alternative
friction based processes such as linear and rotary friction welding are also possible(1), and these
methods are therefore a complimentary technology to approaches such as direct metal deposition
using laser or electron beams. Power beam processes typically build up at a much slower rate,
but are better able to achieve true near net shape performance with only minimal post weld
machining or dressing required. The choice of process is dictated by the size and shape of the
component to be made, and of course by the availability of equipment.
This paper describes some preliminary experiments in Ti-6Al-4V alloy, using stationary shoulder
friction stir welding.
333
Results
All friction stir welding has been carried out using the stationary shoulder variant of the process.
This has the advantage of using contact between the tool probe (rather than the tool shoulder)
and the titanium workpiece to generate the heat, and results in reasonably constant heat
generation through the thickness of the titanium, a distinct advantage in a material of low thermal
conductivity and restricted hot work temperature range. Full details of the process are described
elsewhere (2).
Welds were made on the ESAB Superstir machine at TWI’s Cambridge Laboratory. Although an
inert gas shield is not required for aluminium alloys, it is normal to use an argon shield when
welding titanium, but as the contamination depths will normally be much less than the machining
allowance, the need for the shielding is questionable. However, the concept of an oxidized
surface on welded titanium rests very uneasily with traditional titanium fabricators and their
customers, and so the shielding gas is probably a worthwhile investment.
Initial trials were used to build up layers of a Ti-6Al-4V alloy in 3mm layers. Figure 1 shows the
completed structure with four deposited layers after machining to a 9mm width. The original
width was greater, as it is not straightforward to weld right up the edge by this process. A macro
section is shown in Figure 2, and the approximate positions of the layers are marked. A Vickers
hardness map of the same section is shown in Figure 3.
Figure 1. Appearance of structure after build-up with four 3mm layers, after machining.
On the macrograph shown in Figure 2 the microstructure within the deposited layers appears to
be relatively uniform and typical of that found in the thermo-mechanically affected zone
(TMAZ) of a friction stir weld in this alloy. At the interface between the deposited layers and at
the interface between the base material and the first deposited layer there appears to be small
HAZs of 0.2 and 0.5 mm in thickness, respectively, which again is typical for this alloy. The
uniformity of microstructure is also confirmed by the micro-hardness map (using a 0.3kg load)
shown in Figure 3 which shows a small increase in hardness in the deposited layers in
comparison to the base material but no significant variation in hardness within each deposited
layer or between each layer. It is clear that the material has been heated significantly above the
beta transus (approximately 996±14°C), although the peak temperature is not accurately known,
but believed to be approximately 1100° to 1200°C. The reasonably rapid rate of cooling gives a
very fine transformation product, but there is little evidence for the hard martensitic phases
which can form with very rapid cooling. It is also interesting to note that at the scale of
334
observation in Figure 2 the typical microstructure of the first pass is virtually indistinguishable
from that of the third pass. This is clearly demonstrated in Figure 4.
f
d
e c
a b
Figure 2. Macrograph of the base material and a 4 Figure 3. Vickers micro-hardness map of
layer build up of Ti-6Al-4V. Letters a-h refer to the base material and a 4 layer build up of
locations of micrographs in Figure 5. Ti-6Al-4V.
Figure 4. Microstructures from first (left) and third friction stir passes.
To investigate the microstructure and its evolution during the depositing process in more detail
scanning electron microscopy was undertaken throughout the cross-section of the deposited
layers and typical microstructures at different locations are shown in Figure 5. The exact
locations of the micrographs in Figure 5 are marked in Figure 2. The base material (Figure 5(a))
is typical rolled microstructure consisting of equilibrium volume fractions of globularized alpha
and beta, with the beta located mostly at triple points of the alpha grains. In the region of base
material that is in the outer region of the HAZ (Figure 5(b)), the beta phase becomes more
equiaxed/rounded and increases in volume fraction. Further into the HAZ (Figure 5(c)) the beta
grains start to contain very fine surface relief indicating they have transformed to non-
equilibrium alpha suggesting that the increase in beta volume fraction is greater than the room
temperature equilibrium. Volume fraction of these beta grains continue to increase and they
335
(a) (b)
5 µm 5 µm
(c) (d)
5 µm 5 µm
(e) (f)
5 µm 10 µm
(g) (h)
10 µm 10 µm
Figure 5. Scanning electron micrographs of typical microstructures observed in the base
material and deposited layers. Location of individual micros graphs can be seen in Figure Y.
become the continuous phase (Figure 5(d)), however, the isolated alpha grains pin the
microstructure and prevent beta grains from growing. The alpha grains have a surface ring effect
336
which we believe might be due to shrinking during heating and then regrowth during cooling.
Once the alpha grains have almost completely disappeared and the pinning effect is lost (Figure
5(e)), there is a substantial coarsening of the beta grain structure with a grain size in the order 10-
15 µm. Figure 5(e) also confirms the idea that the cooling rates are not especially rapid as there
is clear formation of grain boundary alpha on the prior beta grain boundaries. In the weld proper,
the microstructures (Figures 5(f) and (g)) are 100% transformed beta with the microstructures
best described as either Widmanstätten or basket weave, with some grain boundary alpha in
places. These microstructures were uniform throughout the deposited layers and there was no
evidence of parent material suggesting that all the deposited material has gone through the same
thermo-mechanical cycle. The HAZs between the deposited layers possibly appeared to be
coarser than the weld material but as can be seen by Figure 5(h) in comparison to Figures 5(f)
and (g) the differences are minimal. Work is now underway using high resolution backscatter
diffraction to see if the underlying crystallographic texture also shows similar consistency
throughout the deposited layers.
Clearly, building up in 3mm thick layers is less attractive than building up in thicker layers. At
the time of writing, the stationary shoulder friction stir welding process can comfortable build up
layers of ~8mm thickness, and there is no known metallurgical reason why this figure should not
be significantly increased. Recent work has examined structures made by adding 6mm thick
layers, and in this case there have been two welds in each layer. Figure 6 shows a macrosection
from an early trial, and it is clear that an encouraging result has been obtained. Although detailed
characterization of the microstructure is still underway, initial results have indicated that the
microstructures are similar to those reported above for 3mm layers, and this is as would be
expected.
Figure 6. Additive manufacture using 6mm layers of Ti-6Al-4V
Discussion
The potential for the use of stationary stir friction stir welding for manufacturing preforms is
clearly encouraging, and after these initial trials it appears that no major obstacles exist to further
development of the technique. The prospects for scaling up the process appear to be good, as it is
already possible to make lap welds using the stationary shoulder friction stir welding approach in
thicker layers than the 3 and 6mm used here. However, it is not claimed that this process will
always be the most attractive, as the choice between this and several other competing processes
will depend on the particular geometries.
337
The microstructures obtained have presented re-assurance rather than surprises, and appear at
this stage to be the same as for friction stir welds previously reported in Ti-6Al-4V (3,4). Since
the heat is generated more or less uniformly through the thickness in stationary shoulder friction
stir welding, distortion levels have to date appeared to be low, and certainly lower than those
found when using conventional friction stir welding for this alloy.
This paper presents a snapshot of work in progress, and further work on the optimization of tool
design and tool material, process parameters and detailed microstructure is underway. Work on
residual stresses is also required, as this, along with a more detailed appraisal of the
microstructure, will determine the need for heat treatment before or after final machining. There
is a good prospect of improving productivity by optimizing the welding conditions, thus adding
to the economic benefits of the process. Finally, further work also needs to be done to quantify
the economic benefits. This is a complex procedure, but it is confidently expected to give a very
attractive result.
Conclusions
Initial studies have successfully demonstrated the use of stationary shoulder friction stir welding
for the additive manufacture of Ti-6Al-4V preforms.
Detailed SEM and optical metallography have shown that microstructures formed are typical of
those expected, and that there is limited variation in microstructure in the fabricated areas.
Initial studies of mechanical properties, as measured by micro-hardness tests, are re-assuring.
References
1. Threadgill P L and Russell M J: “Friction welding of near net shape preforms in Ti-6Al-4V”.
Proc Ti-2007, Kyoto, Japan, 3-7 June 2007.
2. Russell M J, Threadgill P L, Thomas M J and Wynne B P: “Stationary shoulder friction stir

welding of Ti-6Al-4V; process and evaluation”. Proc Ti-2007, Kyoto, Japan, 3-7 June 2007.
3. Ronald E. Jones R E and Zachary S. Loftus Z S: “Friction stir welding of 5 mm titanium 6Al-
4V”. Proc 6th Int. Symp on Friction Stir welding, saint-Sauveur, Quebec, Canada, October 2006.
(TWI).
4. Jata K V; Subramanian P R; Reynolds A P; Trapp T; Helder E: “Friction stir welding of

titanium alloys for aerospace applications: microstructure and mechanical behaviour”.
Proceedings, ISOPE-2004, (Fourteenth International Offshore and Polar Engineering
Conference), Toulon, France, 23-28 May.2004.
338
Bonding of Steel Inserts During Aluminum Casting

Q. Han , S. Viswanathan2, K. L. More3, M. R. Myers4, M. J. Warwick4, and Y.C. Chen4
1
1
Dept. of Mechanical Engineering Technology, Purdue University, West Lafayette, IN 47907
2
Dept. of Metallurgical and Materials Engineering, Univ. of Alabama, Tuscaloosa, AL 35487
3
Materials Science and Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN
37831
4
Columbus Technical Center, Cummins, Inc., 1900 McKinley Ave, Columbus, IN 47201
Keywords: Aluminum Casting, Dissimilar Metal Bonds, Casting Technology Development
Abstract
Technologies have been developed to reinforce aluminum castings with steel inserts. Defect-free
bonds have been consistently obtained between the steel insert and the aluminum casting. A
push-out experiment indicated that the bond strength was higher than previous approaches. This
paper presents the results of the technology development and the characterization of the bonds.
Introduction
The use of steel reinforcements in aluminum castings could significantly decrease the weight of
heavy duty diesel engines, thus improving handling, fuel economy, and payload. The goal of this
project was to develop the technology for the production of aluminum alloy castings reinforced
with steel inserts, and to produce a metallurgical bond between the steel inserts and the
aluminum casting for superior interfacial strength and heat transfer characteristics. The
technology to be developed had to be superior to that of the Al-Fin method, which involves dip
coating the steel insert in molten metals with low melting temperatures, such as zinc or
aluminum alloys, and casting-in the coated steel into aluminum castings. The project goals were
successfully attained. [1, 2] This paper details the technology development and the
characterization of the bonds in the following sections: coating development, cast-in method, and
results and discussion.
Coating Development
Coating Material Selection
Sacrificial coatings were designed in order to protect the steel insert from contamination and,
more importantly, to prevent the formation of unfavorable intermetallic phases at the steel-
aluminum interface. In addition, the coatings were diffusion bonded to the steel insert to prevent
them from spalling off during casting. This resulted in coatings that protected the steel prior to
casting, partially melted during the casting process to provide a clean interface for bonding, and
prevented direct contact between the aluminum and steel and the resulting formation of
undesirable phases.
In the early stages of the project, a single layer coating using a number of materials was tested.
Later, it was decided to use a dual layer coating on the steel insert. Coating materials considered
were copper, nickel, silver, and chromium. The thickness of each coating layer varied from 25 to
100 μm. The steel inserts were made of 1144 steel. The inserts were approximately 51 mm long
and 13 mm in diameter.
The selection criteria for the materials used in the dual layer coating were:
• The material used for the outer layer should have a larger thermal expansion coefficient than
that used as the inner layer. Both coating materials should have a larger thermal expansion
339
coefficient than steel. This is to ensure that the coatings physically bond to the steel during
cooling.
• The coating materials should have a large solubility range for each other and the material
used as the inner coating should have a large solubility in iron. This is to ensure that the
coatings can metallurgically bond to each other during diffusion bonding.
• The outer layers act as a sacrificial coating to help bonding between the inner layer and the
aluminum casting.
Based on the above three criteria, two steel coating systems were selected. They were
steel/nickel/copper (SNC) and steel/nickel/silver (SNS). Both systems were tested but the
development effort focused on the SNC system.
Electroplating technique
Electroplating techniques were used to plate the dual layer coatings on steel inserts. Initially,
standard commercial techniques of electro-plating were used. After the nickel layer was plated
at 77ºC, the hot steel inserts were immediately dipped in a solution at room temperature for
coating the copper layer. Optical microscopy revealed that a gap was formed at the
nickel/copper interface as shown in Figure 1. After careful review of the processing steps, it was
deduced that when the hot insert was dipped into the electrolytic liquid at room temperature, a
thin layer of copper likely formed immediately on top of the nickel layer. Subsequently, the
nickel-coated steel insert cooled and contracted during cooling, causing the nickel to pull away
from the copper and leave a gap at the nickel/copper interface.
Based on the proposed mechanism of gap formation, the electro-plating technique was modified.
After nickel was plated, the inserts were cooled to room temperature. The copper layer was then
coated at 43ºC. Figure 2 shows the SNC interfaces using the modified plating technique. No
gap was found between the SNC layers. In order to strengthen the steel-nickel interface, the
plating technique was further modified. The steel surface was deep etched to make the surface
rougher.
The final electro-plating procedure was as follows:
1. Soak, clean, and degrease inserts
2. Remove rust on steel surface using 30% HCl solution
3. Deep etch the insert surface using 50% HCl solution at 40 ºC
4. Plate nickel at 77ºC
5. Rinse in tap water at room temperature
6. Dip in 30%HCl solution at room temperature
8. Plate copper at 43ºC
340
Figure 1. The gap formed at the nickel/copper interface Figure 2. The modified coating technique resulted in
when the nickel and copper layers were coated using better bonding between the nickel and copper layers. No
standard commercial electro-plating techniques. gap was found at the steel/nickel/copper interfaces.
Diffusion bonding
The electroplated coating layers were then diffusion bonded. The coated inserts were loaded into
a vacuum furnace at room temperature, heated to 900ºC, held at 900 ºC for 4 hours, and furnace
cooled to room temperature. Figure 3 shows the composition profiles in the steel substrate and
the two coating layers. Nickel diffuses into both the steel substrate and the copper layer. Under
the conditions used, there is no diffusion of the copper into the steel or vice versa.
Cast-In Method
After diffusion bonding, the coated inserts were cast in place using a sand mold. The mold
consisted of a pouring basin connected to a runner that subsequently fed three casting cavities.
Each casting cavity contained two inserts that were vertically placed in the cavity and held in
place in depressions in the sand mold. Figure 4 illustrates the location of the steel inserts and the
casting configuration used.
100
Gating system
80
Atomic Percentages
Casting
60
Fe
Ni
40
Cu
20
Steel Inserts
0
0 50 100 150 200
Distance in Microns
Figure 3. Composition profiles in the copper (left), nickel
(middle) and steel (right) layers after diffusion bonding at
900ºC for four hours.
Figure 4. Schematic illustration of the locations of
steel inserts in castings.
The procedure for casting-in of steel inserts was as follows:
1. Dry sand mold for 6 hours using heat lamps
2. Pre-heat the coated inserts at 120ºC for 15 minutes
3. Melt and maintain aluminum alloy A354 at 720ºC
341
4. Degas the melt at 720ºC using argon+4% chlorine gas
5. Add 0.375 wt.% Strontium and 0.5 wt.% grain refiner
6. Place 2 preheated coated steel inserts in each mold cavity
7. Pour the melt into the mold under argon protection
8. Allow melt to overflow casting cavities to ensure that the leading metal front (possibly
containing oxides) does not freeze around the inserts.
The quality of the bond between the steel insert and the casting was affected by many factors
such as the melt quality, hydrogen content of the melt, pour temperature, and the temperature of
the steel insert. However, the critical parameters that affected bond quality were hydrogen
content and melt quality (in particular, entrained oxides at the leading edge of the metal front).
Hydrogen Content
Figure 5 shows the influence of melt hydrogen on the quality of the bond. When degassing was
insufficient, a substantial amount of porosity formed at the insert/casting interface. The bond
quality improved with improved degassing. Ultimately, a defect-free bond was obtained.
Experimental results indicated that defect-free bonds were obtained when degassing was
sufficient such that no porosity could be observed with the naked eye at the center of a Reduced
Pressure Test (RPT) specimen sectioned in half. The use of an argon cover during casting
noticeably improved the results.
Figure 5. The effect of hydrogen content on the quality of

the bond between the steel insert and the casting. The
bond is defective when the hydrogen level in the melt is
high.
Melt Over Flow
During mold filling, the leading edge of the melt entrains oxide and loose sand as it flows over
mold surfaces. The use of an over flow prevented the initial metal from freezing on the inserts.
It is assumed that with sufficient overflow, even if part of the leading edge froze on the inserts,
subsequent flow was sufficient to remelt and remove this material from the interface.
Interface Quality
Figure 6 shows the steel/casting interface in three different castings (containing 6 steel inserts).
No defects are observed at the steel/casting interface.
Bond strength Measurements
Push-out experiments were carried out to investigate the bond strength under various conditions.
This included varying the thickness of the nickel coating (25 to 75μm – 1 to 3 mils) and
342
diffusion bonding times of 1 to 4 hours at 900ºC. Figure 7 shows the interfacial strength of the
as-cast specimen as a function of nickel thickness and diffusion bonding time. The bond strength
is between 8,000 to 12,000 psi (higher than that of the Al-Fin bond which is typically 7,200 psi).
The data suggests that the bond strength is not affected by the diffusion bonding time in the
range between 1 and 4 hours. The bond strength is not affected by the thickness of the nickel
coating in the range between 12 and 65 μm (0.5 to 2.5 mils).
1.4 10 4
1.2 10 4
Interfacial Strength (psi)

1 10 4
8 10 3
6 10 3
Diffusion Bonding Time
4 10 3
4 hours
2 10 3 2 hours
1 hour
0 10 0
0.5 1 1.5 2 2.5
Ni Thickness (Mil)
Figure 6. Defect-free bonds obtained in castings by Figure 7. The relationship between the measured as-cast
careful degassing and the use of an argon blanket during bond strength, the thickness of nickel plating, and the
casting. diffusion bonding time. Good bonding strength was
obtained under as-cast conditions.
Bond strength after T6 heat treatment
The castings were then heat treated under T6 conditions (solutionized at 526ºC for 10 hours,
quenched to 71ºC, and aged at 150ºC for 10 hours). Figure 8 shows a comparison of the as-cast
bond strength with that after T6 heat treatment. The results show that T6 heat treatment did not
reduce the bond strength significantly. This indicates that aluminum alloy castings with steel
inserts bonded using the techniques outlined in this report can be safely T6 heat treated.
1.4 10 4
1.2 10 4
Interfacial Strength (psi)
1 10 4
8 10 3
6 10 3
4 10 3
As Cast
2 10 3 T6
0
0 10
0.5 1 1.5 2 2.5
Ni Thickness (Mil)
Figure 8. A comparison of bond strengths of as-cast
specimens with those of specimens after T6 heat treatment.
The bond strength is not reduced after T6 temper.
Conclusions
A methodology has been developed to produce defect-free bonds between steel and aluminum
alloys using the cast-in method, which is the most economical way of reinforcing aluminum
parts with steel inserts. The strength of the bond obtained is better than those obtained with the
traditional Al-Fin method.
343
References
1. Martin R. Myers, Michael J. Warwick, Y.C. Chen, R. Subramanian, S. Viswanathan, K.
More, and Q. Han, “Metallurgical Bonding of Inserts Having Multi-Layered Coatings within
Metal Casting,” Patent Number US 6,443,211 B1, Sep. 3, 2002.
2. Martin R. Myers, Michael J. Warwick, Y.C. Chen, R. Subramanian, S. Viswanathan, K.
More, and Q. Han, “Metallurgical Bonding of Coated Inserts Within Metal Castings,” Patent
Number US 6,484,790, November 26, 2002.
344
LOW TEMPERATURE ELECTROCHEMICAL SYNTHESIS OF Ti-Al

ALLOYS USING IONIC LIQUID ELECTROLYTES
D. Pradhan1 and R. G. Reddy2
1
Graduate Student, 2ACIPCO Professor and Department Head
1, 2
Department of Metallurgical and Materials Engineering
The University of Alabama, Tuscaloosa, AL 35487, USA
Keywords: Ionic Liquid, Electrodeposition, Ti-Al Alloy
Abstract
The synthesis of Ti-Al alloys were carried out using AlCl3-1-butyl-3-methyl imidazolium
chloride (BmimCl) electrolyte at different temperature between 70°C and 125±3°C. The alloy
was deposited on titanium cathode at various voltages between 1.5V and 3.0V. The molar ratio
of AlCl3 and BmimCl is 2:1 for all experiments. Titanium sheet (>99.99 wt %) was used as
anode. Morphology and composition of electrodeposited Ti-Al alloy were characterized using
SEM/EDS and ICP-OES respectively. Also, the effect of applied voltage and temperature on
cathode current density, current efficiency, composition and morphology of electrodeposit were
investigated. The Ti-Al alloys containing 26-37 wt% Ti were produced with a current efficiency
of about 80-85%.
1. Introduction
The electrochemical production of Ti and Ti-Al alloy is complicated due to the variable
oxidation states of titanium Ti+2, Ti+3 and Ti+4. The electrochemical behavior of titanium in
Lewis acidic chloroaluminate melt was investigated [1-2]. The electrochemistry of TiCl4 in
strong Lewis acid molten salt (AlCl3-EtMelmCl) at room temperature was reported by Carlin et
al. [3]. It was found that the reduction of tetravalent titanium occurs in three consecutive steps.
Ti (IV) first reduced to Ti (III) and then subsequently reduced to Ti (II) and Ti (0). But when the
concentration of Ti (III) i.e. β-TiCl3 exceeds the solubility limit then Ti (III) was passivated on
the electrode surface and also precipitated [1, 4-5]. This passive film blocks the electrodes and
prevents oxidation and reduction. It was reported that at higher applied voltage this film breaks
down to produce Ti (IV).
Recently, Reddy et al. [6-9] investigated the electrorefining of aluminum alloy in 1-butyl-3-
methyl imidazolium chloride (BmimCl) and the production of high-purity aluminum deposit
from AlCl3-BmimCl melt at 100°C. Karpinski et al [10] studied that when BmimCl is present in
molar excess over AlCl3 i.e. (AlCl3: BmimCl) <1.0, the ionic liquid becomes basic and melt
contains only AlCl4¯ anions. When the molar ratio is 1.0 it is neutral melt and the melt contains
mainly AlCl4¯ anions. But when AlCl3 is present in molar excess over BmimCl i.e. (AlCl3:
BmimCl) >1.0, the ionic liquid becomes acidic and it is mainly composed of Al2Cl7¯ but AlCl4¯,
Al3Cl10¯ and other acidic higher order anions are present in small quantities. Only Al2Cl7¯ is
subsequently reduced to aluminum at the cathode.
In our previous investigation [11], Al-Ti alloy was deposited from the electrolyte containing
AlCl3, BmimCl and TiCl4 with molar ratio of 2:1:0.019 (TiCl4 concentration is 0.05 mol/l) at a
temperature of 100 ± 3°C on copper cathode. Although this process produces Ti-Al alloy with
high Ti content (17-37 wt %), it is not energy efficient (15-25 % cathode current efficiency).
This is due to the formation of passive layer (composed of TiCl3 and ionic liquid) on the
electrode surface. This type of passive layer of TiCl3 was reported by other investigators [4-5].
345
The black passive layer on the electrodes prevents the redox reactions, hence decreasing the
cathode current density as well as the current efficiency.
In this study, we report electrodeposition of Ti-Al alloy from the acidic melt of AlCl3-1-butyl-3-
methyl imidazolium chloride (BmimCl) at 70°C to 125 ± 3°C.
2. Experimental Procedure
The procedure for synthesizing 1-butyl-3-methyl imidazolium chloride (BmimCl) ionic liquid
was described in details elsewhere [6-9]. Anhydrous AlCl3 (Alfa Aesar®, 99.985 %) was used
without further purification. Chloroaluminate electrolytes were prepared by mixing weighed
quantities of AlCl3 to the BmimCl ionic liquid into a Pyrex electrochemical cell. All weighing,
electrolyte preparation and experiments were carried out in argon filled Labconco® glove box.
All experiments were conducted in a 40 ml Pyrex® glass beaker fitted with Teflon/Perspex cap.
A thermometer was inserted through the cap to measure temperature. The schematic diagram of
the experimental setup is shown in Figure 1. Titanium sheet (15 x 0.5 mm), titanium sheet (15 x
0.5 mm) and titanium wire (0.5 mm diameter) were used as cathode, anode and reference
electrode, respectively. The experimental procedures and calculations were done similar to our
previous study [11]. All experiments were carried out between 70°C and 125 ± 3 °C for duration
of 4 hours with applied voltage between 1.5V-3.0V.
Reference Thermometer
Electrode
(Ti wire)
Cathode Anode
Electrolyte
Stirrer
Reactor
Figure 1. Schematic diagram of the experimental setup.

The morphological characterization and quantitative analysis of the electrodeposited Ti-Al alloy
samples were carried out using Philips® XL30 scanning electron microscopy (SEM) with
attached EDAX facility. The X-ray diffraction (XRD) analysis of the electrodeposited alloy was
performed using Philips® PW3830 X-ray diffractometer which uses monochromatic CuKα
radiation (λ = 1.5406 Å). The elemental analysis was done through Inductively Coupled Plasma-
Optical Emission Spectrometer (ICP-OES, Perkin Elmer® Optima 3000V).
3. Results and Discussion
3.1 Electrodeposition from AlCl3-BmimCl electrolyte
As the electrolyte is highly acidic (molar ratio of AlCl3: BmimCl = 2:1), it mainly consists of
Al2Cl7¯ and other higher order ions. The Al2Cl7¯ ions traverse through the electrolyte and get
reduced at the cathode to deposit aluminum. Dent et al. [11] and Abdur-Saha et al. [20] have
346
studied the structure of various divalent metal chlorides dissolved in acidic AlCl3-1-ethyl-3-
methylimidazolium chloride (EMIMC) ionic liquid electrolyte. They have reported that divalent
Ti (II), which allows the process control and optimum deposition is present in the form of [Ti
(AlCl4)3] ¯. The electrolyte mainly consists of Al2Cl7¯ ions, while Ti (II) may be present as [Ti
(Al2Cl7)4] 2¯. The possible reactions are
Anodic reactions:
Ti (Anode) + 4 (Al2Cl7) ¯ = [Ti (Al2Cl7)4] 2¯ + 2e¯ (1)
AlCl3+7AlCl4¯ = 4Al2Cl7¯+1.5Cl2+ 3e¯ (2)
Cathodic reactions:
[Ti (Al2Cl7)4] 2¯ + 2e¯ = Ti (Cathode) + 4 (Al2Cl7) ¯ (3)
4 Al2Cl7¯ + 3e¯ = Al (Cathode) + 7 AlCl4¯ (4)
The reduction of tetravalent titanium occurs in three steps Ti (IV) →Ti (III) →Ti (II) →Ti (0).
As the electrolyte does not contain TiCl4 initially, there was no violet colored precipitation on
electrodes or in the bottom of the reactor as we have seen earlier [11].
In the present study, Ti-Al alloy deposited at a temperature between 70°C and 125 ± 3°C was not
identified by XRD analysis. It may be due to the disordered structure of Al3Ti that is prevailing
at the temperatures used in the current study. Hence, individual diffraction peaks for titanium
alloy (Ti-Al) cannot be differentiated from that of aluminum. Takenaka et al. [13] also observed
the similar behavior that Al-Ti intermetallics are not detectable by XRD.
The experimental parameters, EDS analysis and Inductively Coupled Plasma-Optical Emission
Spectrometer (ICP-OES) analysis of samples are tabulated in Table 1. EDS and ICP-OES
confirm the presence of Ti and Al in the electrodeposit. The wt% of Ti and Al from EDS and
ICP-OES analysis varies closely and confirms that Ti and Al are co-deposited from the
electrolyte.
Table 1. The average composition of the electrodeposited Ti-Al
alloys at different of applied cell voltages (vs ETi immersion).
Applied Cell Average cathodic Average Composition of deposited
Voltage (V) current density Ti-Al Alloy
(A/m2) Elements EDS Analysis ICP-OES Analysis
(Wt %) (Wt %)
3 187.06 Al 73.10 82.87
Ti 26.90 17.13
2.5 147.98 Al 77.32 78.89
Ti 22.68 21.09
2 93.30 Al 64.38 72.74
Ti 35.62 27.26
1.5 36.66 Al 62.69 82.30
Ti 37.31 17.69
3.2 Effect of cell voltage

The effect of applied cell voltage on the cathodic current density, current efficiency and deposit
morphology of Ti-Al alloy was investigated in the range of 1.5-3.0V applied voltage at constant
experimental temperature of 100°C. Figure 2 shows the variation of average current density with
applied cell voltage. The plot shows that the current density varies nearly linear with applied cell
voltage. Increase in cell voltage also enhances the cathodic reduction reaction, hence increase the
current density.
347
200
150
2
Current Density, A/m 100
50
0
1.0 1.5 2.0 2.5 3.0 3.5
Voltage, V
Figure 2. Variation of average current density with applied cell voltage (vs ETi immersion).
Variation of cathodic current efficiency with applied cell voltage is shown in Figure 3. High
current efficiencies (78-85%) were achieved for all the applied voltages. In our previous study
[11] we achieved much lower current efficiency (20-25%) for AlCl3-BmimCl-TiCl4 electrolyte.
The lower current efficiency for AlCl3-BmimCl-TiCl4 electrolyte is due the passive layer
formation of TiCl3 on electrodes. As the AlCl3-BmimCl electrolyte does not contain TiCl4, the
passive layer formation diminishes. Hence, current density as well as current efficiency
increases.
As the applied cell voltage increases, the total charge passed through the cell increases and hence
the total amount of deposited Ti-Al alloy also increases. But with increasing applied cell voltage,
the wt% of Ti decreased as shown in Figure 4 and Table 1. This is probably due to mass transfer
controlled deposition at very higher cell voltage or higher cathodic current density (130-190
A/m2). The concentration of titanium ion in the electrolyte is low with compared to aluminum
ion, hence deposition of Ti is mass transfer controlled at high applied cell voltage.
100 100
90 Al
90
Ti
Cathodic Current Efficiency, %
80 80
70 70
Average Wt% (Al, Ti)
60 60
50 50
40 40
30 30
20 20
10 10
0 0
1.0 1.5 2.0 2.5 3.0 3.5 1.0 1.5 2.0 2.5 3.0 3.5
Voltage, V Voltage, V
Figure 3. Variation of cathodic current density Figure 4. Variation of average wt% of Al and Ti
with applied cell voltage (vs ETi immersion). with applied cell voltage (vs ETi immersion).
The morphology of Ti-Al alloy deposits and its composition at four different applied voltages are
shown in Figure 5 and Table 1. The SEM micrographs show that the deposits are nodular but not
348
so dense or compact. The EDS and ICP-OES analysis confirms the presence of Al and Ti on
titanium cathode. It was clearly seen from Figure 5 and Table 1 that as the applied voltage
decreases from 3.0 to 1.5 V, the titanium content in the Ti-Al alloy increases from 26.90 to 37.31
wt% and average nodule size or particle size decreases. But typically at higher applied voltage
the average particle size should be smaller which conflicts our observation. This can be
explained by considering nucleation phenomenon. At lower applied voltage, especially at 1.5 V,
titanium content in the alloy increases drastically which leads to increase in the nucleation sites
and produce finer particles. Therefore, lower applied voltage (1.5-2.0V) recommended not only
for finer particle size but also for higher Ti content in Ti-Al alloy.
(a) (b)
(c) (d)
Figure 5. SEM micrographs of Ti-Al electrodeposit at different applied voltages

(a) 3.0 V, (b) 2.5 V, (c) 2.0 V and (d) 1.5 V.
Further analysis on the composition of the deposited alloy was performed using EDS on different
particles (Figure 6) and are presented in Table 2. It can be seen that all the particles have
approximately identical elemental compositions. The analysis also confirms that no individual
aluminum or titanium particles were deposited. Hence, Ti and Al were co-deposited from the
electrolyte.
349
Table 2. The EDS analysis of particles
shown in Figure 6.
A Composition of particle
Nodules (EDS analysis)
Wt %
D E A Al 72.20
C Ti 27.80
B B Al 60.01
Ti 39.99
C Al 67.69
Ti 32.31
D Al 65.43
Figure 6. SEM micrograph of Ti-Al alloy Ti 34.57
electrodeposited from AlCl3-BmimCl E Al 61.86
electrolyte at 2.0 V applied voltage. Ti 38.14
3.3 Effect of temperature
The effect of temperature on cathode current density, cathodic current efficiency, composition of
Ti-Al alloy and morphology of deposit was investigated at a fixed applied cell voltage of 2.5 V.
Figure 7 depicts that cathodic current density increases with increasing temperature. The increase
in temperature increases the concentration of reducible ions in the cathode diffusion layer; this is
because the diffusion rate and convection increase with temperature. Hence concentration
polarization reduces and cathode current density increases.
Figure 8 and Figure 9 show the variation of current efficiency and composition respectively. It
can be seen that at all temperature range the cathodic current efficiency varies closely (80-85%).
The higher current efficiency is due to absence of initial TiCl3 passivation layer, which retards
the kinetics.
250
225
200
2
Cathode Current Density, A/m
175
150
125
100
75
50
25
0
60 70 80 90 100 110 120 130
0
Temperature, C
Figure 7. Variation of average cathodic current density with temperature.

Figure 9 shows that the wt% of Ti in Ti-Al alloy increases as the temperature increases from
70°C to 125°C, Ti wt% increases from 21.31% to 27.62%. This is because of the deposition
voltage of titanium is nobler than aluminum. And for the low concentration/weight ratio of Ti to
Al in the initial electrolyte with deposited Ti-Al alloy, Ti deposits preferentially and increasing
temperature always increases the Ti content in the Ti-Al alloy [14]. But the effect of temperature
is not so significant for improving Ti content in Ti-Al alloy.
350
100 100
90 90 Al
Ti
80 80
Cathode Current Efficiency,%
70 70
Average Wt% (Al, Ti)

60 60
50 50
40 40
30 30
20 20
10 10
0 0
60 70 80 90 100 110 120 130 60 70 80 90 100 110 120 130
0 0
Temperature, C Temperature, C
Figure 8. Variation of current efficiency Figure 9. Variation of Ti-Al composition

with temperature. with temperature
The morphological variations of Ti-Al alloy at different operating temperatures are shown in
Figure 10. Figure 10 (a) and (b) show almost similar type of microstructure. The deposit is flat
and few particles were seen in microstructure. But as temperature increases to 100°C, see Figure
10 (c), the particles began to cluster which leads to porous microstructure. At 125°C, clustering
of particles and particle growth occurs (average particle size 60-80 μm) as shown in Figure 10
(d). At higher temperature particle growth prevails which produces larger particle size.
(a) (b)
(c) (d)
Figure 10 SEM micrographs of Ti-Al electrodeposit at different temperatures
(a) 70°C, (b) 85°C, (c) 100°C and (d) 125°C.
351
4. Conclusions
The production of Ti-Al alloy was successfully carried out on titanium cathode from AlCl3-
BmimCl (molar ratio 2:1) electrolyte at an applied voltage ranging from 1.5 to 3.0 V and
temperature from 70°C to 125 ± 3°C. Ti-Al alloy produced at higher applied voltage (2.5-3.0 V)
becomes dark, non-uniform and coarse grained. But at lower applied voltage (1.5V-2.0V) a
bright deposit of Ti-Al alloy was obtained. The electrodeposited alloy containing up to 37.31
wt% of Ti was produced. Higher current efficiency up to 85% was achieved due to the absence
of passivating layer of TiCl3 on electrodes. Although higher temperature (125°C) does not
improve the current efficiency but increases the Ti content in the Ti-Al alloy. In summery, 1.5-
2.0 V cell voltage and 70-100°C temperature are recommended for finer particle and high Ti
content in the Ti-Al alloy.
Acknowledgements
The authors gratefully acknowledge the financial support from ACIPCO and The University of
Alabama.
References
1. A. Dent, K. Seddon and T. Welton, Journal of Chemical Society, Chem Commum, 4 (1990), pp. 315.
2. G. R. Stafford, “The Electrodeposition of Al3Ti from Chloroaluminate Electrolytes,” Journal of
Chemical Society, 141, (1994), pp. 945.
3. R. T. Carlin, R. A. Osteryoung, J. S. Wilkes and J. Rovng, Inorg. Chem. 29, (1990), pp. 3003.
4. M. R. Ali, A. Nishikata and T. Tsuru, “Electrodeposition of Ti-Al alloys from Aluminum Chloride-N-
(n butyl) pyridinium Chloride Room Temperature Molten Salt,” Indian Journal of Chemical
Technology, Vol. 10, January (2003), pp. 21-26.
5. T. Tsuda, C. L. Hussey, G. R. Stafford and J. E. Bonevich “Electrochemistry of Titanium and the
Electrodeposition of Ti-Al Alloys in the Lewis Acidic Aluminum Chloride-1-Ethyl-3-
Methylimidazolium Chloride Melt,” Journal of Electrochemical Society, 150 (4) (2003), pp. C234-
C243.
6. V. Kamavaram and R. G. Reddy “Thermal Stabilities and Viscosities of Low Temperature Aluminum
Electrorefining Electrolysis: Di-alkylimidazolium Chloride Ionic Liquid,” Light Metals 2005, TMS,
(2005), pp. 501-505.
7. M. Zhang, V. Kamavaram and R. G. Reddy, “New Electrolytes for Aluminum Production-Ionic
Liquids,” Journal of Metals, (2003), pp. 54-57.
8. V. Kamavaram and R. G. Reddy, “ Aluminum Electrolysis in Ionic Liquids at Low Temperature,”
Metal Separation Technologies III, R. E. Aune and M. Kekkonen (editors), Helsinki University of
Technology, Espoo, Finland, (2004), pp. 143-151.
9. V. Kamavaram, D. Mantha, and R. G. Reddy, “Recycling of Aluminum Metal Matrix Composite
using Ionic Liquids: Effect of Process Variables on Current Efficiency and Deposit Characteristics,”
Electrochimica Acta, 50, (2005), pp. 3286-3295.
10. Z. J. Karpinski and R. A. Osteryoung, Inorg. Chem., 23, (1984), 1491-1494.
11. D.Pradhan, R. G. Reddy “Production of Al-Ti alloys using Ionic Liquid Electrolysis at Low
Temperatures”, Innovation in Titanium Technology Symposium, 2007 TMS Annual Meeting,
Orlando, Florida, 25th Feb-1st March, 2007, pp. 79-86.
12. A. Abdur-Saha, A. Greenway, K. R. Sodden and T. Walton, Org Mass Spectrom, 27 (1992), pp 648.
13. T. Takenaka, M. Kawakami, “Electroplating of Al-Ti and Ti in room temperature melt”, Int. J.
Materials and Product Technology, Special Issue, SPMI, 2001, pp. 500-506.
14. A. Brenner, “Electrodeposition of Alloys- Principles and Practice”, Academic Press, New York
(1963), p. 75-85, 139-146.
352
RESIDUAL LIFE EXTENSION OF AGED TRANSFORMERS IN

ALUMINIUM SMELTERS
Santhosh Kumar Rajamoorthy, Saravanan Krishnamoorthy
The Madras Aluminium Company Limited

(Unit of Vedanta Resources Plc.)
Mettur Dam – 636 402,
Salem District, Tamil Nadu. India
Keywords: Residual Life Extension, Reclamation, Reliability Of Transformers
Abstract
The modern world is increasingly dependent on electricity for economic prosperity. Without
doubt the single most important piece of equipment in electrical networks in Aluminium
Smelters is the Power transformer. However the average age of transformers around the world is
increasing rapidly with transformer failures rising exponentially, and to replace all of the aged
power transformers at risk would be prohibitively expensive. This paper focuses on the extension
of residual life of these aged transformers through ONLINE RECLAMATION of oil a process
through which the parameters of the oil are improved better than the new oil (Specified in IS
335) thereby life extension.
Introduction
It is known today for sure that, inside the transformer a complex chemical reaction is taking
place every day between oil, cellulose, other organic material and the metallic parts, such as
copper and iron. Moreover the aged oil will dissolve more water than new one. However, on the
other hand, the chemical background is highly complicated as there is really some water bound
in the different ageing products in the old oil. The life of a power transformer can be assessed
through the following lifetime Indicators:
• Furan-DP- Furfural
• CO2/CO content
• Acidity
• Particles (fibers)
• Water content
• Electrical strength/BDV
• Tan Delta
• Interfacial tension
• The Color of the oil
It is necessary to look ALWAYS at the complex system of cellulose and oil as a whole. The
ageing or deterioration of insulating oil is normally associated with oxidation. Due to the omni
presence of oxygen and water, insulating oil oxidizes even under ideal condition. The insulating
properties of the oil also affected by contaminants from the solid materials in the transformer
dissolving in the oil. The reaction between unstable hydrocarbons in the oil, oxygen and other
353
catalysts such as moisture, with the assistance of accelerators such as heat, results in decay
products (oxidation by-products) in the oil.
Heat and moisture are the main enemies of the solid (paper) insulation with oxidation as the
primary accelerator. Ageing of the insulation system could accelerate by 40 to 60 years through
an increase in operating temperature.
Oil oxidation can unfortunately not be eliminated but it can be controlled (slowed down) through
applying preventative maintenance procedures. The key to preventive maintenance of
transformers is annual oil analysis. The results of oil analysis reveal information regarding the
condition of a transformer’s insulating system. Oil, the lifeblood of the transformer, contains the
information about the health of the whole system. An oil sample is similar to taking blood from a
human being to make all kinds of analysis. A change of blood will not usually help the healing
process, so will not an oil change solve the most problems.
If well-targeted measures are not taken anytime soon, a virtually insurmountable reinvestment
load combined with unforeseeable stochastic failures will soon be bitter reality!
The Catalysts that Drove Us
• The pathetic but factual Oil test reports from CPRI- Bangalore.
• The age of the transformers (Installed in the Year 1964).
• The Dark brown color of the oil.
• Periodical augmentation in the loading pattern of the electrical system.
• The impact of blackout of the electrical system on the hot metal production.
Why Online Oil Reclamation
Heavily aged oils, especially acid ones harm the transformers residual lifetime and must be changed or
better regenerated.
To treat the problem we have to take care of three points:
1. Treating the oil correctly, i.e. by regeneration, this can eliminate acidity, polar products and sludge.
2. Treating the cellulose, this means drying.
3. The next and third point to the complete treatment system should be to conserve the transformer by gas
conditioning, in order to prevent further deterioration and conserve the residual lifetime strength of the
system in the future!
On line regeneration is a technically improved process where the oil is processed on site in the
transformer tank. It is circulated from the bottom of the main tank, heated and directed through ‘structural
clay columns’, then filtered to particulate removal of 0.2 micron, vacuum treated and dehydrated before it
is returned to the top of the unit via the conservator tank. The process is continuous until the oil exceeds
the IS 335 specifications. The method employs adsorption and thermo vacuum (dehydration and
degassing) treatment in restoring the oil.
The difference between regeneration and purification is that purification cannot remove substances such
as acids, aldehydes, ketones, etc. in solution, and can therefore not change or improve the colour of the
oil. The regeneration process incorporates purification as part of the refining process. While transformer
oil meets the requirements in just one cycle of the oil through the regeneration plant, more cycles are
required to sufficiently clean the inside of the transformer and to remove the contaminants adsorbed by
the cellulose insulation.
Furthermore
• -No shutdown
• -No production loss
• -And regenerated oil is often more stable than new one because it is defined treated.
354
Our Journey
Our 110 KV rectifier station was installed in the year 1964.It houses 8 Nos of power
transformers at 110 KV level ranging from 7.5 MVA to 25 MVA to feed the auxiliary and
smelter lines power requirements. The recent oil test reports of these transformers instigated us
to go for this residual life extension program, as power is the key driving force in any aluminium
smelter. So, to ascertain the reliability of these transformers we explored the various treatments
available in India as well as worldwide. Of the various treatments available online oil
reclamation suited our requirement as this helps in conserving the ageing products as well as in
flushing with high solvent active oil base. Moreover dark brown colour of the oil due to ageing is
fully treated and the oil regains the original pale yellow colour and much more stability than the
new oil due to due treatment. As a consequence we went in to this ONLINE RECLAMATION
process to treat our aged transformers to extend the residual life to ascertain utmost reliability to
our Aluminium smelter lines without much expenditure thereby uninterrupted hot metal
production.
Here follows the Oil Reclamation test results of one of our 7.5 MVA, 110/6.6 KV Auxiliary
transformers and 23.5 MVA 110/33.1 KV Regulating transformers. The results (Tables I & II)
will give a clear picture of the parameter improvement of the oil, and the colour change is
evident from Figs 1&2.Thus there is an extension of residual life.
Figure 1. 7.5 MVA 110/6.6 KV Transformer (Oil samples after reclamation)
355
Figure 2. 23.5 MVA 110/33.1 KV Transformer (Oil samples after reclamation)
Oil Reclamation Results
Table I: 7.5 MVA 110/6.6 KV Transformer

Sl. NO Test Description UOM Before Regeneration After Regeneration
1 Interfacial Tension mN / M 23.09 38
2 Flash Point Deg. C 149.81 153.81
3 Neutralization Value mg KOH / g 0.116 0.013
4 Electric Strength kV 42 85
5 Dielectric Dissipation factor 0.178 0.0026
6 Specific Resistance 90 Deg X 10^12 Ohm-cm 0.12 11
27 Deg X 10^12 Ohm-cm 1.3 280
7 Water content ppm 45.9 9
8 Sediment & Sludge Nil Nil
9 Dissolved Gas Analysis
Total Gas Content micro L / L 96690 79110
Methane ppm 35 2
Ethane ppm 7 1
Ethylene ppm 7 1
Acetylene ppm Not detected Not detected
Hydrogen ppm Not detected Not detected
Oxygen* ppm 11992 20536
Nitrogen* ppm 9999 53794
Carbon monoxide ppm 732 Not detected
Carbon dioxide ppm 3753 244
356
Table II: 23.5 MVA 110/33.1 KV Transformer
Sl. NO Test Description UOM Before Regeneration After Regeneration
1 Interfacial Tension mN / M 22 42.05
2 Flash Point Deg. C 158 161.81
3 Neutralization Value mg KOH / g 0.15 0.014
4 Electric Strength kV 31 72.1
5 Dielectric Dissipation factor 0.17 0.00156
6 Specific Resistance 90 Deg X 10^12 Ohm-cm 0.11 38.4
27 Deg X 10^12 Ohm-cm 1.5 970
7 Water content ppm 55 6.2
8 Sediment & Sludge Nil Nil
9 Dissolved Gas Analysis
Total Gas Content micro L / L 105480 105480
Methane ppm 28 1
Ethane ppm 6 1
Ethylene ppm 10 1
Acetylene ppm Not detected Not detected
Hydrogen ppm Not detected Not detected
Oxygen* ppm 18574 30140
Nitrogen* ppm 69026 61566
Carbon monoxide ppm Not detected Not detected
Carbon dioxide ppm 1472 476
* The oxygen and nitrogen content is bound to vary depending on the sampling ambient conditions, transportation to
the testing laboratory and other factors. These gases are not generated due to the process unlike the hydrocarbons,
which are generated by the chemical reaction (like deterioration of the insulation) in the transformers.
Results
It is clearly evident from the oil reclamation test results that the acidity and dielectric dissipation
factor of oil (the Killers) have improved drastically resulting in regaining the quality of oil,
which is now as good as new oil. Moreover the ionic and polar surfactants are remove
from paper, which has resulted in sustaining the healthiness of cellulose. This combined
improvement effect of oil and paper insulation has led to the extension of residual life of the
transformer by another 5 years.
Figure 3. Ageing behavior of a Power Transformer.
357
Conclusion
Thus the Online reclamation process has resulted in the extension of residual life of the aged
transformers which has led to the deferment of the new transformer procurement thereby an
estimated saving of INR 16,000,000 per transformer. If the transformer oil is regenerated as soon
as the acidity level exceeds 0.11 mg KOH/g, degradation of the transformer oil, a wet core
condition, sludge forming and subsequent damage to the transformer insulation will be prevented
and the life of the transformer could be extended by up to 20 years. Thus through on-site
regeneration, millions of Rupees could be saved on the maintenance budget and through
improving the general condition of the oil; the risk of failures is also minimized. Regeneration of
transformer oil is an important preventive maintenance tool and transformer oil should therefore
be treated before it reaches levels of deterioration that is known to cause damage to the
transformer insulation. If a maintenance program is followed, the accumulation of moisture and
sludge in the transformer’s solid insulation could be prevented. For better results the team
recommends the following preventive maintenance strategy:
• Purify when the acid levels is still below <0. 10 mg KOH/g, color is still yellow to light
amber, and the moisture is 20 ppm and / or when the dielectric strength is <50kv.
• Regenerate when the oil reaches 0. 10 mg KOH/g, to avoid precipitation of sludge. If
transformer oil is regenerated from an acidity level of 0.10 mg KOH/g oil, the moisture in
oil levels will be reduced at the same time, thereby preventing a wet core condition.
• De-sludge when acid level is 0. 20 mg KOH/g.
• Dry out when solid insulation is wet 3.5%
To monitor the sustenance of the results the team has framed the following action plan in
MALCO:
• Biannual Oil Screening
• Biannual DGA Tests
These points will help in having a check on the oil parameters periodically thereby to initiate
action as and when required.
Acknowledgement
Authors are thankful to MALCO management for their encouragement to implement this Oil
Reclamation process. Our special thanks to Mr.P.Kumar for his support throughout in making
this happen. The opportunity and freedom provided to implement the same has given the team a
lot of learning, confidence, boost and a sense of satisfaction. We also thank our operations and
maintenance team for their overwhelming support throughout this journey.
References
[1] Michel Belanger “Technique for drying out oil-filled transformer while still in service”
[2] Paul J. Griffin “How to prevent rain in power transformer”
[3] Mario Scala “Moisture model for transformer online”
358
Revamping of Rodding Shop Worldwide

Jean-Jacques Grunspan
BROCHOT SA, 52 avenue Marcel Paul, Tremblay en France, France
Keywords: Revamping, Rods, Anodes, Power, Free
Abstract
The decision to revamp a rodding shop after 20 or 30 years use is a strategic decision for an
aluminium smelter in view of its potential threat to the continuity of supply of rodded anodes to
the potrooms. BROCHOT has undertaken the revamping of 3 rodding shops in 3 different
smelters (PNL Netherlands, Lynemouth UK and DUBAL in UAE). In this article, it shares its
experience by highlighting those factors which must necessarily be considered before
undertaking any such revamping project so as to prevent major problems
Introduction
As improved methods develop, smelters are often faced with the need to replace or upgrade
their equipment to remain competitive.
The question is then whether to completely rebuild or to upgrade the existing plant section
by section. There are, of course, advantages and disadvantages in both options :
On the one hand, one has a purpose built and fully integrated design — and a potentially
expensive solution.
On the other hand, one has the possibility of considerably reducing the cost and of maintaining
production throughout the operation. This, however, may be limited or offset by the presence of
existing installations that will have to remain and which may force the new plant to adopt a less
than optimal layout.
additionally, as revamping generally takes place while the plant is still in operation, without
interfering with production, this will be an additional constraint — but may be also have the
advantage of reviewing and updating production methods.
The Brochot Company has just revamped the rodding shop at Dubai Aluminium (DUBAL)
and an account of this operation is of undoubted interest.
SOME GENERAL COMMENTS.
First and foremost the plant it is proposed to revamp has to be assessed to determine, as far as
possible, the constraints and hazards.
SAFETY.
Since the plant will be in full operation, safety is paramount. A rodding shop is a dangerous
place in which to work — the rods, full anode assemblies and the butts returning for recycling
are all in constant movement. The last, in particular will be hot and so especially dangerous. In
addition, there is the movement of forklifts carrying anodes as part of normal production and
also carrying cherry-pickers for maintenance operations. Visibility is often poor, not only
because of existing plant obstructing vision but also because the atmosphere can be heavily
loaded with dust in some areas. There is also shot and bath material underfoot, which can also
be a hazard for men working there.
359
INSTALLING NEW EQUIPMENT IN AN OLD PLANT.
The type and condition of the existing plant must also be assessed to ensure compatibility with
the new. Being old there will be wear and so some play, especially of the components of the
conveying system. Thus the question of tolerances must also be assessed — of the equipment
(trolleys, P & F track, tension-adjusters, drives etc) and of the material being handled (rods,
brackets, pins, anodes, thimbles but also bath level which determines the size of the returning
stubs).
PRIME PREREQUISITE: SURVEY THE P & F AND RELATED SUPPORTING
STRUCTURES.
The rodding shop’s roof structure must also be surveyed and its ability to support additional
items of plant assessed or whether new foundations need to be built for some of these. An
important part of the revamping operation will be the installation or modification of new
powered and free overhead conveyors. This generally also involves the design and supply of
intermediate supporting structures, which could weigh several tens of tons.
Such surveying must also cover access — both for the revamping teams, their equipment and
materials but also for the plants own maintenance teams, since revamping will, as often as not,
be carried out during the plants maintenance shutdown periods.
The documentation of the existing plant, especially the electrical drawing, must be surveyed and
checked against the actual site conditions.
SURVEY THE PROCESS AS A WHOLE.
This enables one to take advantage of the revamping project to increase capacity and flexibility
by identifying and eliminating bottlenecks.
For this, an excellent tool is computer simulation, to optimise:
9 The P&F layout
9 The list of machines to be replaced or added
9 The cycle time and, consequently, the output
9 The overall schedule of the revamping operation by breaking down the
rodding shop into different areas.
After completing the scheduling of the project and before starting the work, complete a layout of
the final result planned, to ensure that nothing has been overlooked and to prevent major
unfortunate surprises.
SCHEDULING.
Ensure that all the equipment needed, together with all related tools and appliances, is actually
on site. Only then can one ensure the rapid mobilisation of resources needed for efficient
operation and avoid losing time.
PLANNING OF SHUTDOWNS.
It must be born in mind that, for the plant’s management, the maintenance and continuity of
production is their most important concern. Thus the revamping programme depends on close
cooperation with the production personnel. As far as the latter are concerned, ideally, the
revamping should only be carried out during normal stoppages, such as routine maintenance —
360
generally a single shift of 8 to 10 hours. This is excessively restrictive and, where possible,
additional time can be bought using loops and synopsis.
MAIN OBJECTIVE OF THE OPERATION.
Since the Pots need to be continuously supplied with fresh anodes, and spent ones also need to
be removed in the same way, it is essential that there be sufficient storage space to ensure this
continuity of production, should longer shut downs, in at least some areas, be needed. Creation
of such additional storage may, therefore, be one of the first requirements of a successful
revamping programme.
COOPERATION BETWEEN ALL PARTIES INVOLVED.
Since close cooperation between the contractor’s team and the production personnel is the key to
success, the working habits and customs of the plant operators must be properly understood. As
the plant will probably have been expanded more than once in the past, this will have
conditioned the logic of the movement and storage of the materials (rods, anodes etc.), which
may not be immediately obvious to newcomers. This emphasises the need for establishing and
maintaining proper understanding and cooperation.
Both sides, at times, may need to alter their usual styles of work, but the contractor teams must
be especially flexible to cope with last minute changes imposed by production requirements
(which will always have priority) — for example the sudden cancellation of a stoppage planned
to allow revamping work to be carried out in a particular area. This will, necessarily, mean rapid
deployment of the contractor teams to other tasks, which means planning of the revamping
operation must allow for working in two or more places at once — and switching between them.
This also means that there can be no delays about getting tools, equipment or materials on site.
This is even more important than in the case of a green-field site (important though it is there
too) since the times available for working are so restricted — a task will often have to be
completed within a single shift — or be so delayed as to upset other planned work. This means
very strict scheduling of all on-site work and condensing the time taken for such tasks to the
minimum.
This need for cooperation covers the maintenance teams as well as production because:
preventive maintenance needs be extended to cover the new items of plant installed by the
contractors who will have to brief and/or train maintenance crews in this area
to enable both maintenance and contractors to take full advantage of the shutdowns and outage
granted by production to contractor and fulfil, without friction, tasks that both are unable carry
out during normal operation time.
MAN-MACHINE INTERFACE AND PROGRAMMING.
Since the revamping will inevitably involve new methods and technology, the man-machine
interface must be clear and user-friendly — all the more so to the extent that it is new and
unfamiliar, and the time for retraining is very limited.
Design, of course, involves interlocking between the new and the existing equipment and
processes, particularly the automation processes. The new automatic systems and philosophy
have to be adapted to cover the old technology.
DESCRIPTION OF THE DUBAI REVAMP OPERATION
361
The operation at Dubai was broken up into seven phases.
Bath cleaning Areas.
The butts underwent some preliminary cleaning of bath material in the Potrooms. They now
pass through two further cleaning stages, the first using a chain flailing machine followed
by a shot-blasting unit. Both have to cope with a wide range of tolerances.
This new area deals with the butts coming from the original bath cleaning area. It consists
of a chain-flailing machine to remove pieces of bath still adhering to the carbon after the
original cleaning operation. The chain-flailing is followed by a shot-blasting unit that
removes the last traces of bath material, ensuring that the carbon recycled in the next stage
(not altered) is really free of any bath material. The new section is connected to the old by a
new P & F overhead conveyor and enclosed in a de-dusting system. It is designed not only
to handle the increased production of the revamped rodding shop, but also to deal with the
entire rodding shop production whenever the original butt cleaning plant is out of order.
This new area has the dual advantage of improving the quality of the cleaning operation
without breaking the carbon block, making for cleaner separation of recycled materials.
The Butt Cleaning operations.
There were two aspects to the revamping of this area of the revamping operation:
9 modifying the powered and free overhead conveying system to increase
production and allow more storage, with facility for bye-passing the storage area
when necessary.
9 adding the two additional butt-cleaning stages mentioned above, to improve the
elimination of bath material prior to carbon recovery and increase production of
this operation.
Owing to the time constraints already mentioned, the first of these was carried out in three
phases, (Phases 1 to 3) the second being postponed (Phase 6) to follow the new thimble
stripping machine, as too great an increase in the butt cleaning production before this would
have created a major bottle neck at that point.
The New Triple-Thimble Stripping Machine.

Thimbles are the stubs of cast iron adhering to the pins at the bottom of the recycled rods
after removing the bath and carbon from used anodes. The usual procedure is that, after the
carbon has been removed, the rod is held while a splitter blade, driven by a hydraulic ram,
strips the cast iron from each pin in turn. Depending on the design of the anode, there can be
2, 3 or more pins to each rod, which means presenting each one to the splitter blade in turn.
In DUBAL’s case, the rods have three pins, which fit into the three holes in their anodes.
In the course of its revamping, DUBAL decided to install Brochot’s new triple-thimble
stripper. Here, instead of having a single splitter blade, to which each pin in presented in
turn, there are three splitter blades, which strip all three thimbles simultaneously. This
obviously reduces the cycle time of this operation and speeds up production overall.
Brochot’s new triple-thimble stripping machine was thus installed as Phase 4 of the
revamping operation, making full use of the increased production and storage potential
created in the first three phases as well as of the increased throughput from the improved
butt cleaning achievable by the subsequent phases.
362
It should be mentioned that one of the problems at DUBAL is that the pins here are not
straight but bowed or bent, especially the outer ones (the so-called “cowboy effect”) —
sometimes by as much as 60mm. This called for a special design to meet these conditions:
this machine had to be fitted with floating jaws that followed the shape of the pins so as to
be able to treat over 97% of the rods.
Anode transfer conveyor.
In view of the overall increase in production capacity, it was necessary to increase the
capacity of a transfer system used for conveying anodes. This, Phase 5 of the operation,
consisted of building a bridge over a busy existing road, in parallel with an already existing
bridge. The new bridge was built with an elevator to transfer the anodes onto a roller
conveyor running over it. This was done alongside the old bridge, which was thus able to
keep running during the whole operation. Only when the new bridge and conveying system
was fully in operation were the old system stopped and its bridge dismantled.
Rod repair area.
This involved creating a new loop in the powered and free overhead conveying system,
installing a pin cutting machine and a welding machine to weld new pins onto the rods.
Whereas pin cutting is usually effected by disk saws with carbide tips, Brochot preferred to
use a band saw. This has the advantage of exerting less strain on the pin and the cutting
tools. Consequently tool costs are considerably reduced their operating lives are increased.
Fresh pins are welded onto the rods with a fully automatic robotic welding machine. This
has proved to be particularly efficient, reducing the operating cost of straightening the pins
PIN WELDING ROBOT
PIN CUTTING - BAND SAW
363
HOW TO COPE WITH A RANGE OF SIZE VARIATIONS.
Since old plants may have fairly large tolerances, it is best to start by setting up an acceptable
range of tolerances and then arrange to cope with variations that, initially, will exceed them. In
the first place this will be needed to ease the sorting and cleaning of rods and butts. At Dubai
this was achieved by having floating tools, essentially on the chain flailing machine and the
thimble press.
CONCLUSION.
Such a revamping project provides more than an opportunity to increase the capacity of the
rodding shop — which, indeed, it does. It also provides a very real opportunity of reviewing and
improving the whole operating process as well as maintenance schedules. The fact is that, in
order to carry out an effective revamping operation, one has to dovetail the three operations of
production, maintenance and revamping. To do this effectively, both production and
maintenance are obliged to review their methods, to call them into question. This is, inevitably,
a healthy operation, allowing old habits to be challenged and old methods to be improved —
thus not only revamping the plant but the whole operating philosophy.
364
ELECTRICAL CONDUCTIVITY OF MOLTEN ELECTROLYTES

FOR LIGHT METAL PRODUCTION
Alexander A. Redkin, Olga Yu. Tkacheva, Anatoly P. Shuryghin
Institute of High Temperature Electrochemistry

S. Kovalevskaya 22, Yekaterinburg, Russia, 620219
Keywords: Electrical Conductivity, Molar Volume, Molten Electrolytes
Abstract
Expert system for molten electrolyte properties is proposed. It based on dependence of specific
conductivity and other properties on molar volume. It allows describing concentration and
temperature changes in molten electrolytes by one equation. The scientific basis of this system is
shown in this article on the example of electrical conductivity.
Introduction
Electrical conductivity is a basic property for the molten electrolytes used for light metal
production. Usually the conductivity of the molten salts mixtures is considered as additive
combination of the pure salts conductivities. The electrical conductivity of pure molten salts
depends on ionic potential of cation [1]. According to this approach all molten salts can be
divided into 4 groups:
1. ideally conducting salts
2. good conductors
3. bad conductors
4. isolators
Ionic potential of cations calculated as z/r (where z – charge of ion in relative units, r - ionic radii
in nm) [10] is given in Table 1. Salts having cation with ionic potential (IP) less 30 nm-1 form
the first group of ideally conducting salts and salts with IP more 30 nm-1 and less than 50 nm-1
form the second one (good conductors). Salts with IP in range 50-100 nm-1 are bad conductors.
Such rather relative classification of molten salts allows describing the electrical conductivity of
molten electrolytes used for light metal production.
Table1. Ionic potential of some cations (нм-1)

Li(+) Be(2+) B(3+) C(4+)
17 64 150 250
Na(+) Mg(2+) Al(3+) Si(4+) P(5+)
10 31 66 100 132
K(+) Ca(2+) Sс(3+) Ti(4+) V(5+)
8 20 40 61 92
Rb(+) Sr(2+) Y(3+) Zr(4+) Nb(5+)
7 17 33 55 78
Cs(+) Ba(2+) La(3+) Hf(4+) Ta(5+)
6 15 28 55 78
365
Electrolyte for magnesium production is a mixture of alkali chlorides (NaCl, KCl) and alkaline
earth chlorides (MgCl2, CaCl2 and BaCl2). Their specific conductivity depending on molar
volume at temperature 1200 K is presented on fig.1. The specific conductivity and density data
were taken from [3-5]. It is seen from the figure that there is a straight line for the alkali
chlorides conductivity. It allows deriving dependence of conductivity on molar volume at
constant temperature: lnχ = K1+K2/V. Here K1 and K2 are temperature dependent constants.
Consequently it is possible to present the specific conductivity of molten alkali chlorides as a
function of molar volume and temperature. The conductivity of alkaline earth chlorides can be
also described by the same equation with some additionally coefficients.
2.5
2
LiCl
1.5
NaCl
Lnχ
1 CaCl2
SrCl2 KCl
BaCl2
RbCl
0.5 CsCl
MgCl2
0
0.01 0.015 0.02 0.025 0.03 0.035
Reciprocal molar volume, 1/V
Fig.1 Specific conductivity of alkali chlorides and alkaline earth chlorides at 1200 K
Electrolytes for magnesium electrolysis
As far as the magnesium electrolytes is a mixture of alkali and alkaline earth chlorides the main
regularities of electrical conductivity change in these systems must be considered. For the pure
molten alkali chlorides the electrical conductivity can be presented as temperature – molar
volume dependence [1]:
lnχ = 4,9·exp[-(2747-33724/V)/T]·exp(53,7/V) (1),
where V - molar volume, cm3 /mol; χ - specific conductivity, Ohm-1·cm-1; T - temperature, K.

It means that integral cation mobility changes proportionally to reciprocal molar volume. This
relationship is also valid for most of alkali chloride mixtures which can be considered as ideal
ones. The system NaCl-KCl is close to ideal because Na+ and K+ have very similar electronic
potentials. At mixing of molten NaCl and KCl molar volume is found to be additive and the
enthalpy of mixing is very low. In this case the equation (1) can be used for calculation of
electrical conductivity of the mixture. Comparison of experimental and calculated conductivity
values for molten mixture NaCl-KCl at 1100 K is given at Table 2. The difference between
experimental and calculated numbers is not exceeding 5 %.
366
The equation (1) with some coefficient (D) is also valid for pure alkaline earth chlorides:
lnχ = 4,9· exp[-(2747-33724/V)/T]· exp(53,7/V) ·exp(D) (2).
The values of coefficient D: for MgCl2 (-0,35), for CaCl2 (+0,2) and for BaCl2 (+0,14). It
reflects the specific features of each salt and can be regarded as a deviation from ideal values of
conductivity. As it is seen from the fig.1 the MgCl2 conductivity is rather lower compare to ideal
one and it has negative magnitude of D. CaCl2 and BaCl2 have slightly positive magnitude of D,
it means that their conductivity is very close to ideal. The comparison of experimental and
calculated conductivity values for MgCl2, CaCl2 and BaCl2 is given on fig 2.
Table 2. The comparison of experimental and calculated electrical conductivity in

KCl-NaCl molten system at 1100 K
Molar fraction of Experimental values [5], Calculation on equation (1),
NaCl Ohm-1·cm-1 Ohm-1·cm-1
0,00 2,33 2,22

0,20 2,42 2,43
0,41 2,63 2,66
0,51 2,74 2,79
0,73 3,08 3,15
1,00 3,68 3,69
3
Specific conductivity, Ohm-1cm-1
CaCl2
2.5
2 BaCl2
1.5
MgCl2
1
0.5
0
1000 1050 1100 1150 1200 1250 1300 1350
Temperature, K
Fig.2 Specific conductivity of alkaline earth chlorides: open circles – experiment [3], filled
circles – calculation (equation 2).
The mixtures of MgCl2 with alkaline earth chlorides show “ideal” behavior i.e. their molar
volume changes according additive law and enthalpy of mixing is very low. The electrical
conductivity of these mixtures can be presented by equation:
lnχ = 4,9· exp[-(2747-33724/V)/T] · exp(53,7/V) · exp(-0,35· N) (3)
367
where N-molar fraction of MgCl2 . The electrical conductivity of NaCl-MgCl2 and KCl-MgCl2
mixtures calculated on equation (3) and experimental [2] is presented in fig.3. There is a good
coincidence for the NaCl-MgCl2 system but there is some disagreement for KCl-MgCl2 system.
It can be explained by difference in calculated (equation 1) and experimental data for pure KCl.
4
NaCl-MgCl2(calculation)
NaCl-MgCl2 (experiment [2])
-1
3.5 KCl-MgCl2 (calculation)

Specific conductivity, Ohm cm
KCl-MgCl2 (experiment [2])

-1
2.5
1.5
1
0 0.2 0.4 0.6 0.8 1
MgCl2, m. f.
Fig.3 Specific conductivity of NaCl-MgCl2 and KCl-MgCl2 mixtures at 1073 K
The mixtures of alkaline earth chlorides with alkali chlorides change their behavior with the
change of ionic potential difference. Molten systems NaCl-CaCl2 and KCl-CaCl2 show non-ideal
behavior [6-9] but their electrical conductivity can be also described by temperature – volume
equations for certain concentration region of CaCl2 . If the CaCl2 concentration does not exceed
30 mas.% the specific conductivity is as follows:
for KCl-10mas.% MgCl2-CaCl2

lnχ = 4,9· exp[-(2747-33724/V)/T] exp(53,7/V) ·exp(-0,35·0 N1-1,2·N2) (4):
for NaCl-10mas.% MgCl2-CaCl2
lnχ = 4,9· exp[-(2747-33724/V)/T] exp(53,7/V) ·exp((-0,35·0 N1-0,12·N2) (5)
where N1 - molar fraction of MgCl2, N2- molar fraction of CaCl2. The electrical conductivity
isotherms for mixtures KCl-10wt% MgCl2-CaCl2 and NaCl-10wt% MgCl2-CaCl2 are given in
fig.4.
368
NaCl(10 mas%)-CaCl2
4 calculation
KCl(10 mas.%)-MgCl2
calculation
Specific conductivity, Ohm-1cm-1
3,5 NaCl(10 mas%)-CaCl2

experiment [2]
KCl(10 mas.%)-MgCl2
experiment [2]
3
2,5
1,5
1
0 10 20 30 40 50 60
CaCl2, mas.%
Fig.4. Specific conductivity of KCl-10mas.% MgCl2-CaCl2 and NaCl-10mas.% MgCl2-CaCl2

mixtures at 1073 K
In quaternary mixtures KCl-NaCl-10mas.% MgCl2-CaCl2 additional coefficient for CaCl2

changes with relation of alkali chlorides concentration:
lnχ = 4,9· exp[-(2747-33724/V)/T] exp(53,7/V) ·K
K = exp(-0,35·N3) ·exp(-1,2·N1·N4 – 0,12·N2 ·N4) (6)
Where N1 - molar fraction of KCl, N2 - molar fraction of NaCl, N3- molar fraction of MgCl2 N4
- molar fraction of CaCl2. The comparison of experimental and calculated data for these systems
is given at Table 3. Molar volume was calculated using equation proposed by K. Grothiem et al.
[6].
Table 3. The comparison of experimental and calculated conductivity data in

KCl-NaCl -10mas.% MgCl2-CaCl2 molten system
Mas.% of Molar ratio Calculation on eq. 1 Experimental values [2]
CaCl2 NaCl/KCl Ohm-1 ·cm-1 Ohm-1 ·cm-1
0 3 2,76 2,72
30 3 2,13 2,10
0 1 2,44 2,31
30 1 1,87 1,80
0 1/3 2,09 2,00
30 1/3 1,69 1,54
Conclusions
1. There are various processes at mixing of molten salts depending on ionic potential difference.
When ionic potentials are very close the mixture is ideal. It means that enthalpy of mixing is
369
very low, molar volume changes according to additive law, and specific conductivity change
can be described by equation (1).
2. Electrical conductivity of electrolytes for magnesium electrolysis can be calculated via
temperature-volume equation using some additional coefficients
References
1. A.Redkin, in Proceedings of 13th Internat. Symp. on Molten Salts. H. C. Delong, R. W.

Bradshaw, M. Matsunaga, G. R. Stafford, and P. C. Trulove, Eds.; The Electrochemical
Society:Pennington NJ, 2002, pp. 453-459.
2. Ch. L. Strelez, A.Z, Taiz and B. Gulyanitzkii. Metallurgia magniya. Metallurgizdat, Moscow
1960
3. J.O'M Bockris, E.N. Crook and N.E. Richards. Proceedings of the Royal Society, ser. A.
Mathematical and Physical Sciences,V.255, No 1283, 558-578, 1960
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10. J.Huheey. Principles of structure and reactivity. Harper Row Publishers. New York. 1983.
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STUDIES ON ZnO BASED DILUTED MAGNETIC SEMICONDUCTORS
Sasanka Deka1, P. A. Joy2

1
National Nanotechnology Laboratory of INFM, Via Arnesano Km 5, Lecce 73100, Italy
2
Physical Chemistry Division, National Chemical Laboratory, Pune-411008, India
Keywords: Semiconductors, Magnetic Properties, Optical Properties, Doping.
Abstract
The observation of ferromagnetism in the transition metal (TM) doped wide band gap
nonmagnetic semiconductor ZnO opened up a new area of research because of the potential
applications in spintronics devices. These ZnO based diluted magnetic semiconductors (DMS)
combine their transport and optical properties with magnetism. We have carried out synthesis
and studies on the magnetic and optical properties on TM doped ZnO powders in nanocrystalline
form. Our studies give evidence for the origin of ferromagnetism as extrinsic due to the presence
of metal nanoclusters as secondary phases in the Co and Ni doped ZnO systems although the
optical and electronic structure studies indicate the incorporation of divalent metal ions inside the
ZnO crystal lattice.
Introduction
The carrier induced ferromagnetism in the transition metal doped wide band gap II-VI and III-V
nonmagnetic semiconductors opened up a new area of research because of the potential
applications of these materials based on their magnetic and semiconducting properties [1]. These
new functional materials, known as diluted magnetic semiconductors (DMS), exhibit inherent
properties from the charge and spin of an electron in a single material and the ability of DMSs to
combine their transport and optical properties with magnetism can be made use of in spintronics.
In 1999, Fiederling et al.[2] and Ohno et al.[3] successfully showed the controlling of
polarization of light by using III-V based DMS as the spin polarizer in a p-(i)-n junction.
ZnO is a II–VI semiconductor with a band gap of 3.3 eV at 300 K, almost identical to that of
GaN of the III–V system. Therefore ZnO based DMS would be very interesting from the
viewpoint of forming transparent ferromagnetic materials. From ab initio calculations, it has
been predicted that ZnO doped with several 3d transition metal ions such as V, Cr, Fe, Co and Ni
may exhibit ferromagnetism [4]. Based on these theoretical calculations, several experimental
investigations have been carried out by different researchers on the II-VI semiconductors.
Almost all the studies on ZnO based DMSs have been performed on thin film samples made by
different techniques. Observation of ferromagnetism at or above room temperature is reported
for Co-doped ZnO [5], Mn-doped ZnO [6] and Ni-doped ZnO [7] thin film and powder systems.
There are also few reports where a secondary phase or impurity or metal cluster phase is found to
be responsible for ferromagnetism in the oxide semiconductors [8].
There are not many studies reported on the absence or presence of ferromagnetism in
polycrystalline samples. If transition metal doping can induce ferromagnetism in ZnO thin film
samples, it is expected that this should be possible in polycrystalline materials also. There are
some reports on the absence of ferromagnetism in polycrystalline samples [9] and direct or
indirect evidence for Co metal clusters and secondary phases as the origin of ferromagnetism in
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thin film samples of Co doped ZnO [10]. We have attempted to deduce the origin of
ferromagnetism in Co-doped and Ni-doped polycrystalline ZnO synthesized by a low-
temperature combustion method. Ferromagnetism at room temperature is observed in the
nanocrystalline powders of Zn1-xCoxO and Zn1-xNixO, even for smaller values of x, and direct
and indirect evidences for the presence of metallic Co-nanoclusters and Ni- nanoclusters in all
the samples are obtained.
Experimental
Zn1-xCoxO (x = 0, 0.05 and 0.1) and Zn1-xNixO (x = 0, 0.025 and 0.05) samples were synthesized
by a combustion method from the nitrates of Zn and Co or Ni taken in the approximate ratio and
glycine as the fuel, as reported previously [11]. The as-synthesized powder samples were
characterized by powder X-ray diffraction (Philips 1730, Cu Kα radiation). The particle selected
area electron diffraction (SAED) patterns were obtained using a JEOL model 1200 EX
transmission electron microscope. Magnetization measurements as a function of magnetic field
were carried out using a vibration sample magnetometer (EG&G PAR 4500). Electronic
absorption spectra were recorded on a JASCO V-570 spectrophotometer.
Figure 1. Powder XRD patterns of different compositions in (a) Zn1-xCoxO (x = 0.05 and 0.1)
along with the simulated pattern for Wurtzite ZnO, and (b) Zn1-xNixO (0 ≤ x ≤ 0.05)
Figure 1 shows the powder X-ray diffraction (XRD) patterns of the as-synthesized Zn1-xCoxO
and Zn1-xNixO. For x = 0 (see figure 1b), all the reflections correspond to the wurtzite structure of
ZnO (JCPDS #5-664), whose simulated XRD pattern is shown as ZnO in Figure 1a. The XRD
patterns for x > 0 show that the ZnO structure is not disturbed on substitution. All the reflections
for different compositions are somewhat broad and this is due to the smaller crystallite sizes of
the compositions synthesized by the low-temperature method. The average crystallite size is
calculated from X-ray line broadening using the Scherrer formula, t = 0.9λ/βcosθ, where t is the
crystallite size in Å, β is the half maximum line width and λ is the wavelength of X-rays, and is
obtained as ~40 nm for all compositions. No additional peaks due to any impurities are observed
for x ≤ 0.10 in the case of Zn1-xCoxO. On the other hand, in the case of Zn1-xNixO, an additional
very low intense peak is observed at 2θ = 43.2° for x = 0.025, which is the most intense peak of
NiO (figure 1b). Apart from this peak with enhanced intensity, an additional weak reflection is
374
observed for x = 0.05, close to the reflection from NiO. This weak extra peak in the XRD
patterns is found to be due to Ni metal. Thus the powder XRD studies directly indicate the
presence of Ni metal, apart from NiO, in the polycrystalline Zn1-xNixO samples. The observation
of reflections in the XRD patterns due to impurities such as NiO in x = 0.025 and NiO and Ni
metal in x = 0.05 indicate that, either Ni2+ is not substituted for Zn2+ in the ZnO lattice or that
may be very small amounts of Ni2+ is substituted and the rest of the nickel is converted to NiO
and partly to Ni metal clusters. In the case of Zn1-xCoxO, formation of other impurity phases can
not be ruled out. It is possible that Co metal particles, in minor amounts, may be formed and it is
not detected in the XRD patterns due to its very low concentrations.
Figure 2. Magnetization as a function of magnetic field, measured at room temperature for

different compositions in (a) Zn1-xCoxO (x= 0.05, 0.1) and (b) Zn1-xNixO (x = 0.025, 0.05).
Figure 2 shows the magnetization of the different compositions, as a function of magnetic field,
measured at room temperature. The Ni-doped samples are found to be ferromagnetic at room
temperature. Weak ferromagnetism (0.1 and 0.15 emu/g for x = 0.025 and 0.05, respectively),
which is saturated just above 1 kOe, is observed at 300 K. Since Ni metal and NiO are observed
as impurities present in the as-synthesized samples, it can be assumed that magnetic contribution
comes mainly from these two phases. Bulk NiO is antiferromagnetic with a Neel temperature of
520 K and nanocrystalline NiO shows weak ferromagnetic or superparamagnetic behaviour at
low temperatures [12]. The fraction of NiO in the x = 0.025 sample is very small and is not likely
to contribute much toward the observed ferromagnetism. For the x = 0.05 sample also, the
antiferromagnetic (linear M-H variation) or weak ferromagnetic contribution will be much less
than that expected from NiO. Very weak ferromagnetism, 0.08 and 0.28 emu/g at 10 kOe, is
observed in case of Zn1-xCoxO for x = 0.05 and 0.1, respectively. However, as no indication for
the presence of Co impurity phase is observed in the powder XRD patterns of Zn1-xCoxO (x =
0.05, 0.1) and weak ferromagnetism is observed for smaller Co concentrations in Zn1-xCoxO also,
it may be assumed that, at least, for x ≤ 0.1, ferromagnetism originates on doping Co2+ at the Zn
sites in ZnO.
The colour of the Co-doped samples was found to be greenish. The change in the colour of the
as-synthesized samples from colourless (slightly greyish due to residual carbon content) for x = 0
to pale green (for x = 0.05 and 0.1) is an indication for the incorporation of some of Co2+ in the
ZnO lattice. Further evidence for this is obtained from the optical absorption studies. The room
temperature optical absorption spectra of the as-synthesized samples including that of ZnO (x =
0) are shown in Figure 3a. The band gap transition for the un-doped compound is observed at
385 nm (3.27 eV). On the other hand, additional absorption features are observed in the case of
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Zn1-xCoxO. The additional absorption bands are at 2.18, 2.03 and 1.89 eV. These absorption
bands are assigned as 4A2(F) → 2A1(G), 4A2(F) → 4T1(P) and 4A2(F) → 2E(G), respectively, due
to the crystal field transitions in the high spin state of Co2+ (3d7) in the tetrahedral coordination
environment [13]. Since Zn2+ in ZnO is situated in tetrahedral coordination, these observations
clearly indicate that cobalt is substituted for Zn in ZnO and that the oxidation state of Co ions in
the polycrystalline Zn1-xCoxO is Co2+ which are tetrahedrally coordinated.
Figure 3. Electronic spectra of the samples of different compositions in (a) Zn1-xCoxO and (b)
Zn1-xNixO. Inset of (b) shows the ligand field transitions of Ni2+ in tetrahedral symmetry.
Figure 3b shows the variation of optical absorbance with photon energy, near the band edge for
the as-synthesized Zn1-xNixO samples. The band edge is shifted to the lower energy side for the
Ni-doped samples, as shown in Figure 3b. The band edge is obtained as 3.242 eV for both the x
= 0.025 and 0.05 samples. The decrease in the band edge is a clear indication for the
incorporation of Ni inside the ZnO lattice. The red shift in the band edge is due to the increased
sp-d exchange interactions between the band electrons and the localized d-electrons of the
substituted Ni2+ ions [14]. Inset in Figure 3b shows the spin-orbit split 3T1(F)→3T1(P) ligand field
transitions of Ni2+ in tetrahedral symmetry, for the as-synthesized and annealed samples of x =
0.025 and 0.05. The electronic transitions are observed in all cases, indicating that Ni2+ is
substituted in the tetrahedral Zn2+ site and is in a stable environment [15]. The decrease in the
band edge and the observation of the electronic transition of Ni2+ are clear indications for the
incorporation of Ni inside the ZnO lattice. This shows that a small fraction of Zn is substituted
by Ni in the ZnO lattice. Since the band edge remains the same for both the doped samples, the
degree of substitution of Ni for Zn is likely to be the same in both samples.
Figure 4. Comparison of selected area electron diffraction patterns of as-synthesized

Zn0.975Ni0.025O and Zn0.95Ni0.05O.
Further evidence for the presence of Ni metal and its oxides in the doped samples is obtained
from electron diffraction studies. The selected area diffraction patterns of the x = 0.025 and 0.05
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in Zn1-xNixO are compared in Figure 4. Many additional diffraction spots and rings, apart from
those from the ZnO lattice, are observed in both the patterns. The additional spots and rings in
the electron diffraction patterns are identified as those from fcc Ni and cubic NiO.
Figure 5. Selected area electron diffraction patterns of (a) ZnO, (b) Zn0.95Co0.05O and (c)
Zn0.9Co0.1O.
Though no direct evidence for the presence of Co or its oxides in the lightly doped samples is
obtained from XRD studies, clear evidence for the presence of Co metal and its oxides in x ≤ 0.1
compositions Zn1-xCoxO is obtained from electron diffraction studies. The selected area electron
diffraction patterns of the as-synthesized samples of x = 0, 0.05 and 0.1 are compared in Figure
5. Many additional diffraction spots and rings, apart from those from the ZnO lattice are
observed in the patterns of the x = 0.05 and 0.1 samples. The additional spots and rings in the
electron diffraction pattern are identified as those from Co metal, CoO and Co3O4. The presence
of these impurities in the lightly doped samples could not be detected from powder XRD studies
probably because of their very low concentrations. Since information for the presence of Co
metal in the x = 0.05 and 0.1 samples is obtained now, it can be concluded that the observed
ferromagnetism of these samples also is coming from Co metal impurities.
Conclusions
A combination and comparison of the results from different characterization techniques used in
the present study give direct and indirect evidences for the presence of Co metal impurities in the
Co-doped and Ni metal impurities in the Ni-doped ZnO samples. Evidence is also obtained for
the incorporation of Ni2+ and Co2+ in the ZnO lattice from optical absorption studies. Hence it
can be concluded that part of the cobalt or nickel added during the synthesis of the
polycrystalline sample is incorporated in the ZnO lattice and the rest of the cobalt or nickel is
converted to respective metal and its oxides, which remain as separate phases. Though the ZnO
lattice is partially doped with Co2+ or Ni2+, this is not responsible for ferromagnetism. The
changes in the optical (electronic) properties or the properties associated with the charge of the
electron in Zn1-xCoxO or Zn1-xNixO is due to the doped Co2+ or Ni2+, respectively, in the ZnO
lattice and the changes in the magnetic properties or the properties associated with the spin of the
electron is originating from the ferromagnetic impurities, present in the samples. That is, the
apparent spintronics properties observed for the Co-doped ZnO and Ni-doped ZnO samples are
originating from different sources.
References
1. S.J. Pearton et al., “Wide band gap ferromagnetic semiconductors and oxides,” J. Appl.
Phys., 93 (1) (2003), 1-13.
377
2. R. Fiederling et al., “Injection and detection of a spin-polarized current in a light-emitting
diode,” Nature, 402 (1999), 787-790.
3. Y. Ohno et al., “Electrical spin injection in a ferromagnetic semiconductor heterostructure,”

Nature, 402 (1999), 790-792.
4. K. Sato and H. Katayama-Yoshida, “Material Design for Transparent Ferromagnets with

ZnO-Based Magnetic Semiconductors,” Jpn. J. Appl. Phys. Part2, 39 (2000), L555-L558.
5. (a) H-J. Lee et al., “Study of diluted magnetic semiconductor: Co-doped ZnO,” Appl. Phys.
Lett., 81 (21) (2002), 4020-4022. (b) D. Rubi et al., "Reversible ferromagnetic switching in
ZnO :(Co, Mn) powders," Phys. Rev. B, 75 (15) (2007), 155322.
6. N.S. Norberg et al., “Synthesis of Colloidal Mn2+:ZnO Quantum Dots and High-TC
Ferromagnetic Nanocrystalline Thin Films,” J. Am. Chem. Soc., 126 (2004), 9387-9398.
7. D.A. Schwartz and D.R. Gamelin, “Reversible 300 K ferromagnetic ordering in a diluted
magnetic semiconductor,” Adv. Mater., 16 (2004), 2115-2119.
8. (a) D.C. Kundaliya et al., “On the origin of high-temperature ferromagnetism in the low-
temperature-processed Mn–Zn–O system,” Nature Mater., 3 (2004), 709-714. (b) J. Blasco et
al., "Magnetic properties of doped ZnO prepared by different synthetic routes," J. Magn.
Magn. Mater., 316 (2) (2007), e177-e180.
9. (a) C.N.R. Rao and F.L. Deepak, “Absence of ferromagnetism in Mn- and Co-doped ZnO” J.
Mater. Chem., 15 (2005), 573-578. (b) G. Lawes et al., “Absence of ferromagnetism in Co
and Mn substituted polycrystalline ZnO,” Phys. Rev. B, 71 (2005), 045201.
10. J.H. Park et al., “Co-metal clustering as the origin of ferromagnetism in Co-doped ZnO thin
films,” Appl. Phys. Lett., 84 (8) (2004), 1338-1340.
11. S. Deka, R. Pasricha, and P.A. Joy, “Synthesis and Ferromagnetic Properties of Lightly
Doped Nanocrystalline Zn1-xCoxO,” Chem. Mater., 16 (7) (2004), 1168-1169.
12. R.H. Kodama, S.A. Makhlouf, and A.E.Berkowitz, “Finite size effects in antiferromagnetic
NiO nanoparticles,” Phys. ReV. Lett., 79 (7) (1997), 1393-1396.
13. S. Deka, R. Pasricha, and P.A. Joy, “Experimental comparison of the structural, magnetic,
electronic, and optical properties of ferromagnetic and paramagnetic polycrystalline
Zn1−xCoxO (x = 0, 0.05, 0.1),” Phys. Rev. B, 74 (2006) 033201.
14. K.J. Kim and Y.R. Park, “Spectroscopic ellipsometry study of optical transitions in Zn1–
xCoxO alloys,” Appl. Phys. Lett., 81 (2002), 1420-1422.
15. S. Deka and P.A. Joy, “Direct Observation of Ni Metal Impurities in Lightly Doped
Ferromagnetic Polycrystalline (ZnNi)O,” Chem. Mater., 17 (26) (2005), 6507-6510.
378
TANTALUM ELECTROLYTIC CAPACITORS

Rizwan Abdul Rahman Rashid, Siva Jyoth, Rajkiran, Prasad Goud
Mahatma Gandhi Institute of Technology
Solid electrolyte tantalum capacitors have been a major contribution to the miniaturization of
electronic circuitry. They also operate over a wide temperature range and have good shell life,
long service and are useful in extreme environments. Surface mount technology tantalum
capacitors are increasingly being used in new circuit designs because of their volumetric
efficiency, basic reliability and process compatibility. It is also of interest that because of the
solid nature of the tantalum capacitor’s construction, there is no known wear out mechanism in
tantalum capacitors. The most popular use for tantalum capacitors are in personal computers,
disk drives, cellular phones, printers, hand held pagers, automobiles and in military equipments.
Currently, tantalum powders suitable for utility in high performance capacitors are produced by
one of two different methods. The first of these powder production methods involve the sodium
reduction of potassium fluorotantalate. In the second method, powder is produced by hydriding a
melted tantalum ingot, milling the hydrided chips, followed by dehydriding. In general, sodium
reduced tantalum powder have provided high surface area, resulting in high capacitance values
per gram of powder. Sodium reduced powder is useful in lower voltage applications. Ingot
derived tantalum powders are extremely pure with contamination levels an order of magnitude
lower than sodium reduced powders. Ingot derived powders typically provide lower D.C.
leakage, longer life, and higher voltage capability. Because of the high purity and other
characteristics, capacitors made from ingot derived powder are used in systems where high
reliability is a prime requisite.
The performance characteristics of capacitors or electrodes formed from capacitor grade powders
are expressed in terms of specific charge and electrical current leakage. The specific charge,
normally expressed in µFV/g is a measure of electrical charge capacity of the capacitor and is
proportional to the surface area of the powder as sintered and anodized pellet. The electrical
leakage, normally expressed in units of nA/µFV, is an indication of how well the capacitor holds
the specific charge. Capacitors with improved electrical leakage characteristics are recognized as
having higher reliability.
Tantalum capacitors typically are manufactured by compressing agglomerated tantalum powder
to form a pellet, sintering the pellet in a furnace to form a porous tantalum body and then
subjecting the porous body to anodization in a suitable electrolyte to form a continuous dielectric
oxide film on the sintered body. Development of powders suitable for making tantalum
capacitors has resulted from the efforts by both capacitor procedures and tantalum processors to
delineate the characteristics required for tantalum powder in order for it to best serve in the
production of quality capacitors. Such characteristics include specific surface area, purity,
shrinkage, pressability, green strength, flowability and die filing capabilities. First of all, the
powder should provide an adequate electrode surface area when formed into a porous body and
sintered. The µFV/g of tantalum capacitors is proportional to the specific surface area of the
sintered porous body produced by sintering tantalum powder pellet; the greater the specific
surface area after sintering, the greater the µFV/g. The specific surface area of tantalum powder
is related to the maximum µFV/g attainable in the sintered body.
Purity of the powder is an important consideration. Metallic and non-metallic contamination
tends to degrade the dielectric oxide film in tantalum capacitors. While high sintering
temperatures serves to remove some volatile contaminations; high temperatures tend to shrink
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the porous body reducing its net specific surface area and thus the capacitance of the resulting
capacitor. Flowability of the tantalum powder and green strength are also important
characteristics for the capacitor producer inorder to provide efficient production. The flowability
of the agglomerated tantalum powder is essential to proper operation of automobile pellet
presses. Green strength is a measure of a pellet’s mechanical strength. Sufficient green strength
permits handling and transport of a pressed product without excessive breakage. The term
pressability describes the ability for a tantalum powder to be pressed into a pellet. Tantalum
powder that forms pellet that retain their shape and have sufficient green strength to withstand
ordinary processing manufacturing conditions without significant breakage have good
pressability.
Inorder to increase the specific capacitance (and volumetric efficiency); the particle sizes of the
tantalum powder used to form capacitors have been reduced to a smaller and smaller size. With
the reduction in size, the temperature required to sinter the particles drops drastically. However,
it is also necessary to raise the temperature of the particles high enough during sintering to purify
the particles, which has in turn limited the smallest particle size capable of being used so as to
not excessively fuse it during the high temperature purification. Another problem associated with
using very small particles is encountered during the subsequent anodisation of the capacitor
anode body. This is because when the dielectric is produced, it grows out of the surface of the
tantalum powder by about one third of the thickness and into the powder by around two thirds,
thus if small particle size powders were used, each particle would quickly become consumed and
isolated.
It is well known in the tantalum powder industry that certain powder characteristics as powder
flow, specific surface area, oxygen content and other measurable physical and electrical
properties can be modified in the course of production. However, in most cases that alteration
will most likely have an adverse effect to one or more of the other measured physical and
electrical properties. Certain electrical properties of tantalum capacitors can be improved as the
pressed density of a tantalum pellet is decreased. For example; the lower the pressed density, the
higher the specific capacitance. Other measurable electrical properties such as ESR (Equivalent
Series Resistance) are improved as pressed density is decreased. There is of course, a limit to the
minimum pressed density achieved while retaining the ability of a pressed green pellet to
maintain its structural integrity when ejected from a pellet pressing machine. A way to compare
the minimum pressed densities at which given tantalum powders can be used to produce green
pellets of acceptable structural integrity is to compare the crush strength of the pellets. The
higher the strength at a given pressed density, the lower the green pressed density obtainable.
Tantalum capacitor fabrication
The tantalum powder is mixed with a suitable binder/lubricant to ensure that the particles will
adhere to each other when pressed to form the anode, and flow easily into the press tool. The
powder is then compressed under high pressure around a tantalum wire to make a tantalum ‘slug’
(tantalum anode element). The riser wire will eventually become the anode connection to the
capacitor. The binder/lubricant is driven off by heating the slugs under vacuum at temperatures
around 150 0C for several minutes. This is followed by sintering at high temperature (typically
15000 – 2000 0C) under vacuum. This causes the individual particles to join together to form a
sponge-like structure. This structure is of high mechanical strength and density, but is also highly
porous giving a large internal surface area. If the anodes are sintered for too long or at too high a
temperature, the particles fuse together too much, and thus the capacitance of the anode will be
too low. Similarly, if the anodes are sintered for too short a time, or the furnace temperature is
380
too low, the capacitance will be too high and also the DC leakage. Verification is made on each
sinter lot by anodizing several quality control anodes and performing a wet capacitance check.
The tantalum slugs are now welded onto a metal carrier strip to enable subsequent processes of
manufacture, and a Teflon washer is added to the riser wire, which will prevent the manganese
dioxide counter electrode passing up to the carrier strip. They are then referred to as a ‘stringer’
of anodes.
The next stage is the production of the dielectric layer of tantalum pentoxide. This is produced
by the electrochemical process of anodisation. The slugs are dipped into a very weak solution of
acid, for example, phosphoric acid, at an elevated temperature, for example, 850 C, and the
voltage and current are controlled to form the pentoxide layer. Tantalum is a valve metal, and the
amorphous pentoxide grown is able to form a uniform, closely coupled layer over the tantalum
surface. The dielectric thickness is controlled by the voltage applied during the formation
process. Initially the power supply is kept at a constant, until the required formation voltage has
been reached. The power supply is then kept at a constant voltage to ensure the correct dielectric
thickness is formed all over the tantalum slug’s surface, and therefore the forming current
decays.
The chemical equations describing the anodization process are as follows:
Anode:
2Ta Æ 2Ta5+ + 10e-
2Ta5+ + 10OH- Æ Ta2O5 + 5H2O
Cathode:
10 H2O + 10e- Æ 5 H2 + 10OH-
For each unit of oxide one-third grows out and two-thirds grow in. The formation voltage can be
checked visually by examining the color of the slug. This is because different thicknesses of
dielectric create different interference patterns when light is shown onto them, similar to an oil
film on water. For example, a light green color could mean a formation voltage in the range of
100-104 volts and a light purple color to a range of 72-76 volts. The capacitor’s formation
voltage is typically 3 to 4 tomes the capacitor’s rated voltages, this is to ensure good reliability.
The next stage of manufacture is the production of the cathode electrode plate. This is achieved
by pyrolysis of manganese nitrate into manganese dioxide. The ‘slug’ is dipped into an aqueous
solution of manganese nitrate and then baked in an oven at approximately 2500 C to produce a
dioxide coat.
The chemical equation in a simplified manner is:
Mn (NO3)2 Æ MnO2 + 2NO2
This process is repeated several times through varying concentrations of nitrate solution to
ensure good penetration of the anode, and to build up a thick outer coat on the surface of the
capacitor.
The stringers are now dipped into an acid bath, generally of acetic acid, and a voltage applied of
approximately half the original forming voltage. This removes manganese from high leakage
current areas within the slug and grows a dielectric layer to plug the site. The stringer is then
dipped into graphite dispersion and transferred to an oven where it is heated to ensure good
adherence to the slug. The process is then repeated with a silver dispersion to provide the final
connection layer to the cathode terminal. The graphite layer is used to prevent the silver layer
coming into direct contact with manganese dioxide.
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If this were to occur a chemical reaction would take place, and the silver would be oxidized to
high resistivity silver oxide, and the manganese dioxide reduced to manganese (III) oxide, which
again has a high resistivity. The part would therefore become high resistance, and the capacitor
cease to function adequately.
Ag + 2MnO2 Æ AgO + Mn2O3
Advantages of tantalum capacitors:

1. No Wear out Mechanism
Tantalum capacitors have a unique "self-healing" mechanism that results in a decreasing
failure rate over time. If a tantalum capacitor has an impurity or imperfection in the dielectric
layer, a heavy current will flow through the site when a DC current is applied. Resistance of
the MnO2 layer to this current causes localized heating and converts the MnO2 to a more
resistive form, typically Mn2O3. This new oxide plugs up the fault site and reduces the
current flow.
2. Better Frequency – ESR
Tantalum capacitors have better frequency characteristics than other types of capacitors,
especially aluminum electrolytic capacitors. Typically, an identical CV tantalum has 10 times
better ESR than aluminum.
3. High Volumetric Efficiency
Tantalum capacitors offer high volumetric efficiency (CV/cc) compared with other capacitors
types. In many applications, 100 microfarad aluminum can be replaced with a 10 microfarad
tantalum. Because of their package dimensions, tantalum capacitors enable circuit designers
to optimize powder dissipation capability within the confines of precious circuit space. Also,
their compact shape and flat top surface allow them to be easily handled and mounted onto
circuit boards.
4. High Reliability
Unlike liquid electrolytic capacitors, tantalum capacitors do not lose capacitance from the
"deform effect." Due to their solid construction, electrical performance does not degrade over
time, which is why the shelf life of tantalum capacitors is considered to be infinite.
5. Better Temperature Performance
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Tantalum capacitors have a wide operating range, -55 degrees C to +125 degrees C, and
experience minimal degradation in electrical properties over this temperature range. The
variation is dependent to some extent on the rated voltage and capacitor size.
The following conclusions are drawn from the experiments carried out in this investigation:-
1. The density of compact is found to depend on the particle size and its distribution.
Coarser particles lead to lower density and vice-versa.
2. In the electrical characterization, the CV/g values of the slugs are dependent on the
formation voltage applied. The CV/g values increases with an increase in the formation
voltages.
3. CV/g values are also dependent on the size of the tantalum particles. The coarser the
tantalum powder, the less the CV/g value and vice-versa.
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Experimental Study of Co-Deposition of SiO2 and GeO2 in a

Modified Chemical Vapor Deposition (MCVD) Reactor
S. Zhan1, M. Hasan1, T. Wang2 and Z. Chen2
1
McGill University, Dept. of Mining & Materials Engineering
Montreal, Quebec, Canada H3A 2B2
2
Shanghai University, School of Communication and Information Engineering
Shanghai, China 200072
Keywords: SiO2, GeO2, Co-Deposition, MCVD
Abstract
MCVD reactors are used to commercially manufacture high quality optical fibers. An MCVD
reactor consists of a slowly rotating, fire polished silica tube wherein a mixture of gaseous
silicon tetrachloride (SiCl4), germanium tetrachloride (GeCl4) and carrier oxygen gas is
introduced at one or both ends of the tube. The tube is heated by slowly traversing an oxy-
hydrogen torch to allow for the high temperature chemical reactions to produce fine particles of
SiO2 and GeO2. These particles move with the un-reacted gas mixture and deposit onto the inner
surface of the tube. Co-deposition experiments were carried out on a laboratory scale MCVD
reactor. The thickness of the deposited layer and the concentrations of germanium, silicon and
oxygen were measured by scanning electron microscopy (SEM) and energy dispersive
spectrometer (EDS). Experimental results were obtained by varying the torch heat fluxes
(temperatures), torch moving speed, and in-take ratio of GeCl4/SiCl4.
Introduction
The silica-based fibers were found to be used as a transmission medium by Kao and Hockham [1]
in 1966. Since that time, substantial progress has been made in the development of processing
techniques to fabricate optical fiber. With the uprising demand of optical communications,
optical fibers are no longer just high technology materials but have become commodity products
now [2]. Any slight improvement in the manufacturing process can yield substantial economic
benefit.
Fiber production can be divided into two process steps, namely, preform fabrication and fiber
drawing. There are four most popular preform processes, which are Modified Chemical Vapor
Deposition (MCVD), Plasma Chemical Vapor Deposition (PCVD), Outside Vapor Deposition
(OVD), and Vapor Axial Deposition (VAD)[3]. Among these four core deposition processes, the
MCVD process is relatively flexible and versatile and requires the least investment and staffing
for equivalent capacity.
The SiO2/GeO2 concentration and the non-uniformity of deposition thickness will affect the
quality of preforms. Microstructures in MCVD preforms were studied using optical and electron
microscopic techniques available during the early development of the process. [4] With the
development and availability of new measuring instrumentations, MCVD optical fibre preforms
quality have recently been re-examined using modern micro-analytical instrumentation and
techniques, such as back-scattered electron (BSE) imaging and X-ray chemical mapping [5].
Although the preform material properties will affect the optical fiber properties, to the best of our
knowledge, there are no published qualitative experimental data on the measurements of
concentration of SiO2/GeO2 and the thickness of the deposition layer for an MCVD process.
385
This paper presents the experimental investigation of the morphological details, thickness and
Si/Ge concentration in the deposition layer of preforms manufactured by an MCVD process.
Experiments
Fabrication of preform
MCVD preforms were fabricated from substrate tubes of approximate dimensions 0.0018 m
(outer diameter) and 0.0015 m (inner diameter) with 0.3m length by a laboratory scale MCVD
reactor using a standard MCVD process, as displayed schematically in Figure 1[6]. Figure 2
shows the MCVD lathe applied to manufacture the preform.
Figure 1 Schematic diagram showing a typical MCVD process
Figure 2 MCVD lathe employed in this study

During the process of deposition, a controlled gaseous mixture of SiCl4, GeCl4 and oxygen were
continuously fed into the rotating preheated tube. As the burner passed over the deposition soot,
it was then fused in a thin glassy layer by viscous sintering. The temperature was kept
sufficiently high to sinter the deposited material but not so high to cause the distortion of the tube.
Typically, preforms are formed by multi-pass techniques. In this paper, the thin film layer which
formed on the inner surface of the silica tube due to only one pass of the torch was studied. The
typical overall chemical reactions which occur in the gaseous phase inside the heated rotating
tube are as follows:
SiCl 4 ( g ) + O2 ( g ) → SiO2 ( s ) + 2Cl 2 (g) (1)
386
GeCl4 ( g ) + O2 ( g ) ↔ GeO2 ( s ) + 2Cl2 (g) (2)
The important parameters in an MCVD process are torch temperature, inlet concentrations of
gases and torch moving speed for co-deposition of SiO2 and GeO2. A set of experiments were
carried out and the physical input conditions of the experiments are listed in Table 1.
Table 1 Experiment Conditions
Characterization of preforms
Each preform tube of 0.3 m length was cut into five samples which were located at 0, 0.056m,
0.13m, 0.186m and 0.242m. The thickness of each sample is 0.02m. Figure 3 schematically
shows the preparation of a sample for measurement. The surfaces examined for the deposition
concentrations and thicknesses are perpendicular to the longitudinal direction. Samples were
mounted and polished down to 1 μm diamond slurry. Five points were tested at the each sample
and the each point was tested three times. In some cases, the surfaces perpendicular and
tangential to the horizontal directions were observed as well. Secondary electron image (SEI)
detector, SEM and EDS were applied to quantitatively measure the relevant parameters.
Figure 3 Schematic diagram illustrating a sample cut from a tube.
387
A typical deposition layer observed by FE-SEM (Model: Hitachi S-4700) is presented in Figure
4. Since the co-deposition chemical reactions occurred only at a narrow range near to the moving
torch where the residence time was short, the deposition layer is very thin as seen in this picture.
Figure 4 Morphological detail of a deposition layer

The corresponding chemical analysis by EDS is shown in Figure 5. Four main elements were
observed in the deposition layer, namely, O, C, Si and Ge. While there were only Si and O in the
known existing elements in the substrate tubes, this figure clearly indicates that the co-deposition
have occurred on the inner surface of the silicon tube from chemical reactions.
Figure 5 EDS spectra for a deposition layer on the SiO2 substrate in Figure 4
Figure 6 shows a typically thickness of the deposition layer for one sample tested by SEI. Here
the thickness is 1.71 μm . The deposition layer appears uniform and continuous in this sample.
388
Figure 6 A typical thickness layer observed by SEI
The measurements of Ge deposition concentrations obtained under different conditions are
presented in Figure 7. In Case 1, the Ge deposition concentration is higher than that in Case 2.
This is because the inlet concentration of GeCl4 is higher for case 1. The Ge deposition
concentration is not only affected by the GeCl4 inlet concentration but also by the reaction (2).
High temperature can increase the forward chemical reaction. Hence, the Ge deposition
concentration was improved, leading to higher Ge concentration in Case 3 than that in Case 4.
Some variations of Ge concentration were found in Case 5 and Case 6. In Case 5, the torch
moved faster. So the residence time was shorter than that in Case 6 and hence resulted in a lower
concentration profile. Because the inlet concentration of SiCl4 in case 7 was lower than that in
Case 8, the GeCl4 concentration is higher in Case 7. This resulted in a higher Ge concentration in
the deposition layer in Case 7.
Figure 7 Ge concentrations in the deposition layers.

Summary
The use of SEM-EDS technique has provided a good insight into the investigation of optical
fiber preform manufacturing process using MCVD. This study presented the morphological
details, thickness and Si/Ge concentration in the deposition layer.
389
From the limited experimental findings, the following conclusions can be drawn:
1. Inlet concentration of precursors can significantly affect the deposition concentration of
Germanium dioxide.
2. High temperature can increase the GeO2 concentration in the deposition layer.
Acknowledgments
This research was sponsored by the Natural Sciences and Engineering Research Council of
Canada through the discovery grant of Prof. Mainul Hasan. The authors are grateful to Dr. Lan
Jiang of McGill University for technical assistance with respect to scanning electron microscopy.
References
1. Kao K.C., Hockham G.A., “Dielectric-fibre surface waveguides for optical frequencies”,
IEE Proc., 113 (1966),1151-1158
2. Sarkar, A., “Economics of single mode fiber production using MCVD & VAD processes”,
Proceedings of SPIE - The International Society for Optical Engineering, 3666 (1999),18-22
3. Koel, G. J., “ Technical and economic aspects of the different fibre fabrication processes”,
European Conference on Optical Communication, 1982,1-8
4. Yan M.F., MacChesney, J.B. Nagel S.R. and Rhodes W.W., “Sintering and optical
waveguide glasses”, J. Mater. Sci., 15(1980), 1371-1378
5. Mcnamara P., Lyytikainen K.J., Ryan T., Kaplin I.J., Ringer S.P., “Germanium-rich
“starburst” cores in silica-based optical fibers fabricated by Modified Chemical Deposition”,
Optical communications, 230(2004),45-53
6. Walker K.L., Geyling F.T. and Nagel S.R., “Thermophoretic deposition of small particles in
the modified chemical vapor deposition (MCVD) process”, J. Am. Ceram. Soc.,63 (1980),
552-558
390
LIGHTNING CAUSES AND EFFECTS – A SYSTEMATIC

PROTECTION APPROACH FOR THE ALUMINUM INDUSTRY
Franco D’Alessandro
ERICO Products Australia
c/o 37 Ogilvie Street, Mt Stuart, Tasmania. 7000. AUSTRALIA
Keywords: Lightning Protection, Grounding, Surge and Transient Protection, Six Point Plan
Abstract
Each year, lightning and over-voltage transients cause millions of dollars of damage in different
industries. The aim of this paper, therefore, is to provides readers with an understanding of the
most important aspects of lightning protection, grounding and surge protection for industrial
sites, with an emphasis on the aluminum industry. The paper firstly considers the process of
carrying out a risk assessment and managing the risk to a tolerable level. Secondly, the paper
describes the key points and application of the “six-point protection approach”, a comprehensive
checklist covering the major lightning damage mechanisms.
Introduction
Aluminum is the most abundant metal in the Earth’s crust and its consumption has been growing
more than other metals, at a rate of about 3% per annum. There is currently increasing demand
for the metal from aircraft manufacturers and China, the world’s largest user of aluminum, for
the construction of bridges, skyscrapers and power- transmission lines.
The production of primary aluminum relies on an electrolytic process and is electricity-intensive.
The US aluminum industry consumes a quadrillion Btu of energy each year, including losses
associated with the generation and transmission of electricity at utilities, and about 1% of
domestic energy use and 3% of all US manufacturing energy use [1].
Furthermore, the global primary aluminum industry has been pressing the limits of technology as
a means of improving productivity, cutting costs, streamlining operations and hence raising
profits [2]. The modern primary aluminum production plant utilises a plethora of data
acquisition, process automation and control equipment. As noted in [3], “The pails, yard sticks,
and stop watches of yesteryear have yielded to computer-integrated casting process controls that
include accurate measurement and control of water flow rates, water temperature, metal levels,
drop rates, CO2 and air injection ramping, metal temperatures, in-line systems operation,
electrical systems, lubrication, air flow for air-injected molds, and lengths. These systems
include automatic shutdown provisions.”
The losses incurred as a result of a lightning incident in the aluminum industry cannot be
underestimated. On April 16, 2007, Alcoa announced that the severe electrical storms that hit the
south-eastern United States resulted in a power outage at the company’s Tennessee operations
aluminum smelter [4]. In this particular incident, a power substation serving the smelting
operations was directly hit by a lightning strike, resulting in a complete power outage at the
plant. Fortunately, there were no injuries or deaths, but one of the pot lines at the plant,
representing approximately 107,000 metric tons per year, could not be restarted. On July 9, 2007,
Bloomberg News reported that Alcoa’s second-quarter profit fell 3.9% as costs for shutdowns at
two US smelters, one of which was the Tennessee operation, eroded the benefit of rising metal
prices. The loss was estimated to be about US$36 million. Around mid-June 2007, The Times-
391
Tribune reported that Alcoa had restarted their pot-line, which produces about 107,000 metric
tons per year, and expected it to be fully operational by the end of the month. Hence, the
downtime was almost 8 weeks.
In this regard, the proposed paper presents and discusses the following topics:
1. A review of the deleterious effects of lightning;
2. The risk management approach to lightning protection;
3. A comprehensive checklist approach to lightning protection in order to cover the major
damage mechanisms.
The proposed approach is applicable to the protection of aluminum electricity supply substations
against direct lightning strokes and aluminum production facilities as a whole against both direct
and indirect lightning strokes.
Deleterious Effects of Lightning Discharges
Each year, lightning and over-voltage transients cause millions of dollars of damage in different
industries. Damage to equipment in the USA alone is estimated to be more than US$1 billion
annually, before including the loss of productivity from industrial and business downtime [5].
Apart from the very obvious, visible direct lightning strikes at a particular site, high-energy
“over-voltage transients” are also produced as a result of strikes elsewhere that may be
conducted on services entering the site or facility. Even more common is the scenario in which
damaging transients are induced as a result of nearby strikes due to capacitive or inductive
coupling – the so-called indirect lightning strike.
Some of the specific characteristics of lightning strikes that present dangers to industrial sites and
facilities include [6]:
• Extremely high space voltages (10’s to 100’s of millions of volts) with resulting:
• Charge transfers to ground as high as 400 C;
• Peak “return-stroke” currents up to 200 kA;
• These voltages and currents are characterized by extremely fast rise times, with peak values
being reached in as little time as a fraction of a microsecond;
• There can be up to 30 or more “strokes” in a single lightning “flash”, resulting in multi-pulse
surges separated in time by tens of microseconds;
• “Continuing currents” of 200-500 Amperes, lasting 1-2 seconds, may also occur.
These characteristics result in a variety of undesirable effects and damage, with resultant
material, human, and service losses as well as associated downtime expenses. These lightning
effects act in combination, but they can be identified individually as follows [7]:
(i) Thermal effects
• Thermal damage at the lightning attachment point which is proportional to the “specific
energy” of the current impulse (J/Ω) and the charge of the lightning current (Q);
• Resistive heating of conductors and equipment, proportional to the “specific energy” of the
current impulse;
(ii) Mechanical effects
• Electrodynamic forces, which relate to the peak current (I) and geometrical configuration;
• Acoustic shock wave damage, which depends on the peak current and the rate of rise of
current (dI/dt);
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(iii) Sparking
Sparking is a dangerous effect in flammable environments. Two different types of sparking can
occur:
• Thermal sparking (or arcing), which is proportional to the charge of the lightning current,
occurs when a large current must pass across a gap between two conductors;
• Voltage sparking, or a “side-flash”, occurs when the voltage induced on a conductor exceeds
the breakdown strength of air (or other intervening medium). The voltage is proportional to
the self-inductance of the conductor and the steepness of the lightning current. It is not
unusual for voltages in the order of 1 million volts to be induced if inadequate bonding and
grounding practices are not implemented.
As we will see later in the paper, all of these effects can be dramatically reduced through the
installation of a properly designed lightning protection system.
Lightning Risk Assessment
A key first step in today’s highly technological environment is the implementation of a risk
management plan. In particular, before any lightning protection system is designed, it is
important to carry out a lightning risk assessment. This must be done using international best
practice, e.g., see [8], along with an understanding of lightning principles and the statistics
associated with this stochastic phenomenon.
The need for protection and the level of protection applied should always be considered in terms
of the assessment of risk due to lightning and the management of that risk to an acceptable level.
The approach involves an evaluation of the risk to a structure or site, including persons and
equipment inside, as well as any incoming services associated with the structure or site. The
evaluation considers direct and indirect strikes, mechanical damage to the structure and contents,
damage and failure of equipment, potential differences causing step and touch injuries to people,
and fire damage that may result from the lightning discharge. The procedure involves the
comparison of the evaluated risk with the tolerable or acceptable limit of the risk and allows for
the selection of appropriate protective measures to reduce the risk below the tolerable limit.
Table I summarises all of the risk components and causes and types of damage that are
considered in the new risk management approach. Given its moderate complexity, it is often
implemented via a calculation spreadsheet or software package.
Checklist Approach to Lightning Protection
There is no single, practical technology that can eliminate all of the risk of lightning and its
transients. Hence, 100% prevention of damage cannot be guaranteed. However, a huge reduction
in the risk can be effected via the “six-point protection approach”, a comprehensive checklist
covering the major damage mechanisms. It commences with an effective means to capture,
conduct and then safely dissipate the energy in direct lightning strikes down to ground, and then
continues with clamping and diverting transients that are induced in the electrical systems or
which arrive at the site from external sources (indirect strikes).
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Cause Lightning
of Damage
Direct Indirect
Type of C1 C2 C3 C4
Damage Strike to Strike to ground Strike to Strike to ground
the structure near the structure incoming line near incoming line
Rh Rg Rt = Rh + Rg
D1 Component due to step and touch Component due to touch
Injury of living beings voltages outside the structure voltages transmitted through Risk due to shock of living beings
causing shock to living beings incoming service lines causing
shock to living beings inside
the structure
Rs Rc Rf = Rs + Rc
Component due to mechanical Component due to mechanical
and thermal effects or dangerous and thermal effects or Risk due to fire or physical damage
D2
sparking causing fire or physical dangerous sparking from
Physical destruction
damage incoming service lines (mainly
at the point of entry to the
structure) causing fire or
physical damage.
Rw Rm Re Rl Ro = Rw + Rm + Re + Rl
D3 Component due to overvoltages Component due to Component due to Component due to induced
Failure of electrical and on internal installations and overvoltages on internal overvoltages transmitted overvoltages transmitted Risk due to the failure of electrical
electronic systems incoming services causing failure installations and equipment through incoming lines to the through incoming lines and electronic systems from
of electrical and electronic (induced by the magnetic structure causing failure of causing failure of electrical overvoltages
systems field associated with the electrical and electronic and electronic systems
lightning current) causing systems
failure of electrical and
electronic systems
Rd = Rh + Rs + Rw Ri = Rg + Rc + Rm + Re + Rl R= Rt + Rf + Ro
Total risk
Risk due to direct strikes to the Risk due to indirect strikes to the structure (including direct and indirect strikes to the service due to
structure lines) lightning
R= Rd + Ri
Total risk due to
lightning
Table I. Risk components, their effects and relationships.

In order to minimise equipment damage and costly operational downtime, the following plan
should be implemented:
P1. Capture the direct lightning strike at a preferred point using the appropriate number,
dimensions and type of strike receptors called “air terminals” or “air terminations”;
P2. Conduct the lightning current to ground safely via an appropriate downconductor system to
minimise the danger of side-flashing, conducted currents and magnetic induction;
P3. Dissipate the energy into the ground with minimal rise in ground potential through a low
impedance grounding system;
P4. Eliminate earth loops and differentials by creating an equipotential grounding plane under
transient conditions;
P5. Protect equipment from surges and transients on power lines; and
P6. Protect equipment from surges and transients on data, signal and control lines.
Figure 1 is a schematic representation of a comprehensive protection plan for a typical industrial

facility. The sections that follow address each of the points in the plan in more detail.
Point 1: Capture the lightning strike at a preferred point
One of the key components of any direct-strike protection system is the lightning rod or air
terminal placed on the structure. Two related and equally important aspects that must also be
considered are the: (i) “protection area” provided by each air terminal, and (ii) positioning of the
air terminals on the structure to achieve the desired “interception efficiency” or “protection
level”. Both of these aspects must be taken into account by the lightning protection method used.
In general, the tallest and most exposed points on a site are the most vulnerable to a direct strike.
Regardless of the type of structure or site being protected, the correct installation of air terminals
near these vulnerable points is the key element in Step 1 of the plan. In this way, direct lightning
strikes can be captured to a preferred point and the current carried away from sensitive
394
equipment, minimising the risk of damage to the equipment from the direct force and energy of a
lightning discharge.
Point 2: Conduct the lightning current to ground safely
Once the lightning has been captured to a preferred point, it is necessary to convey the discharge
current safely to ground, and to minimise the conduction of lightning currents on ancillary
conductors as these can carry dangerous lightning energy directly to the equipment within the
structure. This function is achieved via the use of “downconductors”. Two main types of
downconductors are in common use – “conventional” bare downconductors, which are
commonly copper conductors of circular cross-section or of the “flat tape” variety, and “non-
conventional” downconductors that are designed for particular applications and provide
protection by isolation.
Figure 1. Comprehensive six-point protection plan for a typical industrial facility.

Points 3 and 4: Dissipate the energy into the ground and eliminate ground loops and
differentials
Once the energy is conducted to ground level, a low impedance grounding system is essential to
dissipate the lightning energy into the earth mass as effectively as possible. The grounding
systems for dedicated lightning protection terminals, tower footings, electronic equipment rooms
and control centres are critical design elements. The attributes of an ideal grounding arrangement
are as follows:
395
• Each grounding system (lightning, electrical, communications, and equipment room) must
be individually of high integrity, as well as being considered a component of an overall
grounding network. Where separate grounds exist, they must be bonded together, especially
under transient conditions.
• Because lightning is a multiple frequency event, it is the high frequency “impedance” that is
the critical design element, not the DC or power-frequency resistance;
• Ring electrodes are an effective means of reducing the risk of potential gradients across the
facility;
• The lightning protection grounding system should be directly bonded to the facility ring
electrode(s);
• There should be a “single point” connection to the ground network from all equipment
within a facility, i.e., no daisy-chaining. Rather, a star network arrangement should be used;
• The use of “crows foot” radial electrodes for the lightning protection grounding system
allows the lightning energy to diverge as each conductor takes a share of the current. This
can lower the impedance and the voltage gradients, so the dangers posed by “step potential”
are reduced;
• Electrolytically copper-plated steel, galvanised steel or stainless steel electrodes provide a
cost-effective means of grounding for most standard applications. Solid ground plates, steel
grates, safety mats, ground (mesh) grids, custom-designed terminals, braids and bridges are
used in grounding and bonding applications for high-voltage or heavy current environments
such as near industrial furnaces or around electrical substations; and
• “Ground enhancing materials” can be used to reduce the grounding system resistance by
more than 50% at locations where the ground resistivity is high such as in rocky, sandy or
mountainous areas with large particle soil sizes.
Point 5: Protect equipment from surges and transients on power lines
Even if a structure is provided with an effective direct strike protection system, there remains the
risk that over-voltage transients may arrive via external cables. Furthermore, high-energy over-
voltage transients can arise from capacitive and inductive coupling from nearby lightning strikes
in addition to power transients caused by switching and irregular power distribution. Efficient
clamping and filtering of power transients at the point-of-entry of power lines to facilities is
essential to minimise the risk of physical equipment damage, loss of operations and economic
loss.
Space constraints in this paper do not permit a detailed analysis, so only a brief summary can be
provided here of the important issues to consider when selecting suitable surge protection for
power circuits within a facility. Many different types of SPD’s and technology are available on
the market. To enable the selection of effective protection at the best value for money, one needs
to make a selection based on the most important technical performance specifications. Of the
following parameters for selection, the first three are the most critical: (i) Maximum Continuous
Operating Voltage (MCOV), (ii) Clamping voltage, (iii) Surge rating & protection modes, (iv)
Indication & life, (v) Physical & environmental issues and (vi) Standards compliance.
Parameters that are not as important, and can be very misleading are: (vii) Speed of response,
(viii) Energy (Joule) rating, and (ix) Technology.
Point 6: Protect equipment from surges and transients on data, signal and control lines
The protection of land-based telephone, signal and data lines into a facility is an issue requiring a
careful analysis and comprehensive protection. Transients up to 20 kA (8/20µs) injected onto
396
telecommunications and signal lines can damage and destroy sensitive terminal equipment and
lead to facility down time. Protecting data and communications equipment necessitates the same
concepts as used in Point 5, however due to the differing exposure levels, much lower operating
currents and voltages and increased sensitivity of equipment, the parameters of each SPD needs
to be carefully selected. Communications devices are at risk from transients being induced onto
the interconnecting signal lines. The use of surge protection barriers, installed at either end of the
lines, provides cost effective mitigation. The highest risk is posed by communication or signal
lines that enter or exit the building. In such circumstances, protection devices should be installed
at the point of entry or at the equipment termination itself. Internal wiring that extends more than
10-15 m should also be protected. Twisting or shielding of cables provides a level of protection,
however this should not be regarded as sufficient for the sensitive interfaces that characterize
today’s communication devices.
Five parameters must be considered to ensure that surge protection devices for use on data,
signalling or control circuits are effective and do not adversely affect the operation of the circuit,
namely: (i) As a guide, the SPD clamping voltage should be selected to be approximately 20%
higher than peak working voltage of the circuit; (ii) The line current rating of the SPD should be
sufficient to handle the maximum expected signalling current; (iii) The SPD bandwidth should
be sufficient to allow correct operation of the system without adverse attenuation; (iv) The
connection termination, mounting method, number of lines to be protected and other physical
aspects must be considered, and (v) The SPD surge rating should be appropriate for the intended
location. For circuits internal to the building, surge ratings of 1-5 kA are generally sufficient. For
the protection of circuits that connect to exposed lines entering or exiting the facility, 10-20 kA
is recommended. Alternatively, a protocol or standard may be specified that defines the above
parameters.
Conclusions
Direct lightning strikes and over-voltage transients can create major equipment failures and
downtime in industrial facilities. Whilst 100% protection is not practicable, i.e., there is no such
thing as economical “lightning immunity”, using a risk management approach, it is possible to
provide comprehensive protection to a pre-determined level by employing an integrated, six-
point plan approach to the protection of facilities and assets against the deleterious effects of
lightning discharges.
References
[1] DOE, “Energy and Environmental Profile of the U.S. Aluminum Industry” (Energetics, Inc.
for the U.S. Department of Energy, July 1997).
[2] Evans, J. & Kvande, H.,, 2005, “The Role of Technology in the Global Primary Aluminum
Industry Today and in the Future”, JOM, vol. 57, pp. 21-25.
[3] H.A. Øye et al, “Aluminum: Approaching the New Millennium”, JOM, 51 (1999), 29-42.
[4] Insurance Information Institute (New York Press Release, August 1989).
[5] RP News Wires (June 2007).
[6] M.A. Uman, The Lightning Discharge (New York: Academic Press, 1987).
[7] CEI, “IEC 62305-1 Ed. 1.0: Protection against lightning – Part 1: General Principles”
(Geneva, Switzerland, 2006).
[8] CEI, “IEC 62305-2 Ed. 1.0: Protection against lightning – Part 2: Risk Management”
(Geneva, Switzerland, 2006).
397
Magneto-Optical Study of Cobalt Ferrite Nanoparticles
B.L. Scott, C. Radu, D. A. Smith, and Kevin L. Stokes
Department of Physics and Advanced Materials Research Institute

University of New Orleans
New Orleans, LA 70148
Keywords: Magnetic nanoparticles, magneto-optical properties, magnetic oxides
Abstract
We present a magneto-optical study of CoxFe1-xFe2O4 nanoparticles, where 0≤x≤1. The ferrite

nanoparticles were produced using a generic wet-chemical synthesis procedure. Stoichiometric
amounts of Fe2+, Fe3+ and Co2+ salts are dissolved in a non-aqueous polar medium (diethylene
glycol). A coprecipitation reaction with sodium hydroxide produces ferrite nanoparticles with
average diameter of 6 nm. The nanoparticles can be stabilized by tetramethyl ammonium
hydroxide in water, or, alternatively, the nanoparticles can be treated with a hydrophobic capping
ligand with a carboxylic acid or amine head group and suspended in a non-polar organic solvent.
Faraday rotation was measured on nanoparticle samples dried on an amorphous silica substrate.
The magneto-optical spectra show the characteristic features of both Fe3O4 and CoFe2O4 as x
increases as well as evidence of electronic transitions involving both Co2+ and Fe2+. The results
are discussed in terms of the distribution of cations in the crystal lattice.
Introduction
Cobalt ferrite (Co2Fe2O4) and magnetite (Fe3O4) are ferrimagnetic oxides with an inverse spinel
structure. Although the properties of bulk ferrites have been studied extensively1, nanometer-
scale ferrites display interesting magnetic and magneto-optical effects which have yet to be fully
investigated. Among these are quantum confinement of itinerant electrons2, photomagnetic
effects3, and near-field optical interactions4,5. In addition, ferrites have high cubic anisotropy and
high coercivity which makes nanophase ferrites potentially useful for magnetic data storage
applications. Flexible composites containing superparamagnetic nanoparticles may also find
applications in magnetic shielding and flux concentrators. This motivates us to develop a
generic procedure capable of producing a full-range of ferrite samples with controllable magnetic
moments and magneto-optical properties in the visible region.
Several methods have been explored have been explored to synthesize cobalt ferrite
nanoparticles including chemical reactions in water-in-oil emulsions6, sol-gel chemistry7, and
templated assembly8. Here, we modify the coprecipitation method of Caruntu, et.al9, and
exclude the addition of any capping ligand during synthesis. We have produced a series of six
samples of CoxFe1-xFe2O4 nanoparticles, where 0 ≤x ≤1, and studied the structural, magnetic, and
magneto-optical properties of these materials which collectively allow us to qualitatively
determine the composition of the products. Our analysis of the key electronic transitions
responsible for the magneto-optical response leads us to conclude that have one homogeneous
spinel product, for all x, with three type of cations (Co2+, Fe2+, Fe3+) in an octahedral field with
both Co2+ and Fe3+ occupying the tetrahedral sites and not a physical mixture of CoFe2O4 and
Fe3O4.
399
Experiment
CoxFe1-xFe2O4 fine powders were synthesized based on the coprecipitation mentioned above.
Approximately 640 mg of NaOH pellets were dissolved in 40 ml DEG at ~80°C overnight in a
sealed 150 ml bottle. In a separate 125 ml round-bottomed 4-neck flask, y mmol of FeCl2⋅4H2O,
z mmol of CoCl2⋅6H2O (where y + z = 2mmol) and 4 mmol FeCl3⋅6H2O were dissolved in 40 ml
diethylene glycol at room temperature under argon. Table I contains the corresponding values
for all values of x. The warm NaOH/DEG solution was added to the metal chlorides in DEG and
an immediate color change took place. Upon adding NaOH, the reaction flask was slowly heated
to 215°C over 90 minutes and allowed to continue at this temperature for an additional 30
minutes. After 30 minutes, the reaction flask was slowly cooled to room temperature where the
product was centrifuged and collected. Following three methanol washes and subsequent
centrifugation, all products were dried and collected.
Table I. Precursor quantities for cobalt ferrite synthesis

Metal salt amount (mg)
Cobalt mole
CoCl2·6H2O FeCl2·4H2O FeCl3·6H2O
ratio, x
0 0.0 397.0 1081.0
0.2 95.2 317.5 1081.0
0.4 190.4 238.0 1081.0
0.6 285.5 158.5 1081.0
0.8 380.7 79.5 1081.0
1.0 475.9 0.0 1081.0
Structural characterization was performed by x-ray diffraction (XRD), transmission electron

microscopy (TEM), and a vibrating sample magnetometer (VSM). 50 mg of dried powder of
each product was placed in a Vector VSM and the magnetic moment of the total sample was
measured from -10000 G to 10000 G. XRD analysis was carried out on a PANalytical X’Pert
Pro diffractometer, where 20° ≤ 2θ ≤75°. Particle sizes and elemental distribution were obtained
on a JEOL-2010 Supertwin TEM with the aid of energy dispersive x-ray spectroscopy (EDS),
also equipped on the JEOL-2010. Ferrofluids of each mixed ferrite were prepared by suspending
approximately 2 mg of dried powder in 1 mL of 1 M tetramethyl ammonium hydroxide and 2
mL of deionized water. A few drops of this solution (∼50 μL) were placed on silica substrates
and dried overnight at approximately 40°C. Spectral Faraday rotation measurements were made
using the photoelastic modulator technique5,10. The light source was a 100 W halogen lamp with
wavelengths selected by a 0.3 m monochromator and detection was made with a silicon
avalanche photodiode. The films were placed between the poles of an electromagnet with the
magnetization parallel to the optic axis (polar configuration). Magneto-optical spectra were
obtained for the entire sample series from 400-1000 nm under an applied magnetic field of
4000 G.
TEM observations confirm the presence of 5-8 nm particles exclusively for all studied values of
x and EDS analysis confirms the correct Fe/Co ratio for all samples. A representative TEM
image is shown in Figure 1. X-ray diffraction patterns are shown in Figure 2 for the complete
data series. Patterns from all samples index to a spinel-group structure but the type of spinel for
400
each in is indiscernible here as the sizes of the cations in this system are nearly identical. While
all samples are indeed spinels, the pattern for x=0.6 returns much broader peaks with lower
intensities than the rest of the series. Application of the Debye-Scherrer equation to these peaks,
indicate an average grain size ~3 nm, significantly smaller than TEM images imply. If these
features are not due to smaller particles, then they arise from inconsistencies in the crystal lattice
13,14
. Magnetic data is shown in Figure 3 and also returns the expected trends in that saturation
magnetization decreases considerably as x increases. This behavior is as predicted, based on the
superparamagnetic properties of cobalt ferrite nanoparticles smaller than ~20 nm14, and provides
further evidence of the incorporation of Co2+ into the final product. However, we again observe
inconsistencies with the x=0.6 sample as it displays more paramagnetic character than when
x=0.8.
Figure 1. Transmission electron microscope image of Fe3O4 nanoparticles.
Figure 2. X-ray diffraction for cobalt ferrite nanoparticles. x indicates the mole ratio of cobalt in the
compound.
401
Figure 3. Room temperature magnetization of cobalt ferrite nanoparticles.
Analysis of the magneto-optical spectra of thin films of these samples gives us the strongest
insight into the properties of this series. The magneto-optical spectra of Fe3O4 derive primarily
from intervalence charge transfer (IVCT) and intersublattice charge transfer (ISCT) electronic
transitions11,12. As the names suggest, IVCT involves the transfer of an optically excited electron
to a neighboring cation while ISCT refers to the same type of electron transfer but between like
ions on different lattice sites. In CoFe2O4, there are two additional transitions which are
magneto-optically active: that is, the single-ion, crystal field transitions (CF) for tetrahedrally
coordinated cobalt12.
Figure 4. Faraday rotation spectra for the CoxFe1-xFe2O4 nanoparticles. The spectra are offset for clarity; the
value for x on the right hand side is next to the zero for that spectra.
402
For analysis of the electronic transitions in CoxFe1-xFe2O4, we note that the Faraday rotation, θF,
is given by12,
π ⎡ ε ⎤
θ F = Re ⎢ xy ⎥ (1)
λ ⎣⎢ ε xx ⎦⎥
where λ is the vacuum wavelength of the incident light, ε xy is the off-diagonal element of the
dielectric tensor, and ε xx is the diagonal element equal to the index of refraction n . The real
parts of this tensor result from normal dispersion through the medium of interest while the
imaginary parts account for energy lost during propagation and the processes initiated by
absorption such as IVCT, ISCT, and vibronic excitations. As our intention here is not to
quantify any part of the dielectric tensor for these samples, it will suffice to say here that the
magneto-optical spectra discussed presently are the result of both normal dispersion and
absorption.
For the range 400-500 nm, observed Faraday rotation is large indicating the characteristic feature
associated with all ferrites,11-12 an IVCT between A2+ and B3+. This phenomenon occurs as the
result of an octahedral A2+ absorbing a photon and promoting the short-term transfer of an
electron to a neighboring tetrahedral B3+ quickly loses the electron back to A2+ and the process
repeats as more photons are absorbed. When x < 4, this region is dominated by an Fe2+ ↔ Fe3+
transfer that returns a negative Faraday rotation where as the corresponding cobalt transition
returns the opposite orientation above x=4 and has a maximum around 340 nm15. There is also
an ISCT between Fe3+ ions around 475 nm.15 Moving towards the IR (longer wavelengths), a
prominent maximum centered around 550 nm emerges, for 2 ≤x≤ 4, which diminishes as x→1.
Possible causes of this feature will be discussed following the identification of all known
transitions. For x ≥ 4, an inconspicuous shoulder appears next around 625 nm which is attributed
to an IVCT between Co2+ and Fe3+ with both on octahedral sites.16 After 700 nm, the spectra for
x > 4 is indicates almost zero rotation of the plane of polarization while the last four samples in
the series exhibit a very noticeable feature around 750 nm which is due to a CF transition from
the double degenerate ground state of tetrahedrally coordinated Co2+. As we have shown that
Co2+ resides in both tetrahedral and octahedral coordination this series, the options for the
unknown peak around 550 nm must now be discussed. The possible reasons for this feature may
seem to be many but, in fact, may be reduced to but three in the visible region: an ISCT between
two Co2+ ions or a CF from a tetrahedral Fe3+ or octahedral Co2+. Any IVCT between the two
divalent species should occur at energies beyond our range. While Fe3+ is forbidden to undergo
CF transitions12, this mechanism would seem to be entirely possible as for Co2+ as x increases
from 0 as the indecisiveness of cobalt to choose a lattice spot at lower concentrations12 decreases
the symmetry of the cobalt octahedron and thus allows CF transitions from an octahedral site.
We note that the area around 550 nm is a very prominent peak which is most likely not
associated with an octahedral CF transition because these are still dipole forbidden. With all
other sources discarded, we conclude the broad peak around 550 nm must be associated with an
ISCT between two Co2+ ions on different lattice sites. This result is consistent with the rest of our
observations and leads to the conclusion that we have, indeed, formed the correct product by
ratio but the coordination of cobalt is extremely sensitive to concentration 13,14. It seems that
CoxFe1-xFe2O4 undergoes a structural change as x increases where Co2+ prefers the octahedral
site (inverse spinel), almost exclusively, at higher concentrations and a mix of both sites for
lower concentrations.
403
Conclusion
A cheap, simple procedure has been developed here capable of producing fine nanopowders with
tunable saturation magnetizations from 30-50 emu/g by adjusting the Co2+/Fe2+ ratio in ferrite
compounds. Manipulating thus ratio also allows control of the degree and orientaion of Faraday
by a sample. Applying the information gathered from the techniques employed, the target
product has been formed but with its structure dependent on this ratio. We have observed a
tendency for cobalt to migrate to the octahedral positions at higher ratios and occupy both sites at
lower ones which has resulted in the identification of an ISCT between cobalt ions around
550 nm. Magnetic and magnetic-optical measurements have been used in this study to gather
essential information concerning the spatial orientations of cations in this compound; a structural
parameter that is difficult to obtain by other methods.
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404
APPLICATION OF AMIDE-IMPREGNATED FIBER TO SEPARATION

OF PRECIOUS METALS
Hirokazu Narita1, Mikiya Tanaka1, Kazuko Morisaku1, Ken Tamura2, Daisuke Sakamoto3,
Masashi Suzuki3 and Tomomi Nadano3
1
Research Institute for Environmental Management Technology, National Institute of Advanced
Industrial Science and Technology (AIST), 16-1 Onogawa, Tsukuba, Ibaraki 305-8569, Japan
2
Chiba Institute of Technology, 2-17-1 Tsudanuma, Narashino, Chiba 275-8588, Japan
3
Saitama Industrial Technology Center, 3-12-18 Kamiaoki, Kawaguchi, Saitama 333-0844,
Japan
Keywords: Solvent Impregnated Fiber, Adsorption, Separation, Gold, Palladium, Platinum,
Amide Compounds, Hydrochloric Acid
Abstract
The separation of precious metals in a hydrochloric acid solution using a solvent impregnated
fiber (SIF) was investigated. N-disubstituted amide compounds and kapok fibers were used as
the separation reagents and the impregnation support, respectively. We synthesized N,N-di-n-
octyl-lauramide (DOLA), N,N′-dimethyl-N,N′-di-n-octyl-thiodiglycolamide (MOTDGA) and
N,N′-dimethyl-N,N′-di-n-octyl-diglycolamide (MODGA) and then prepared the amide-
impregnated fibers (amide–IF). The adsorption of some precious and base metals (Au(III),
Pd(II), Pt(IV), Rh(III), Fe(III), Cu(II), Ni(II) and Zn(II)) in HCl solutions was batchwise carried
out using the DOLA–IF, MOTDGA–IF and MODGA–IF. The results of the metal adsorption
showed that the selective separation of Au(III), Pd(II) and Pt(IV) can be performed by
successively using the DOLA–IF, MOTDGA–IF and MODGA–IF.
Introduction
Significant amounts of precious metals are present in many kinds of electronic products and
automotive catalysts, and these products are increasing [1, 2]. Thus, it is expected that the
amount of their wastes will significantly increase in the future. Accordingly, improvements in
the recovery techniques for precious metals have received much attention.
The separation and purification of PGM are mainly performed by solvent extraction and/or resin
ion exchange [3, 4]. The solvent extraction (liquid-liquid extraction) is not very effective for low
concentrated metal solutions and the loss of organic compounds into the aqueous phase is often
observed, while the resin ion exchange shows a slow complexation with metal ions and is
expensive. In general, solvent extraction and resin ion exchange are used for the recovery of high
and low concentrations of metal ions, respectively. Besides them, solvent-impregnated resins
(SIR) have been shown to be effective adsorbents for metal removal from aqueous solutions [5,
6]. The SIR method has the properties of both the solvent extraction and ion exchange resin
processes; however, its metal separation is slow.
We have developed a solvent-impregnated fiber (SIF) method as a new hydrometallurgical
process, which is prepared by impregnating lipophilic fibers with a hydrophobic separation
reagent. The SIF method using kapok fibers for the support shows the good recovery of metal
ions at low concentrations with an adsorption rate higher than that of the SIR [7, 8]. Since most
hydrophobic extractants for metal ions can be applied to the SIF, many kinds of metal ions will
be covered by the SIF method based on the appropriate selection of the extractants.
407
Recently, we investigated the solvent extraction of precious metals using amide compounds [9-
16]. They are relatively stable against acids, and their hydrophobicity and metal extractability
can be improved by changing the side chain length and/or introducing additional donor atoms
like sulfur and oxygen. We found that gold, palladium and platinum are selectively separated in
the order of using monoamide, thiodiglycolamide and diglycolamide compounds, respectively
[16].
In this paper, we describe the selective separation of precious metals using the kapok fibers
impregnated with the following three amide compounds: N,N-di-n-octyllauramide (DOLA),
N,N′-dimethyl-N,N′-di-n-octyl-thiodiglycolamide (MOTDGA), and N,N′-dimethyl-N,N′-di-n-
octyl-diglycolamide (MODGA) (Fig. 1).
(A) (B)
n-C8H17 n-C8H17 n-C8H17
N n-C11H23 N N
S
n-C8H17 CH3 CH3
O O O
(C)
n-C8H17 n-C8H17
N N
O
CH3 CH3
O O
Figure 1: Structures of extractants
(A) DOLA (B) MOTDGA (C) MODGA
Experimental
Reagents
The amide extractants were synthesized using a procedure described in our previous paper [18].
The stock solutions of metals were prepared by dissolving the metal chlorides (HAuCl4·3H2O,
PdCl2, H2PtCl4·6H2O and RhCl3·3H2O: Soekawa Chemical Co., Ltd.; CuCl2·2H2O, FeCl3·6H2O,
NiCl2·6H2O and ZnCl2: Wako Pure Chemical Industries, Ltd.) into HCl solutions. All the other
chemicals used in this study were of reagent grade.
Support
A sheet of kapok fiber, Oil Catcher KT-65, purchased from Kakui Co., Ltd., was cut into 0.5
cm×0.5 cm pieces and then used as the SIF support. The kapok fiber has a hollow tubular shape
and mainly consists of cellulose (35%), xylan (22%) and lignin (21.5%) [17]. Its large pores are
said to sorb a large amount of organic solvents [17-19], although the presence of organic solvents
in the space among the fibers and/or on the exterior surface of the fiber cannot be ignored.
Impregnation
Amide-IF was prepared by the following wet method: The amide compounds diluted by n-
dodecane to a given concentration were dissolved in ethanol. The fibers after washing with
ethanol and then dried were contacted with the diluted amide solution in the phase ratio of 50
408
ml/g at 298 K at the shaking rate of 140 spm for 12 hours. The fibers were then removed by
filtration and dried at room temperature for 12 hours. The weight of the amide―n-dodecane in
the SIF was determined by the difference in weight before and after the impregnation. It was
difficult to accurately measure the concentration of the amide diluted by n-dodecane in the SIF.
Therefore, in this paper, we described the amide concentration in n-dodecane that was
determined before the impregnation.
Adsorption and elution
All the adsorptions and elutions were performed by a batchwise operation. Ten ml of the HCl
solution containing mixed metal ions (Au(III), Pd(II), Pt(IV), Rh(III), Fe(III), Cu(II), Ni(II) and
Zn(II), 10-4 M each) and 0.1 g of the amide-IF were placed in a stoppered 50-ml conical flask
and shaken at the rate of 140 spm in a water bath at 298 K for one hour. After shaking, the
aqueous solution was separated by filtration. After the adsorption, the metal ions on the amide-IF
were eluted with a thiourea―1 M HCl solution. The metal concentrations in the aqueous phases
before and after the adsorption, and after the elution, were determined by ICP-AES.
DOLA-IF
Figure 2 shows the adsorption percentages (Ad%) of Au(III), Pd(II), Pt(IV), Rh(III), Fe(III),
Cu(II), Ni(II) and Zn(II) by the DOLA-IF (DOLA―n-dodecane ([DOLA]: 0.5 M): 0.51 g/g-SIF)
as a function of the HCl concentration. The Ad% of Au(III) increases with an increase in the HCl
concentration. At ≥1.5 M HCl, an over 90% adsorption is obtained. In contrast, the other metal
ions are hardly adsorbed, except that the Ad% of Fe(III) drastically increases at 5 M HCl.
Therefore, Au(III) can be selectively absorbed at < 5 M HCl. The dependence of the Ad% of the
metal ions on the HCl concentration is similar to that obtained from the solvent extraction study
of the DOLA-Au(III)-HCl system [12, 13]. This means that the reaction between DOLA and
Au(III) in the DOLA-IF system is almost the same as the solvent extraction system (ion-pair
mechanism by a protonated DOLA molecule: the extracted complex [AuCl4(H·DOLA)DOLA]).
The elution of Au(III) adsorbed to the DOLA-IF was performed using 1 M thiourea―1 M HCl
solution; about 70% of the Au(III) were eluted into the aqueous solution.
100
Au(III)
80 Pd(II)
Pt(IV)
Rh(III)
60 Fe(III)
Ad / %
Cu(II)
40 Zn(II)
Ni(II)
20
0
0.1 1 10
[HCl] / M
Figure 2: Effect of the HCl concentration on the Ad% of the metal ions with the
DOLA-IF. DOLA―n-dodecane ([DOLA]: 0.5 M): 0.51 g/g-SIF.
409
MOTDGA-IF
Following the Au(III) separation, the selective adsorption of Pd(II) was investigated using the
MOTDGA-IF. Figure 3 shows the plot of the Ad% of Pd(II), Pt(IV), Rh(III), Fe(III), Cu(II),
Ni(II) and Zn(II) by the MOTDGA-IF (MOTDGA―n-dodecane ([MOTDGA]: 0.1 M): 0.52 g/g-
SIF) versus the HCl concentration. The Ad% of the metal ions except for Pd(II) are poor at < 5 M
HCl, while the Ad% of Pd(II) attains >90% from the 0.1 to 2 M HCl solutions. The decrease in
the Ad% of Pd(II) with the increasing HCl concentration suggests that the mechanism is
coordinative like the solvent extraction system:
PdCl42- + 2MOTDGA ↔ [PdCl2(MOTDGA)2] + 2Cl- (1)
As described in a previous paper [20], the adsorption rate of Pd(II) in the MOTDGA-IF is much
faster than that in the DHS-IF; DHS is one of the most popular Pd(II) extractants. The elution of
Pd(II) from the MOTDGA-IF was studied using a 0.01 M thiourea―1 M HCl solution. The
adsorbed Pd(II) was readily transferred into the aqueous solution with >95% elution.
100
Pd(II)
80 Pt(IV)
Rh(III)
Fe(III)
60 Cu(II)
Ad / %
Zn(II)
40 Ni(II)
20
0
0.1 1 10
[HCl] / M
MOTDGA-IF. MOTDGA―n-dodecane ([MOTDGA]: 0.1 M): 0.52 g/g-SIF.
MODGA-IF
The MODGA-IF was used for the selective adsorption of Pt(IV) after the Au(III) and Pd(II)
separations with the DOLA-IF and MOTDGA-IF. Figure 4 shows the Ad% of Pt(IV), Rh(III),
Fe(III), Cu(II), Ni(II) and Zn(II) by the MODGA-IF (MODGA―n-dodecane ([MODGA]: 0.5
M): 0.54 g/g-SIF) as a function of the HCl concentration. The high Ad% of Pt(IV) is obtained at
a ≥0.5 M HCl concentration while the Ad% of Fe(III) and Zn(II) depends on the HCl
concentration, and thereby Pt(IV) can be selectively absorbed from a low HCl concentration (<1
M). The separation mechanism seems to be similar to the DOLA-IF system (ion-pair), because of
the increasing Ad% of Pt(IV) with an increase in the HCl concentration. The elution of Pt(IV) is
around 80% using the 0.1 M thiourea―1 M HCl solution.
410
100
Pt(IV)
80 Rh(III)
Fe(III)
Cu(II)
60 Zn(II)
Ad / %
Ni(II)
40
20
0
0.1 1 10
[HCl] / M
MODGA-IF. MODGA―n-dodecane ([MODGA]: 0.5 M): 0.54 g/g-SIF.
Conclusions
We prepared three amide-impregnated fibers (DOLA-IF, MOTDGA-IF and MODGA-IF) and
then used them for the selective adsorption of Au(III), Pd(II) and Pt(IV). The DOLA-IF,
MOTDGA-IF and MODGA-IF showed a high selectivity for gold, palladium and platinum,
respectively. The dependence of the Ad% of the metal ions on the HCl concentration in the three
systems was almost the same as that in the corresponding solvent extraction systems. The elution
of the absorbed metal ions was readily performed using thiourea―HCl solutions. Accordingly,
the successive use of these amide-impregnated fibers can provide an efficient process for
precious metal recovery.
Acknowledgement
This work was financially supported in part by the Industrial Technology Research Grant
Program in ’06 from the New Energy and Industrial Technology Development Organization
(NEDO) of Japan.
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411
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412
EFFECT OF Cr ON THE OXIDATION BEHAVIOR

OF Ti-46Al-2V ALLOY
Daniela Pilone, Ferdinando Felli
Dip. ICMA, Sapienza Università di Roma

Via Eudossiana 18, 00184 Roma, Italy
e-mail daniela.pilone@uniroma1.it
Keywords: Chromium Effect, Intermetallics, Oxidation, Titanium Aluminides
Abstract
Titanium aluminide alloys are already widely used because of excellent mechanical properties,
but are limited to low temperature applications due to insufficient high temperature oxidation
resistance. When these alloys are subjected to oxidation in air the scale is not a protective Al2O3
layer, but a mixture of Al2O3 and TiO2. The oxidation resistance of TiAl intermetallics is known
to be significantly affected by the addition of alloying elements. The oxidation behavior of Ti-
46Al-2V (composition in at. %) was studied and compared with the ones of the same alloy
containing respectively 7, 10 and 14 % Cr. Isothermal tests were conducted in air at 850 and 950
°C. The scale’s morphology and composition were studied by means of SEM/EDS and X-ray
diffraction. From weight gain curves and cross-sectional microscopy after oxidation exposure it
was found that more than 7 at.% of Cr improves the oxidation resistance of the alloy, although it
simultaneously reduces its toughness.
Introduction
Intermetallic alloys may be used in a variety of structural materials applications. Among several
classes of intermetallics gamma titanium-aluminide alloys appear to be the most promising. The
emerging success of gamma Ti-Al alloys is due to their properties which allow weight reduction
in high temperature aerospace industry. For aircraft engine applications, small and efficient
turbines are envisaged. Weight savings in private transportation and automotive engines with a
consequent improvement in fuel consumption is also attractive. In fact the high specific
mechanical properties of titanium aluminide alloys push the development of these materials.
Because of their ordered structure, intermetallics have high mechanical strength both at room and
at high temperature [1,2]. Despite that, TiAl-based alloys cannot be used as single phase alloys
since they have a very low ductility at room temperature. The most interesting alloys are called
near gamma. The presence of a second α2 phase allows control of the microstructure. As far as
mechanical properties are concerned, the addition of ternary elements such as Cr, V and Mn
reduces the grain size with consequent ductility improvement.
To date, various TiAl-based alloys have been developed. Adding transition metals with high
melting temperatures is generally beneficial to increasing the high temperature strength of these
alloys [3-5]. Non-metallic elements such as C and N are effective in increasing their strength
because of both solid solution and precipitation hardening effects.
Titanium aluminide alloys are interesting as lightweight structural materials [6] because of their
excellent mechanical properties, but are limited to low temperature applications due to
insufficient oxidation resistance. Poor oxidation resistance currently limits the use of TiAl above
800 °C. When these alloys are subjected to oxidation in air the scale is not a protective Al2O3
413
layer, but a mixture of Al2O3 and TiO2. The oxidation resistance of TiAl intermetallics is known
to be significantly affected by the addition of ternary elements [7-11]. Improvements in the
oxidation resistance of gamma alloys have been achieved by modifying the alloy compositions,
particularly by the addition of Mo, W and Nb [4,7]. There have been various theories proposed
to account for these improvements, but there is considerable support for the suggestion that the
“doping effect” [10] determines the suppression of TiO2 growth. Many authors have postulated
that in TiO2 formed during oxidation, vacancies play a role in inward oxygen diffusion [12].
When ions with valence +5 or +6, such as Nb and W, are incorporated in the scale, oxygen
vacancies should be reduced and this presumably results in the suppression of TiO2 growth.
Cr addition to TiAl intermetallics may decrease the solubility of interstitial atoms such as
oxygen, due to its high electron to atom ratio. The effect of Cr addition is interesting to explore
since it should enhance alumina scale stabilization [8,13].
Experimental
The alloys used in this work were produced by induction melting under an Ar atmosphere from
pure Ti, Al, V and Cr and the molten metal was cast directly into the rotating mold. The ingots
were homogenized at 1100 °C.
Isothermal oxidation experiments were carried out at 850 and 950 °C in air. The specimens used
in the oxidation tests were polished up to 600 grit SiC papers and cleaned with acetone before
oxidation. The weight of the specimen being oxidized was measured by using a Cahan
microbalance in conjunction with a computer.
In order to perform metallographic examinations, test specimens prior to and after oxidation tests
were ground to a mirror-like surface by SiC papers up to 1200 followed by 0.3 μm alumina.
Metallographic structure, scale morphology and specimen cross sections were inspected by
scanning electron microscope (SEM) and microanalyses were carried out by energy dispersion
spectroscopy (EDS). Reaction products formed during the oxidation were examined by X-ray
diffraction (XRD) and SEM equipped with EDS.
Results
The alloy’s microstructure and composition were identified by SEM/EDS and XRD. Figure 1
shows the typical microstructures resulting from casting and homogenization treatment on
(a) (b)
25 μm 25 μm
Figure 1. Back-scattered SEM image showing the microstructure of Ti-46Al-
2V (a) and Ti-46Al-2V-14Cr (b) alloys.
414
TiAlV and TiAlV-14Cr alloys. The microstructure of the Ti-46Al-2V alloy consists
predominantly of coarse γ grains and a lamellar constituent composed of alternating plates of α2
and γ phases. Vanadium seems to be homogeneously distributed in the alloy. The predominant
phases have been identified by XRD (Figure 2).
Counts
Al Ti3
Al Ti; Al Ti3
Al Ti
100
Al Ti; Al Ti3
Al Ti
Al Ti; Al Ti3
50
Al Ti
Al Ti
Al Ti
0
20 30 40 50 60 70 80 90
Position [°2Theta]
Figure 2. X-ray diffraction pattern of Ti-46Al-2V after casting and

homogenization treatment.
The microstructures of the chromium containing alloys are characterized by the presence of a
light grey phase having the composition of Ti(Cr,Al)2 Laves phase in the Ti-Al-Cr phase
diagram [13]. After casting and homogenization, all the produced alloys were subjected to
oxidation experiments carried out at 850 and 950 °C in an air stream under isothermal
conditions. Figure 3 shows mass gain per unit area of original specimens with oxidation time.
20
TiAl - 7 Cr
18
16 TiAl
14
Weight Gain (mg/cm2)
12
TiAl - 10 Cr
10
8
TiAl - 7 Cr
6
TiAl
4 TiAl - 10Cr
2 TiAl - 14 Cr
0 TiAl - 14 Cr
0 200 400 600 800 1000 1200 1400 1600
Time (minutes)
Figure 3. Weight gain per unit area vs. oxidation time in air at 850 °C (broken line)
and 950 °C (continuous line).
415
It can be observed that the curves have a parabolic shape and that at both test temperatures only
chromium contents higher than 7% enable a reduction of oxidation rates. The figure shows also
that adding 14% Cr to the alloys limits weight gain both at 850 °C and 950°C: at 950°C the
weight gain reaches 1.4 mg/cm2 after 24 hours.
After every oxidation test, specimens were sectioned and the transverse sections were examined
by SEM/EDS. Figure 4 shows the cross-section of a 7% Cr containing alloy. EDS analyses
revealed that the primary scale constituents are alumina and titanium oxide (Fig. 5) and that the
oxide layer is a mixture containing in the inner part, also chromium and vanadium oxides. X-ray
maps in Figure 4 show also that a chromium rich layer was formed just below the oxide scale.
XRD analyses, carried out on the oxide external surface, identified as primary phases αAl2O3 and
TiO2 (Fig.5). SEM analyses on the cross-sections of 14% Cr containing alloy (Fig. 6) showed a
very different behavior during oxidation. Figure 6 highlights that at 950 °C this alloy is able to
form on its surface a thin and adherent alumina scale. X-ray maps show also that a rich
chromium phase is formed in the sub-scale area.
(a) (b) (c)
50 μm 50 μm 50 μm
Figure 4. X-ray maps of Cr (b) and Al (c) of the Ti-46Al-2V-7Cr cross section (a) after
isothermal oxidation at 950 °C for 24 h.
Counts
Ti O2
600
400
Ti O2
Ti O2
200
Ti O2
Ti O2; Al2 O3
Ti O2; Al2 O3
Ti O2
Al2 O3
Ti O2
Al2 O3
Ti O2
Al2 O3
Al2 O3
Ti O2
Al2 O3
Al2 O3
Al2 O3
Al2 O3
Ti O2
Ti O2
Ti O2
Ti O2
Ti O2
Ti O2
0
30 40 50 60 70 80 90
Position [°2Theta]
Figure 5. X-ray diffraction pattern of the oxide scale formed on Ti-46Al-

2V-7Cr after isothermal oxidation at 950 °C.
416
Discussion
The weight gain curves reported in Figure 3 highlight that the oxidation resistance of the studied
alloys was influenced significantly by the addition of chromium. The weight gain of Ti-46Al-2V
with no quaternary element was considerable even after 24 h. As already known in literature the
effect of Cr addition on titanium aluminides depends on its content. The present investigation
demonstrated that Cr concentrations lower than 7%at. have a detrimental effect and seem to
increase the oxidation rate at both tested temperatures. X-ray maps carried out on 7% Cr
containing specimen showed just below the oxide layer a Cr rich phase that was not able to
promote formation and stabilization of a protective Al2O3 layer. EDS analyses revealed that
chromium is oxidized together with titanium and aluminum and that Cr oxide is present in the
scale innermost part. In fact X-ray diffraction, carried out on the scale external surface, did not
detect any chromium oxide, but revealed only the presence of TiO2 and Al2O3, which are the
constituents of the scale external layer (Fig.4). This intermixed scale is not protective and tends
to spall off during cooling.
TiAlV-10Cr showed a superior oxidation resistance, although promising results in terms of
oxidation rate are achieved only by adding 14%at. of Cr to the alloy. The alloy containing 14%
of chromium formed under oxidative conditions a thin, even and adherent alumina layer, which
was able to protect the substrate alloy. X-ray maps reported in figure 6 delineate the alumina
layer and show the formation of a rich chromium phase under the oxide scale. EDS analyses
gave for that phase the composition Ti-36Al-29Cr, which is the Ti(CrAl)2 Laves phase. This
suggests that this phase is able to promote a selective oxidation of aluminum and to stabilize the
alumina scale. It is well known that the Laves-phase based alloys exhibit promising oxidation
resistance at high temperatures, due to the low permeability of this phase to oxygen and to the
good adherence of the oxide layer to the substrate matrix. Despite those interesting results, the
TiAlV-14Cr alloy, characterized by a hardness value of about 380 HV, had a low ductility and
toughness at ambient temperature. On the ground of those results this alloy should be used for
the production of components for high temperature applications, only if an effective ductilizing
element is added to the alloy.
(a) (b) (c)
10 μm 10 μm 10 μm
Figure 6. Back-scattered image (a) and X-ray maps of Al (b) and Cr (c) of the
cross section of Ti-46Al-2V-14Cr after isothermal oxidation at 950 °C.
417
Conclusions
The Ti-46Al-2V alloy does not offer good oxidation stability at elevated temperatures due to the
formation of an intermixed and porous oxide layer. The best oxidation resistance is exhibited by
Ti-46Al-2V-14Cr. During oxidation in air this alloy promoted the formation just below the oxide
scale of a Ti(CrAl)2 layer, which was capable of continuous Al2O3 scale formation.
Unfortunately, the Laves phase was also a major source of alloy brittleness. Therefore, it is
crucial to improve room temperature ductility and toughness of this alloy, possibly by selecting
an appropriate further alloying element.
References
1. S. Djanarthany, J.C. Viala and J. Bouix, “An Overview of Monolithic Titanium Aluminides
based on Ti3Al and TiAl”, Materials Chemistry and Physics, 72 (2001), 301-319.
2. D.M. Dimiduk, “Gamma Titanium Aluminide Alloys – an Assessment within the Competition
of Aerospace Structural Materials”, Materials Science and Engineering, A263 (1999), 281-288.
3. H.Q. Ye, “Recent Developments in Ti3Al and TiAl Intermetallics Research in China”,
Materials Science and Engineering, A263 (1999), 289-295.
4. M. Yamaguchi, H. Inui and K. Ito, “High-Temperature Structural Intermetallics”, Acta

Materialia 48 (2000), 307-322.
5. J.P. Lin et al., “High Temperature Deformation Behaviors of a High Nb Containing TiAl
Alloy”, Intermetallics, 15 (2007), 668-674.
6. J.H. Westbrook and R.L. Fleischer Eds., Structural Application of Intermetallic Compounds
(Chichester, UK: John Wiley & Sons, 2000), 75.
7. B.G. Kim, G.M. Kim and C.J. Kim, “Oxidation Behaviour of TiAl-X (X=Cr, V, Si, Mo or Nb)
Intermetallics at Elevated Temperature”, Scripta Metallurgica et Materialia, 33 (1995), 1117-
1125.
8. T. Narita et al., “Sulfidation Processing and Cr Addition to Improve Oxidation Resistance of

TiAl Intermetallics in Air at 1173 K”, Intermetallics, 8 (2000), 371-379.
9. H.G. Jung and K.Y. Kim, “Effect of Ternary Elements on the Oxidation Behavior of
Aluminized TiAl Alloys”, Oxidation of Metals, 58 (2002), 197-216.
10. M. Yoshihara and Y.W. Kim, “Oxidation Behavior of Gamma Alloys Designed for High
Temperature Applications”, Intermetallics, 13 (2005), 952-958.
11. M.P. Brady et al., “The Oxidation and Protection of Gamma Titanium Aluminides”, JOM, 48
(1996), 46-50.
12. P. Kofstad, “Note on the Defect Structure of Rutile (TiO2)”, Journal of Less Common Metals,
13 (1967), 635-638.
13. G.S. Fo-Rabinovich et al., “Oxidation Resistant Ti-Al-Cr Alloy for Protective Coating
Applications”, Intermetallics, 14 (2006), 189-197.
418
ELASTIC-PLATIC STRESS AND DEFORMATION ANALYSIS OF

ANNULAR PLATES UNDER PRESCRIBED RADIAL LOADING
Ahmed H. Elkholy1 and Abdulazim H. Falah1

1
Kuwait University, Mechanical Engineering Department
P.O. Box 5969, Safat 13060, Kuwait
Keywords: Elastic-Plastic Stress, Annular Plates, Symmetric And Antisymmetric Deformation.
Abstract
A modified form of constitutive equation for an isotropic elastic-plastic deformation of circular

plates subjected to radial tensile loading on the inner surface is introduced. The form takes into
consideration the effect of rotation of various principal axes and material hardening during the
process of continued deformation. Plastic instability analysis of plates is carried out to determine
stresses at the onset of cavity formation. Both symmetric and antisymmetric modes of
deformation are determined. It was found out that the modified form which is derived in this
study leads to deformation stresses which are lower than those obtained when classical plasticity
relations are used, and therefore, are comparable with the results obtained experimentally. It is
found also that deformation is asymmetric with respect to the plate axis and depends not only on
the stress in the current state but also on the prescribed incremental traction ratio and material
properties.
Introduction
The incremental or flow theory of plasticity which formulates relationships between stresses and
strain-increments or their rates appears to be more attractive both from the physical and
mathematical point of view. Yet, this theory, when applied to a certain class of bifurcation
problems, predicts values for the critical stress which are considerably higher than the
experimental values or are unattainable in practice. Therefore, a modified form of constitutive
equation based on the incremental theory of plasticity has been suggested in which the plastic
strain increment is assumed to be proportional to the stress deviator in the final state of
deformation [1].
Formulation of the Finite Deformation Problem
Let us consider an annular plate subjected to a finite uniform tensile load on the inner surface. A
cylindrical polar coordinate system x i whose origin coincides with the center of the plate is
chosen as a reference frame.
The plate is assumed to be in equilibrium under the given load on the inner surface. Therefore,
the equation of equilibrium in the absence of any body forces may be obtained from [2] as:
s ij = 0 (1)
i
where ( ) i denotes covariant differentiation with respect to x i and s ij represents the

contravariant components of the nominal stress. The boundary conditions on the inner and outer
surfaces of the plate are expressed as
419
T i = n js ij = given on ri
(2)
=0 on ro ,
where T i is the traction and n j is the unit normal to the loading surface. A plane stress
distribution is assumed and therefore, the following equilibrium equation is obtained:
dτ11 τ11 − τ 22
+ = 0, (3)
dr r
where τ ij denotes the nominal stresses. The constitutive laws for an isotropic elastic solid are
given in [3] as:
e′ije = τ′ij / 2μ ,
1 − 2ν (4)
e ekk = τ kk ,
2μ(1 + ν )
and eij are the strain components, the primed quantities denote deviatoric components, the
superscript e denotes elastic components and 2μ and ν are the elastic shear modulus and
Poisson’s ratio, respectively.
e
In terms of displacement gradient, the radial strain e11 and tangential strain e e22 may be
expressed as [4]
du
e
e11 = 1,
dr
(5)
u
e e22 = 1 ,
r
and u i is the elastic component of displacement in the x i direction.
Substituting (4) and (5) in the equation of equilibrium (3), an ordinary differential equation is
obtained as,
d 2 u1 1 du1 u1
+ − = 0. (6)
dr 2 r dr r 2
Equation (6) has a solution of the form
k
u 1 = k 1r + 2 (7)
r
where k1 and k 2 are constants to be determined from the boundary conditions. Substituting (5)
and (7) in (4) yields the following expressions for the stress components τ11 and τ 22 :
B
τ11 = A + 2 ,
r
(8)
B
τ 22 = A − 2 ,
r
where
− Tr 2
A = 2 i2
ro − ri
(9)
Tro2 ri2
B=
ro2 − ri2
420
and T is the traction boundary condition at r = ri .
Axisymmetric Incremental Deformation
The equation of equilibrium and boundary conditions for axisymmetric deformation is expressed
as follows:
(s ij + Δs ij ) i = 0
T i + ΔT i = n j (s ij + Δs ij ) = given at r = ri (10)
=0 at r = ro ,
where Δ( ) denotes axisymmetric incremental quantities which are assumed to be small
compared to the corresponding quantities at current state. The effective shear modulus 2μ is
then calculated from [5] as:
2μ
2μ = (11)
1 + 2μΔλ
Equation (11) shows that 2μ depends on the incremental traction ΔT as well as the stresses in
the plate in the current state and therefore, it varies along the plate radius. For a work hardening
material under plastic loading, the factor Δλ is positive and hence, the effective shear modulus
2μ is less than the elastic modulus 2μ .
Asymmetric Incremental Deformation
The radial and tangential stress components in the current state are maximum at the inner surface
of the plate, and gradually decrease towards the outer surface. Therefore, the equivalent stress is
also maximum on the inner surface of the plate and decreases towards the outer surface.
Consequently, the inner part of the plate may undergo plastic deformation while the outer part
may still be elastic. As the traction on the inner surface increases, the plastic zone expands. At
the elastic-plastic interface, the effective stress is equal to the yield stress.
For the asymmetric incremental deformation, we consider the following admissible fields,
δu 1 = αrz K o (αr ) cos mθ
δu 2 = mz K 1 (αr ) sin mθ (12)
δu 3 = r K 1 (αr ) cos mθ
where K j is the modified Bessel function of the second kind and order j, α is a constant and m
is a positive integer.
Applications and Discussion of Results
An isotropic elastic-plastic annular plate, which has a ratio of outside radius ro to inside ri of
2(ro / ri = 2) , and thickness to inner diameter ratio of 0.04 (2c / 2ri = 0.04) , is considered for
analysis. The plate material has a modulus of elasticity of 79 GPa, a yield strength of 238 MPa
and a hardening parameter of 10. The plate is subjected to a tensile traction on the inner surface
during the process of continued deformation.
421
Axisymmetric Solution
During the axisymmetric part of deformation, the increase of the inner plastic zone in the plate,
as the traction on the inner surface increases, is determined from Vos Mises yield criterion.
Yielding occurs first at the inner surface when the traction T reaches the value of 101.91 MPa.
An increase in the value of the traction T causes the plastic zone, which develops initially the
inner surface, to expand. At a traction of 356.70 MPa, the entire plate becomes plastic.
Therefore, for the inner part of the plate which has been stressed beyond the yield point, the
work hardening parameter H as well as the effective shear modulus 2μ must decrease with
increasing traction. With an increase in traction, a large drop in 2μ is found to occur in the
plastic part of the plate. The result is shown in Figure (1) for ΔT / T = 0.01 . However, similar
behaviour is found for other values of ΔT / T . At point in the plate where the deformation is still
elastic, or where the yield stress has just been reached, the value of 2μ remains equal to the
elastic shear molulus as shown in Figure (1).
Figure 1. Effective Shear Modulus (Annular Plates under radial stress on the inner surfaces).
It is found that bifurcation does not occur when m = 0 (m is the number of waves in the
circumferential direction) which corresponds to axisymmetric modes. This leads to the
conclusion that asymmetric modes of bifurcation are most likely to occur. The traction on the
inner surface of the plate at the onset of bifurcation is plotted against n (n is the number of waves
in the radial direction) for constant values of m. The results are shown in Figure (2) which
indicates that bifurcation may occur at m = 1 for small values of n while the body still deforms
422
elastically everywhere. On the other hand, for m = 2 and m = 3 , bifurcation may occur for a
value of traction under which the equivalent stress in a part of the plate exceeds the yield stress.
Figure (2) also indicates that the critical traction decreases (initially) as n increases from zero
(n > 0) until a minimum (limiting) traction is obtained. Therefore, the critical traction increases
with an increase in n.
Figure 2. Critical traction at bifurcation of annular plates under radial stress on inner surfaces.
Acknowledgement
The authors acknowledge with gratitude the support of Kuwait University Research
Administration under Grant No. EM 04/06.
References
1. F. Mollica, K.R. Rajagopal, and A.R. Srinivasa, “On the Modeling of the Bauschinger
Effect,” Int. J. Plasticity, 17 (8) (2001), 1119-1146.
2. K.R. Rajagopal, and A.R. Srinivasa, “Mechanics of the Inelastic Behaviour of Materials –
Part I, Theoretical Underpinnings,” Int. J. Plasticity, 14 (10-11) (1998a), 945-967.
3. K.R. Rajagopal, and A.R. Srinivasa, “Mechanics of the Inelastic Behaviour of Materials –
Part II, Inelastic Response,” Int. J. Plasticity, 14 (10-11) (1998b), 948-995.
4. M.A. Khaleel, H.M. Zbib, and E.A. Nyberg, “Constitutive Modeling of Deformation and
Damage in Superplastic Materials,” Int. J. Plasticity, 17 (?) (2001), 277-296.
5. S. Pycko, and G. Maier, “Shakedown Theorems for Some Classes of Non Associated
Hardening Elastic-Plastic Material Models,” Int. J. Plastcity, 11 (4) (1995), 367-395.
423
INOCULATION OF ALUMINUM ALLOYS WITH NANOSIZED BORIDES

AND MICROSTRUCTURE ANALYSIS
H. E. Calderón1, C. Smith2, O. Menéndez3 and O. M. Suárez1

1
University of Puerto Rico – Mayagüez Campus
PO Box 9040, Mayagüez, P.R. 00681-9040
2
Austin College, 900 N Grande Avenue, Ste. 61486 Sherman, TX 75090
3
Intermediate School José C. Rosario; Bo Mora PO Box 8000, Isabela, P.R. 00662
Keywords: Nanoparticles, Inoculation, Grain Refiner.
Abstract
The effect of MgB2, AlB2, HfB2, and NbB2 nanosized particles on the grain structure and
microhardness of AA6061 and AA7075 aluminum alloys was studied. The metal boride powders
were processed with a vario-planetary ball milling unit to be afterwards mixed with pure
aluminum pellets. The resulting mechanical mixtures were added as inoculant to the
aforementioned alloys. For comparison the alloys were separately treated with a commercial
grain refiner. Changes in grain size were observed: while boride-treated AA7075 presented a
dendritic structure, the boride-inoculated AA6061 alloy exhibited equiaxed grain structure.
Vickers microhardness tests showed that MgB2 and HfB2 were most effective in improving
mechanical strength of these aluminum alloys.
Introduction
Aluminum matrix composites (AMCs) have been found to have many industrial and commercial
applications. Such applications are in manufacturing of lightweight aerospace and marine
structures. It has been shown that one of the techniques to improve mechanical properties of
alloys is by inoculating nanoscaled refinements into the alloy in order to refine grain structure
and increase strength and ductility [1].
The grain refinement is promoted by heterogeneous nucleation, where insoluble impurities (in
this case the diboride particles) are used to create stable nuclei. This process requires that a solid
nucleating agent, or substrate, be wetted by the liquid metal to create sufficient integration of the
nuclei and, thus, favor the catalytic nucleation [2].
Borides are among the compounds generally used as substrate [3]. In order to obtain nanoscaled
diboride refiners, mechanical devices such as ball milling are used to reduce size of
reinforcements. This project entails the development and subsequent characterization of
aluminum alloys AA6061 and AA7075, using magnesium diboride (MgB2), aluminum diboride
(AlB2), hafnium diboride (HfB2), and niobium diboride (NbB2) as reinforcements. The goal is to
refine the grain structure of the aluminum alloys using nanosize diboride particles.
A Fritsch Pulverisette P4TM Vario-Planetary ball milling was used as the primary tool to reduce
the particle size (Figure 1). The ball milling uses a combination of centrifugal force and steel
balls to mechanically pulverize and mix materials. Vials containing the solution to be milled are
set on the planetary disks and programmed to rotate at a fixed transmission ratio. The milling
energy of steel balls is used to pulverize and mechanically alloy the material inside [4].
425
S. Hales and P. Vasquez synthesized nano-crystalline γ-TiAl using mechanical alloying of
elemental powders by planetary ball milling and attrition milling of pre-alloyed powders [4].
Also L. Reyes (2007) used high energy ball milling to develop mechanical alloyed (AlMg)B2.
Her project involved structural analysis of the composite by X-ray diffraction and mechanical
characterization via Vickers microhardness test [5]. Since the technique was proven successful to
produce nanosized particles embedded in pure aluminum pellets, it was selected to synthesize the
mechanical mixture containing nanosized diborides to inoculate the aluminum alloys in the
present study.
Figure 1. Fritsch Pulverisette P4TM Vario-Planetary ball milling
The commercial aluminum alloys selected to be treated with the nanosized diborides were two
wrought ones: AA6061 (a magnesium-containing alloy) and AA7075 (a Zn-Mg-Cu structural
alloy). These alloys are preferred materials for aircraft, marine, and electrical fittings. Its high
strength, ductility, resistance to corrosion, and availability also made it a favorable choice in
lightweight structures.
AlB2, HfB2, NbB2 and MgB2 are the four diborides studied. It is known that at temperatures
higher than 850°C AlB2 is unstable [6]. For this reason, the melting process was carried out at
750°C. A comparison of the effect of the different reinforcements on the composite mechanical
properties was assessed with a Vickers microhardness tester, furbished with a square-based
pyramid indenter [7, 8].
The procedure started with the size reduction of the diboride particles using ball milling. The
thirty-eight steel balls used as a crushing mechanism in the ball milling were divided evenly and
placed into the metal jars so as to create equally weighted masses on each side of the supporting
disk. 2.5g of diboride powder were added into the jars, which were again balanced to ensure
equal distribution of weight and the ball milling was set to run for five hours at 800rpm.
After the particle size reduction, A mechanical mixing process was conduced to mechanically
alloy the reduced particles with 17.5g of pure aluminum pellets (17.5g). This was again set to run
for ten hours at 1000rpm, or until the diboride particles were fully mixed, exhibiting a smooth
metallic luster on the surface of the pellets and steel balls. The final product generally consisted
of slightly less than 20g of Al-diboride, a loss due to cold welding.
The inoculation process was the third and final phase in the fabrication. 30g of both commercial
alloys were melted at 750° C. Then, the 20g of Al-diboride mixture were added in small
426
increments to the liquid alloy, while the melt was stirred constantly. During the process, the
diboride particles remained in solid state and were distributed throughout the melt. After this the
samples were cast and prepared to be polished. Additionally, the commercial alloys were
combined with commercial grain refiner in the same manner using 2.5g of TIBOR (5%Ti and
0.2%B) in place of the refined diboride powder. The procedure is summarized in Figure 2.
Reduce Particle size

Diboride (2.5g)
5hr, 800RPM
Mechanical Mixing
Diboride (2.5g) + Al pellets (17.5g)
Melting Process 8hr,1000RPM Melting Process
750ºC 750ºC
AA7075 (30g) Al-Diboride (20g)
AA7075 (30g)
Inoculation (Al-Diboride) Inoculation (Al-Diboride)
Testing and Characterization
Microstructure Analysis Hardness Test
Figure 2. Flow chart of experimental procedure
The microstructure analysis of the samples was done using a Nikon Epiphot 200 microscope
with 5x, 10x, 20x, 50x, and 100x magnifications. Keller’s reagent was selected to etch the
samples in order to study the grain structure. Additionally, to compare the changes in strength of
the aluminum alloy before and after inoculation, Vickers hardness test was performed on the
surface of the sample using the Buehler Micromet II Digital Microhardness Tester. From each
ingot two samples were studied. In each sample a minimum of five trials of indentations were
performed using a load of 50kg for 15 second on six different areas of the surface.
Results
The microstructures of the samples without nanoparticle inoculation, i.e. the base commercial
alloys, are shown in Figure 3a and 3b. In Figures 4a to 4h it can be observed that boride-
inoculated samples have a smaller grain size than the samples without particles. The grain size
reduction was promoted by the presence of reinforcements on the samples. This behavior was
similar in both AA6061 and AA7075. However, the boride-inoculated AA6061 samples
exhibited an equiaxed grain structure (Figures 4a, 4c, 4e and 4g) while the inoculated samples of
AA7075 shown a more dendritic nature (Figures 4b, 4d, 4f and 4h). Due to the particles size
reduction, it was not possible to detect the nanoscale reinforcements in the samples by mean of
optical microscopy.
(a) AA6061 (b) AA7075

Figure 3. Micrographics of base alloys as casting
427
(a) AA6061 + AlB2 (b) AA7075 + AlB2
(c) AA6061 + NbB2 (d) AA7075 + NbB2
(e) AA6061 + MgB2 (f) AA7075 + MgB2
(g) AA6061 + HfB2 (h) AA7075 + HfB2

Figure 4. Grain structure of boride inoculated samples
In both composites, the samples with AlB2 and MgB2 (Figures 4e to 4h) presented a better grain
reduction effect of those inoculated samples. On the other hand, the commercial refiner was
more effective to reduce the grain size of these alloys (Figure 5a and 5b). In both cases, the
samples containing the commercial refiner revealed an equiaxed structure.
(a) AA6061 + Refiner (b) AA7075 + Refiner

Figure 5. Commercial alloys under the effect of commercial grain refiner
428
Results of microhardness measurements on the AA6061 samples are shown in Figure 6. Samples
without reinforcements (referenced as Cast in the bar plot) revealed a hardness of 29.3Hv. The
hardness value produced by the commercial alloy containing the commercial grain refiner was
the highest one at 39.5Hv, which is a 31.6% increase. The alloy inoculated with MgB2 had a
hardness value of 36.5Hv, increasing the hardness in a 25%. Therefore, this composite showed
hardness greater than the other boride-inoculated composites, followed by the composite
containing HfB2, which exhibited a hardness value of 33.5Hv: that is a 14.5% increase with
respect to the uninoculated alloy.
Figure 7 shows the microhardness values obtained on the AA7075 alloy (61.2Hv). In this case,
the alloy treated with the commercial grain refiner produced a hardness of 59.5Hv, which is a
decrease in hardness. The alloys containing AlB2 and NbB2 exhibit hardness values lowers than
the commercial alloy AA7075 without reinforcements. Nevertheless, the alloys inoculated with
MgB2 and HfB2 presented increments of 16% and 10% respectively.
45 90
36.50 70.74 67.45
38.51
40 80
31.42 33.50 61.21
35 70 59.53
29.61 53.98
29.26
30 60
48.06
25 50
Hv 20 Hv 40
15 30
10 20
5 10
0 0
Cast Ref AlB2 NbB2 MgB2 HfB2 Cast Ref AlB2 NbB2 MgB2 HfB2
Figure 6. Microhardness of AA6061 inoculated with Figure 7. Microhardness of AA7075 inoculated with
different grain refiners different grain refiners
Discussion
Microstructure analyses revealed that the grain structure of the commercial alloys can be
changed by inoculating the alloys with diboride particles. The melting and inoculation processes
were conduced under similar conditions for all samples. For this reason the formation of longer
dendrites in the AA7075 samples was attributed to the lack of potency (as nucleants) of the
added diboride particles. Dendritic solidification has been observed when particle sizes are in the
order of the interdendritic spacing or smaller and when the liquid does not wet the particles. The
particles then are pushed by growing dendrites and are eventually entrapped in the interdendritic
regions [9]. This could be the case in this particular alloy.
While the data for the composites containing MgB2 and HfB2 showed a consistent increase in
hardness compared to the commercial alloy (identified as Cast in Figures 6 and 7) in both
AA6061 and AA7075, the results with AlB2 and NbB2 were more difficult to analyze. Obviously
they did not prove to be effective catalysts for primary Al nucleation, i.e as grain refinement
material. For instance, in AA7075 these diborides shown to decrease the amount of hardness of
the original alloy. This unexpected reduction was attributed to the resulting grain structure of the
alloy (see Figures 4b and 4d).
One must also consider the large data dispersion for hardness measurements, indicated by error
bars in the Figures 6 and 7. Other problem was associated with the mechanical mixing of borides
429
and the pure aluminum, which experienced cold welding around the edges of its container after
the first trail run in the ball milling. Nevertheless, this problem was reduced changing the milling
settings. All those factors may be confounding the actual effect of the nanosized particles in the
grain-refining process.
Conclusions
Nanoscale reinforcements of MgB2 and HfB2 could be used as grain refiners. The
aforementioned diborides showed an improvement in hardness in both AA6061 and AA7075.
The results in hardness are confirmed visually from the photomicrographs of the grain structure.
A more refined grain structure corresponds to a stronger material, and vice versa. Additionally,
these diborides produced hardness values higher than the alloy treated with the commercial
refiner on AA7075 based alloys.
AlB2 and NbB2 were not shown to be strong candidates for grain refinement because they did not
significantly affect hardness or can even slightly lower it. The commercial grain refiner was the
better grain refinement in AA6061, yielding a 31.6% increase in hardness with respect to
untreated alloy. However, in the alloy of AA7075 the commercial grain refiner is not effective to
increase the hardness of the alloy.
Acknowledgments
This material is based upon work supported by the National Science Foundation (NSF) under
awards N° 0351449 (PREM Program) and N° 0552673 (REU Program).
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430
MICROSTRUCTURAL CHARACTERIZATION IN CAST AlMg alloy-SiCp

COMPOSITES
A. García H1, S. Valdez2
1
Instituto de Ciencias Físicas-Universidad Nacional Autónoma de México, Av. Universidad S/N,
Col. Chamilpa, 062210, Cuernavaca, Morelos, México. svaldez@fis.unam.mx
2
Facultad de Química-Universidad Nacional Autónoma de México, Cd. Universitaria, 04510,
México, D.F., México.
Keywords: AlMg SiCp Composite, Microstructure, Mechanical Properties
Abstract
On the present investigation, the microstructural behavior of AlMg 10vol% SiCp composite has
been studied to evaluate the composite phases, stiffener distribution and interation of SiC
particulates with the solid solution phase. The composites were produced by vortex process. In the
vortex process, the metallic matrix Al-8.7 wt% Mg as-cast alloy was added with SiC particulates
mixed into the steel tubes at 1500 rpm. Material characterization was made by means of X-ray
diffraction (DRX) and scanning electron microscopy (SEM). The mechanical properties have been
highly sensible to the composite microstructure and theses are indirectly related to the preparation
route, so processing parameters involved have a great importance. The Vortex Method shows less
porosity with not secondary chemical reaction and homogeneous particles distribution.
Introduction
Engineering interest in aluminum-based metal matrix composites (MMCs) has increase,
owing to their high specif strength and high specific Young`s modolus [1]. The composite in as-
cast state is being used or considered for use in transportation vehicles [2]. In addition, the
MMCs have been considered as excellent candidates to be applied as structural materials in the
aeronautic-aerospace transport, the automotive industry, etc. [3, 4]. The key to their property
improvement lies in the structure, chemistry and the nature of bonding of Al-SiC interfaces.
Alloying elements such as Mg, which segregate at particle-matrix interfaces, have been found to
improve the wettability [5, 6].
Metal-matrix composites are conventionally fabricated using different techniques such as
strained, power metallurgy, squeeze casting, and the mixing of partially solidified alloys with
ceramic materials [7]. Stir casting tends to suffer from non-uniformity in the reinforcement
distribution after solidification. Powder metallurgy is expensive. An inherent difficulty
encountered in the fabrication of SiCp-Al alloy composites is that molten Al alloys normally do
not wet considerably the ceramic reinforcements. It is well-known that the SiC reinforcements
tend to react with Aluminum matrix during processing, leading to the formation of Al2O3, Al4C3
and Si [8, 9] at the interface. Efforts have been directed to prevent the chemical reaction at
interfaces by oxidation of SiC [10, 11], coating of SiC particles [12,13], or alloying of Al matrix
with Mg or Si [14].In addition the interfacial segregation or intermetallic component formation at
the SiC particle interfaces in as-cast composites tend to reduce the mechanical properties. Vortex
method diminishes the cost, to generate a homogenate microstructure and decrease casting
porosity. The present work was focused on the study of the microstructure of an Al-Mg metallic
matrix alloy reinforced with silicon carbide particles (SiCp) by Vortex method. Composite
microstructure was influenced by solidification parameters and vortex method conditions. In
consecuence, mechanical properties were highly sensible to the microstructure changes.
431
Figure 1 Schematic representation of the Vortex Technique apparatus.
The Al-Mg alloy was prepared with comercial aluminium and magnesium elements
(98.5% Al and 99.9% Mg of purity) using a resistance electrical furnace, at 750°C, with a flux
mixture of salts to avoid the contact with the environment and the elements oxidation. Its
composition, Table 1, was analyzed by using an ICP (Inductively Couple Plasma). For
composite manufacture the AlMg matrix alloy and SiCp particles were used.
Table1. Phase composition of AlMg-SiCp composite and AlMg metallic matrix, given in at. %.
Si Fe Cu Mn Mg Zn Ni Ti V Al
AlMg 1.16 0.38 0.02 0.24 9.00 0.02 0.03 0.07 0.01 Bal.
AlMg10%SiCp 10.70 0.41 0.06 0.25 8.71 0.03 0.08 0.02 0.02 Bal.
The AlMg alloy was weighed and loaded into a stainless steel crucible. The inner
diameter and the height of the sainless steel crucible were 8 cm and 10 cm, respectively. AlMg
specimen was remelted to 700ºC under an argon atmosphere to reduce the formation of oxide.
After the alloy was completely molten, the BN-coated stanless steel spindle (the inner cylinder)
was introduced into the melt, and 10% SiC particles volume fraction was incorporated by Vortex
Method at 1150 rpm for 15 minutes. Previous to the particulate addition, the SiCp particles were
preheated 10 min at 550ºC. A schematic diagram of the vortex equipmente is shown in Fig. 1
Microstructural characterization specimens were prepared by standard metallographic
procedures: grinding on SiC metallographic paper from 240 to 1200, polished with alumina (5.0
μm, 1.0 μm and 0.5 μm) finally ultrasonically cleaned and attacked with Keller reagent. The as-
cast microstructure was determined from the etching caracteristics, composition and the
morphology of the phases. The samples were examined using scanning electron microscopy
(SEM) Jeol 5900 equipped with an analyzer of Leica images and energy dispersive X-ray
analyses (EDAX). X-ray diffraction was carried out using a filter of Nickel with CuKα radiation
in Phillips diffractometer operated to 40kV. A tension tests were performed using an INSTRON
at a strain rate of 3 x 10-3 s-1 at room temperature. The tensile samples (25 x 6 x 5mm) were
fabricated following ASTM E8M-03.
432
Figure 2. X-ray pattern show the α-aluminum and magnesium presence on the matrix metallic
Al-Mg alloy and just SiC particles in the composite.
Results
The XRD pattern from the AlMg-SiCp composite manufactured by Vortex Method and
AlMg matrix alloy (Figure 2) shows the diffraction intensity corresponding to the α-aluminum
phase, which is a solid solution rich in aluminum (α-Al) of crystalline structure FCC and the
magnesium presence in low intensity. The X- ray diffraction contributes to the main intensities
(111) and (200) of the α-phase appear to 2θ 38.82º y 44.71º respectively. The new composite
show three principal diffraction intensity to 2θ = 35.7º, 60.0o and 71.8º, which corresponds to
(111), (220) and (311) of SiC particles. In such difractogramas, we can evidently deduce the
crystalline phases from the master alloy and the composite material.
Figure 3 displays the Al-Mg phase diagram with AlMg matrix alloy composition, the
figure 3a shows the microstructure of as-cast AlMg matrix alloy, which is formed by Al-Mg
solid solution (SS) rich in aluminum with columnar dendritic structure. Microstructures are
formed at moving solid liquid interfaces. In the case of dendritic structures, the morphology is
influenced by the presence of an anisotropic surface energy. The dendritic microstructure is the
most common microstructure found during the solidification of metals and their alloys.
Depending on the dendrites morphology, whether columnar or equiaxed, resulting materials
properties will be different. The structure is called columnar if the growth is preferentially
oriented in a direction close to the heat flux, whereas equiaxed grains are growing in all space
directions, leading to a material with more isotropic macroscopic mechanical properties and a
more homogeneous composition field than with columnar microstructure.
Composite material microstructure shows an equiaxed grain, due to the equiaxed grain
structure is determined by the existence of substrates in the melt that can act as nucleation sites,
in this case, the SiCp particles provide numerous substrates in the melt. Figure 4 shows the
composite microstructure characteristic under as-cast condition with an EDAX spectrum from a
spot between solid solution phase and SiC particles, evidently it suggest the absence of Al2O3,
whose presence has been reported by Mitra et al. [5]. Mitra et. all [5] have reported the presence
433
of Al2O3, Al4C3 and Si phases formed by chemical reaction between Al matrix and SiC particles,
during processing. However, in case of AlMg-SiCp manufactured with Vortex Method a second
reaction was not observed.
Table 2. Phase chemical analysis obtained from the AlMg-SiCp composite.
Elements
Phase
Al Mg Si C
SSAlMg 92.72 7.28 -- --
SSAlMg + SiC 54.56 7.12 17.42 21.20
SiC 52.78 43.23
Table 2 shows the phase chemical analysis obtained from the AlMg-SiCp composite. It is
clear that Magnesium has been entrapped into Aluminum solid solution. In addition, a secondary
chemical reaction product was not observed.
Figure 3 Al-Mg matrix alloy phase diagram and, 3a shows the Al-Mg microstructure
constituted by solid solution rich in aluminum with columnar dendritic structure.
A homogenous microstructure can be observed avoiding particle agglomeration which
has happened in advanced composite manufacture [15]. Solidification process tends to push the
SiC particles into the areas near dendrite grain boundary, which contributes to SiC particles
agglomeration. Solidification influence on particle distribution and it depends if SiC particles act
as solidification nuclei or SiC particles are rejected towards interdendritic region, being in
significant microstructural differences. With Vortex Method the SiCp particle distribution was
homogeneous and the agglomerates were not seen in the composites samples.
434
Figure 4 AlMg-SiCp composite microstructure. Al-Mg Solid solution with particles of SiC
distributed uniformly and EDAX insert pattern result show the elements in the composite.
SiC particles are homogenously distributed in α-aluminum matrix and boundary grains
(fig. 4). Homogenous distribution is essential to obtain better mechanical properties [16]. Many
composite materials are used by their high-specific elastic modulus, high-specific strength and
good wear resistance, in addition the MMCs has been considered as potential lightweight and
high-performance materials to be used in aerospacecraft, aircraft and engine parts in automobiles
[17, 18].
The present tensile test results (Table 3) clearly indicate that the strength and ductility
from composite samples increase as compared to AlMg matrix unreinforced alloy, in agreement
with P. Poddar et. al. [19].
Table 3 Ultimate tensile stress for Al-Mg matrix alloy and Al-Mg-SiCp composite.
YTS (MPa) UTS (MPa)
Matrix 120 250
Composite 145 290
Conclusions
The advantages of the Vortex Method casting used in this work are: reduced porosity
with not secondary chemical reactions and particles distributed homogeneously compared with a
composite manufactured conventionally. Basically, molten metal is delivered via refractory
feeder tip directly into the steel crucible with SiCp preheated, where it solidifies and eliminate
solidification defects.
i. Vórtex Method allows obtaining a composite with less 5% porosity.
ii. Microstructural examination of composites produced under optimum condition mentioned
above shows that distribution of particle reinforcement is homogeneous and products for
secondary chemical reactions on the SiCp/matrix interface were not observed.
iii. Al-Mg + SiCp composite show an Al-Mg solid solution rich in aluminum and film aluminum
oxide were not observed.
Thus a Vortex technique is an excellent method to obtain composites with a homogeneous
microstructure which allows us to obtain optimal mechanical properties.
435
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AUTHOR INDEX
Paper Selections
Elmustafa, A................................................ 185
A Erdogan, R................................................... 275
Aguilar, J. .................................................... 289
Allison, J........................................................ 15
Alterach, M.................................................. 205
Amerio, O. ................................................... 205 F
Ares, A......................................................... 205 Falah, A.H. .................................................. 419
Favilla, P. .................................................... 205
Felli, F. ........................................................ 413
Ferreira, P. ................................................... 257
B Fujimatsu, T. ............................................... 243
Bauer, R....................................................... 283 Fukumoto, S. ............................................... 243
Baxi, J. ......................................................... 211
Behrens, B. .................................................. 129
Bergmann, S. ............................................... 137
Biermann, D. ............................................... 137 G
Blicharski, M. ................................................ 33 Gallagher, M. ................................................ 55
Buenavista, S. .............................................. 289 Gao, Y. .......................................................... 91
García, A. .................................................... 431
Ghiban, B. ................................................... 193
Goud, P........................................................ 379
C Greenberg, B. .............................................. 165
Calderón, H.E. ............................................. 425 Grunspan, J.................................................. 359
Caron, P. ...................................................... 171 Guo, S............................................................ 85
Celik, O........................................................ 251
Chang, S. ............................................. 247, 267
Chen, Y........................................................ 339
Chen, Z. ....................................................... 385 H
Cimenoglu, H. ............................................. 251 Hamilton, C. .................................................. 33
Cochran, J. ................................................... 177 Han, Q. ........................................................ 339
Çorlu, B. .............................................. 275, 319 Hasan, M. .............................................. 21, 385
Cortés, V...................................................... 289 Hashimoto, K. ............................................. 243
Cu, J. .............................................................. 85 He, J............................................................... 97
Hou, C. .......................................................... 49
D I
D'Alessandro, F. .......................................... 391
Davies, P...................................................... 333 Idenyi, N.............................................. 307, 313
De Cooman, B. ............................................ 247 Inel, C. ......................................................... 319
de Freitas, M.................................................. 27 Ivanov, M. ................................................... 165
Deka, S. ....................................................... 373
Diologent, F................................................. 171
Domínguez, M............................................. 289 J
Dominguez, S. ............................................. 289 Jiang, T. ....................................................... 149
Dou, Z............................................................ 97 Jolly, M. .......................................................... 9
Dündar, M............................................ 275, 319 Joy, P.A. ...................................................... 373
Dursun, A. ........................................... 275, 319 Jyoth, S. ....................................................... 379
Dymek, S. ...................................................... 33
E K
Kalemba, I. .................................................... 33
Egeland, G. .................................................... 79 Kang, J........................................................... 67
Ekuma, C. .................................................... 307 Kar, Y. ......................................................... 211
Elkholy, A.H................................................ 419 Karabelchtchikova, O.................................. 107
Karjalainen, L. ............................................. 257
Kayali, E. ..................................................... 251 O
Kiss, L.......................................................... 115 Ohba, Y. .......................................................... 3
Kitade, S. ......................................................... 3 Ohm, V. ....................................................... 283
Kobayashi, K. ................................................ 61 Okeke, C...................................................... 313
Krimm, R..................................................... 129 Olsen, E. ........................................................ 55
Krishnamoorthy, S. ..................................... 353 Owate, I. ...................................................... 313
Kumar, A. .................................................... 115
Kyröläinen, A. ............................................. 257
P
Park, H......................................................... 247
L Patselov, A. ................................................. 165
Lara, G. ........................................................ 289 Peralta, P. ................................................ 73, 79
Lau, P........................................................... 121 Pilone, D...................................................... 413
Le, Q. ............................................................. 85 Polat, A........................................................ 211
Li, G............................................................. 149 Popa-Simil, L. ............................................. 231
Li, J. ............................................................... 91 Popescu, C................................................... 193
Li, M. ............................................................. 15 Popescu, G................................................... 193
Liang, H....................................................... 211 Powers, M. .................................................. 295
Liang, J. ......................................................... 41 Pradhan, D................................................... 345
Liao, C. .......................................................... 49
Lin, T.Z........................................................ 301
Liu, B. .................................................... 67, 301 Q
Liu, L. ............................................................ 41 Quintino, L. ................................................... 27
Liu, M. ......................................................... 149
Lopez, N. ..................................................... 289
Lv, M. .......................................................... 237
R
Radu, C........................................................ 399
Rajamoorthy, S.K........................................ 353
M Rajasekhara, S. ............................................ 257
Ma, J. ............................................................. 91 Rajkiran ....................................................... 379
Makaraci, M. ............................................... 211 Rashid, R.A.R. ............................................ 379
McClellan, K. .......................................... 73, 79 Reddy, R.G.................................................. 345
McDonald, A. .............................................. 301 Redkin, A.A. ............................................... 365
Menéndez, O. .............................................. 425 Reilly, C. ......................................................... 9
Middlemas, M. ............................................ 177 Reis, L. .......................................................... 27
Miles, M. ....................................................... 55 Rodríguez, X. .............................................. 289
Moldovan, P. ............................................... 193 Rong, Z.......................................................... 67
More, K........................................................ 339 Rosenberger, M. .......................................... 205
Morisaku, K................................................. 407 Russell, M. .................................................. 333
Mueller, S. ................................................... 121
Muntele, C. .................................................. 231
Myers, M. .................................................... 339
S
Sakamoto, D................................................ 407
Santos, T........................................................ 27
N Sato, H......................................................... 199
Nadano, T. ................................................... 407 Schvezov, C................................................. 205
Narita, H. ..................................................... 407 Scott, B.L. ................................................... 399
Nawaz, A. .................................................... 223 Shoda, H. ..................................................... 217
Neife, S. ............................................... 307, 313 Shuryghin, A. P. .......................................... 365
Nelson, T. ...................................................... 55 Sission, Jr., R............................................... 107
Nickel, R...................................................... 121 Smith, C....................................................... 425
Niu, L............................................................. 97 Smith, D.A. ................................................. 399
Song, C. ......................................................... 41
Stokes, K.L. ................................................. 399 Zhang, T. ....................................................... 97
Suárez, O.M................................................. 425 Zhang, Z. ....................................................... 85
Suzuki, M. ................................................... 407 Zhu, H.......................................................... 237
T
Tada, S........................................................... 61
Takai, K. ...................................................... 217
Takasu, I. ......................................................... 3
Tamura, K.................................................... 407
Tan, C. ......................................................... 301
Tanaka, M.................................................... 407
Threadgill, P. ............................................... 333
Tkacheva, O.Y............................................. 365
U
Ucisik, A...................................................... 211
Uddin, S......................................................... 21
Usta, M. ....................................................... 211
V
Valdez, S...................................................... 431
Vazquez, L................................................... 289
Venuturmilli, R............................................ 115
Vilaça, P. ....................................................... 27
Viswanathan, S............................................ 339
Vite, M......................................................... 289
W
Walter, G. .................................................... 115
Wang, L. ........................................................ 41
Wang, T. ...................................................... 385
Warwick, M................................................. 339
Wheeler, K............................................... 73, 79
Wu, Y. ........................................................... 67
Wynne, B..................................................... 333
Y
Yamamoto, A. ............................................. 243
Yang, M....................................................... 237
Yang, Q........................................................ 301
Z
Zhai, Q..................................................... 41, 91
Zhan, S......................................................... 385
Zhang, C. ....................................................... 67
Zhang, J. .................................................. 67, 67
Zhang, R. ....................................................... 15
SUBJECT INDEX
Paper Selections
3
3003 .................................................................................................................................................... 319
8
8006 .................................................................................................................................................... 319
?
?-Titanium-aluminides ....................................................................................................................... 137
A
AA2024-SiC ....................................................................................................................................... 301
AA2024-T851 ...................................................................................................................................... 27
ABAQUS............................................................................................................................................ 185
Actinide ................................................................................................................................................ 73
Additive Manufacture ........................................................................................................................ 333
Adsorption .......................................................................................................................................... 407
Air Entrainment...................................................................................................................................... 9
Al-3Mg-Nb ......................................................................................................................................... 289
Al2O3 Reinforcements....................................................................................................................... 193
Alloy Solidification .............................................................................................................................. 21
Alloying.............................................................................................................................................. 283
Alloying Additions ............................................................................................................................. 283
Alloys ................................................................................................................................................. 289
AlMg SiCp Composite ....................................................................................................................... 431
Alumina Coating ................................................................................................................................ 211
Aluminium-Zinc................................................................................................................................. 307
Aluminum............................................................................................................................................. 33
Aluminum Alloy................................................................................................................................. 295
Aluminum Alloy Matrices ................................................................................................................. 193
Aluminum Casting ............................................................................................................................. 339
Amide Compounds............................................................................................................................. 407
Anistropy .............................................................................................................................................. 15
Annular Plates .................................................................................................................................... 419
Anodes................................................................................................................................................ 359
Artificial Implants .............................................................................................................................. 211
AS-Cast................................................................................................................................................... 3
Austenite............................................................................................................................................. 257
Austenite Grain............................................................................................................................... 3, 243
Austenitic Stainless Steel ................................................................................................................... 251
Automation ......................................................................................................................................... 129
B
Bearing Steel ........................................................................................................................................ 91
Bi-Directional Forging ....................................................................................................................... 121
Bioactivity .......................................................................................................................................... 251
C
Capacitors ........................................................................................................................................... 379
Carburizing Steel................................................................................................................................ 243
Casting.............................................................................................................................................. 9, 67
Casting Technology Development..................................................................................................... 339
Celestite Concentrate.......................................................................................................................... 149
Ceramics ............................................................................................................................................... 73
CFD .................................................................................................................................................... 115
Chromate Conversion Coating........................................................................................................... 295
Chromium Carbide Precipitation ....................................................................................................... 257
Chromium Effect................................................................................................................................ 413
Co-Deposition .................................................................................................................................... 385
Coating ............................................................................................................................................... 237
Compression ......................................................................................................................................... 73
Conductive.......................................................................................................................................... 237
Contact Resistance ............................................................................................................................. 295
Continuous Casting ................................................................................................................................ 3
Continuous Hot Annealing................................................................................................................. 319
Cooling Rate........................................................................................................................................... 3
Core Loss.................................................................................................................................... 247, 267
Corrosion .................................................................................................................................... 307, 313
Cost..................................................................................................................................................... 107
Creep........................................................................................................................................... 171, 185
Creep Transition ................................................................................................................................. 199
D
Damage................................................................................................................................................. 73
Deep Valley ........................................................................................................................................ 165
Deformation........................................................................................................................................ 313
Degassing ........................................................................................................................................... 275
Degradation ........................................................................................................................................ 217
Dendritic Structure ............................................................................................................................... 91
Direct Production ............................................................................................................................... 231
Dislocation.......................................................................................................................................... 217
Dislocation Blocking.......................................................................................................................... 165
Dislocations ........................................................................................................................................ 165
Dissimilar Metal Bonds...................................................................................................................... 339
Dissolution Speed............................................................................................................................... 283
Doping ................................................................................................................................................ 373
Double Decomposition....................................................................................................................... 149
Drilling ............................................................................................................................................... 137
E
Eddy Currents Probe ............................................................................................................................ 27
Efficiency ........................................................................................................................................... 107
Elastic-Plastic Stress .......................................................................................................................... 419
Electric Current Pulse........................................................................................................................... 91
Electrical Conductivity....................................................................................................................... 365
Electrodeposition................................................................................................................................ 345
Embrittlement And Aluminium-Zinc Alloy ...................................................................................... 313
Energy Consumption.......................................................................................................................... 107
Experimental Furnace ........................................................................................................................ 115
F
Films ................................................................................................................................................... 205
Flame Interaction................................................................................................................................ 115
Flash ................................................................................................................................................... 121
Flat Long Pieces ................................................................................................................................. 121
Formability ........................................................................................................................................... 55
Free ..................................................................................................................................................... 359
Friction Stir Welding........................................................................................................ 27, 33, 55, 333
Froude Number....................................................................................................................................... 9
Functionally Graded Material .............................................................................................................. 61
Furnace Modeling............................................................................................................................... 115
G
Gas Carburizing.................................................................................................................................. 107
GeO2................................................................................................................................................... 385
Gold .................................................................................................................................................... 407
Grain Coarsening................................................................................................................................ 243
Grain Growing........................................................................................................................................ 3
Grain Oriented Electrical Steel ............................................................................................................ 49
Grain Refiner ...................................................................................................................................... 425
Grain Size ............................................................................................................................................... 3
Grounding........................................................................................................................................... 391
H
Hard Material ....................................................................................................................................... 61
Heat Affected Zone ............................................................................................................................ 223
High Temperature Deformation......................................................................................................... 199
High-Purity Strontium Carbonate ...................................................................................................... 149
Hot Forging ........................................................................................................................................ 243
Hot Isostatic Pressing (HIPing).......................................................................................................... 301
Hybrid Composites............................................................................................................................. 193
Hydraulic Turbine Blade...................................................................................................................... 67
Hydrochloric Acid.............................................................................................................................. 407
Hydrogen ............................................................................................................................................ 217
I
Impact ................................................................................................................................................... 97
Inoculation.......................................................................................................................................... 425
Intermetallic Compound..................................................................................................................... 137
Intermetallics ...................................................................................................................................... 413
Ionic Liquid ........................................................................................................................................ 345
Irregular Eutectic.................................................................................................................................. 15
L
Lattice Defect ..................................................................................................................................... 217
Lattice Mismatch................................................................................................................................ 171
Life Prediction .................................................................................................................................... 199
Lightning Protection........................................................................................................................... 391
M
Machining Investigations ................................................................................................................... 137
Magnesium Alloys ............................................................................................................................... 85
Magnetic Anisotropy.......................................................................................................................... 267
Magnetic Induction ............................................................................................................................ 267
Magnetic Nanoparticles...................................................................................................................... 399
Magnetic Oxides................................................................................................................................. 399
Magnetic Properties............................................................................................................................ 373
Magneto-Optical Properties ............................................................................................................... 399
Manufacture........................................................................................................................................ 289
MCVD ................................................................................................................................................ 385
Measurement and Control Technology.............................................................................................. 129
Mechanical Properties .................................................................................................................. 33, 431
Melt Quality ....................................................................................................................................... 283
Metal Forming .................................................................................................................................... 129
Microarc Oxidation Method............................................................................................................... 211
Microsegregation.................................................................................................................................. 21
Microstructure .......................................................................................................... 55, 73, 85, 333, 431
Milling ................................................................................................................................................ 137
Mo-Si-B Alloys .................................................................................................................................. 177
Model.................................................................................................................................................. 107
Molar Volume .................................................................................................................................... 365
Molten Electrolytes ............................................................................................................................ 365
N
Nano-Indentation.................................................................................................................................. 79
Nanocrystalline Metal Matrix Composite.......................................................................................... 301
Nanoindentation ................................................................................................................................. 185
Nanomaterials..................................................................................................................................... 231
Nanoparticles...................................................................................................................................... 425
Nitride Reactions................................................................................................................................ 177
Nitriding ............................................................................................................................................. 251
No-Load Heating................................................................................................................................ 165
Non-Oriented Electrical Steel ............................................................................................................ 247
Numerical Method................................................................................................................................ 21
Numerical Simulation .......................................................................................................................... 67
O
Optical Properties ............................................................................................................................... 373
Optimization ....................................................................................................................................... 107
Oscillation Mark..................................................................................................................................... 3
Oxidation .................................................................................................................................... 177, 413
P
Palladium............................................................................................................................................ 407
Parent Metal ....................................................................................................................................... 223
Particle Temperature ............................................................................................................................ 97
Phase Field............................................................................................................................................ 15
Phase Morphology................................................................................................................................ 85
Pile-up................................................................................................................................................. 185
Pipernigrum ........................................................................................................................................ 307
Plasma Spraying ................................................................................................................................... 97
Plastic Deformation............................................................................................................................ 165
Platinum.............................................................................................................................................. 407
Post Weld Heat Treated Metal ........................................................................................................... 223
Potential Relief ................................................................................................................................... 165
Powder Processing ............................................................................................................................. 177
Power .................................................................................................................................................. 359
Precision Forging ............................................................................................................................... 121
Production Process ............................................................................................................................. 137
Properties............................................................................................................................................ 289
Q
Quality Assessment ................................................................................................................................ 9
R
Reactor Fuel ....................................................................................................................................... 231
Reclamation........................................................................................................................................ 353
Recycling............................................................................................................................................ 115
Refining .................................................................................................................................................. 3
Reliability of Transformers ................................................................................................................ 353
Residual Life Extension ..................................................................................................................... 353
Residual Stresses .................................................................................................................................. 97
Revamping.......................................................................................................................................... 359
Reverse Deformation............................................................................................................................ 67
Roasting.............................................................................................................................................. 149
Rods.................................................................................................................................................... 359
S
Salt Bath ............................................................................................................................................. 319
Secondary Recrystallization................................................................................................................. 49
Segregation ........................................................................................................................................... 91
Self-Locking ....................................................................................................................................... 165
Semiconductors .................................................................................................................................. 373
Separation ........................................................................................................................................... 407
Shallow Valley ................................................................................................................................... 165
Si3N4-TiN .......................................................................................................................................... 237
SiC ...................................................................................................................................................... 193
SiO2 .................................................................................................................................................... 385
Six Point Plan ..................................................................................................................................... 391
Slip........................................................................................................................................................ 33
Sol-Gel................................................................................................................................................ 205
Solidification ........................................................................................................................................ 15
Solidification Structure ........................................................................................................................ 41
Solvent Impregnated Fiber ................................................................................................................. 407
Stability of Strain Rate ....................................................................................................................... 199
Stacking Faults ................................................................................................................................... 257
Stainless Steel..................................................................................................................................... 257
Straightening ...................................................................................................................................... 129
Super-Grade........................................................................................................................................ 231
Superalloy........................................................................................................................................... 171
Surface Plasticity.................................................................................................................................. 79
Surge and Transient Protection .......................................................................................................... 391
Symmetric And Antisymmetric Deformation.................................................................................... 419
Synthesis............................................................................................................................................... 61
T
Tantalum............................................................................................................................................. 379
TCS Steel.............................................................................................................................................. 41
Telfera Occidentalis ........................................................................................................................... 307
Temperature.......................................................................................................................................... 73
Texture Factor .................................................................................................................................... 267
Thermal Desorption Analysis ............................................................................................................ 217
Thermal Model ..................................................................................................................................... 33
Ti-6Al-4V ........................................................................................................................................... 205
Ti-Al Alloy ......................................................................................................................................... 345
Tin......................................................................................................................................................... 49
Titanium ............................................................................................................................................. 333
Titanium Aluminides.......................................................................................................................... 413
Titanium Carbide.................................................................................................................................. 61
Titanium Oxide................................................................................................................................... 205
Titanium Silicon Carbide ..................................................................................................................... 61
Traveling Zone Sintering ..................................................................................................................... 61
Twin Roll Casting ...................................................................................................................... 275, 319
U
UHSS .................................................................................................................................................... 55
Ultrasonic Treatment............................................................................................................................ 85
Ultrasonic Vibration ............................................................................................................................. 41
V
Vacancy .............................................................................................................................................. 217
Vernonia Amegdalina ........................................................................................................................ 307
W
Wear ................................................................................................................................................... 251
Y
Yield Event........................................................................................................................................... 79
Yield Strength..................................................................................................................................... 247
Z
Zirconium Nitride................................................................................................................................. 79

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2008

137th Annual Meeting & Exhibition

AM08 Coll.Proc. Book Vol III_ins1 1 1/28/2008 1:49:21 PM

Other TMS 2008 Annual Meeting Publications:

AM08 Coll.Proc. Book Vol III_ins3 3 1/28/2008 1:49:28 PM

About This Volume

AM08 Coll.Proc. Book Vol III_ins2 2 1/28/2008 1:49:25 PM

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Printed in the United States of America

ISBN Number 978-0-87339-718-6

Authorization to photocopy for internal or personal use

For those organizations that have been granted a photocopy

Please direct republication or special copying permission

AM08 Coll.Proc. Book Vol III_ins4 4 1/28/2008 1:49:28 PM

General Abstracts: Materials Processing and

Quality Assessment of Casting Filling Method ....................................................9

Phase Field Simulation of Irregular Eutectic Solidification................................15

A Numerical Scheme for Solving Microsegregation for

Advances in NDT Techniques for Friction Stir Welding Joints

A Thermal Model of Friction Stir Welding Applied to

Effect of Ultrasonic Vibration on Solidification Structure of

Effect of Tin Content on the Magnetic Properties and

Integrated Fabrication of Functionally Graded Ti3SiC2-TiC

Study on Deformation of Large-Scale Hydraulic Turbine

Multi-Temperature Uniaxial Compression Testing of Sintered

A Nano-Indentation Study of Surface Plasticity in Zirconium

Influence of High-Intensity Ultrasonic Treatment on the Phase

Effect of Electric Current Pulse on Solidification Structure of

A Calculation Model for Thermal Performance during Particle

Optimization of Gas Carburizing Process in Batch Furnaces

Experimental and Numerical Study of Flame Load Heat

Controlled Sheet Metal Straightening...............................................................129

Drilling and Milling of Intermetallic γ-TiAl.....................................................137

Preparation of High-Purity Strontium Carbonate from

Subject Index ....................................................................................................443

General Abstracts: Structural Materials Division

Effect of the γ/γ' Lattice Mismatch on the Creep Behaviour at

Oxidation Behavior of Mo-Si-B Alloys Produced by Reaction

Pile-up/Sink-in in Nanoindentation Rate Sensitive Creeping

Researches Concerning the Structural Characterization of

Quantitative Evaluation of Creep Curve of Alloy-Type and

Properties of Titanium Oxide Films Deposited by the Sol-Gel ........................205

Microstructural and Mechanical Properties of Alumina

Brittle Crack Susceptibility of Low Temperature Separator

Direct Production of Super-Grade Materials in Nano-Particle

Synthesis and Microstructure of Si3N4-TiN nanocomposites..........................237

Austenite Grain Stability of Low-Manganese, High-

Development of High Strength Non-Oriented Electrical Steels .......................247

Characteristics of Hybrid Solid Solution Layer Formed on the

Microstructure Evolution in Nano/Sub-Micron AISI 301

Effects of Mo and Ni on Textures and Magnetic Properties in

Subject Index ....................................................................................................443

General Abstracts: Light Metals Division

Methods of Manganese Alloying to Aluminum and Their

Manufacture and Characterization of Al-3Mg-Nb............................................289

An Investigation of Hexavalent-Free Chromate Conversion

Fabrication of AA2024-SiC Nanocrystalline Metal Matrix

Comparative Analysis of the Influence of Inhibitor

The Impact of Corrosion on the Deformation Behaviour of Al-

Effects of Different Annealing Processes on Microstructural

Bonding of Steel Inserts during Aluminum Casting .........................................339

Low Temperature Electrochemical Synthesis of Ti-Al Alloys

Residual Life Extension of Aged Transformers in Aluminium