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Materials Today: Proceedings 00 (2018) 0000–0000 www.materialstoday.com/proceedings

AMPCO-2017

Studies on the Crystallite Growth during Heat Treatment in Fe-

25% Y2O3 ODS Steel Produced by Mechanical Alloying
Sunil Kumar Rajulapati1a*, Avinash Deepak Saggurthi2a, Akeshwar Singh Yadav3a, Sai
Ramudu Meka4a.
a
Metallurgical and Materials Engineering Department, IIT, Roorkee 247667, India

Abstract

The main problem in characterizing the commercial ODS steel to understand fundamentally the underlying
microstructural changes is associated with the very small volume fraction of Y 2O3. In order to overcome this difficulty, in this
study we have ball milled the pure Iron powder with 25wt.% Y2O3 powder and X-ray diffraction is used as a major
characterization tool to trace the microstructural changes as a function of processing steps such as ball milling, after
homogenization at 1200oC and after the following heat treatment at 1060oC. No significant change in the lattice parameter of
ferrite matrix has been observed after ball milling suggesting that there is no dissolution of Y 2O3 into ferrite matrix during ball
milling. During heat treatment at 1200oC the micro strain of the ferrite matrix has decreased with simultaneous increase in
crystallite size and the same phenomena was observed for Y2O3 as well. Heat treatment at 1060oC has refined the crystallite size
of only ferrite matrix suggesting that at 1060oC ferrite crystallites grow but not the Y2O3 crystallites. Finer crystallite size of
ferrite after 1060oC heat treatment, as compared to that of 1200oC heat treatment, has been attributed to the relatively smaller
austenite grain size at 1060oC.

© 2018 Elsevier Ltd. All rights reserved.

Selection and/or Peer-review under responsibility of Advances in Materials & Processing: Challenges & Opportunities (AMPCO-2017).

Keywords: ODS Steels: Mechanical Alloying: X-Ray Diffraction: Heat Treatment

1. Introduction

Oxide Dispersion Strengthened (ODS) steels are the promising candidate materials for the structural
applications in Nuclear reactors[1,2]. ODS steels exhibit excellent high temperature tensile and creep properties,
swelling resistance, irradiation resistance, corrosion and oxidation resistance [3–6]. The main alloying elements in
Ferritic/Martensitic ODS steels are Cr, W, Ti and C while Y 2O3 are dispersion strengthening particles. Cr provides
corrosion and oxidation resistance, W provide solid solution strengthening, addition of C is helpful in phase
transformation, Ti combines with Y2O3 and forms complex oxides (Y2Ti2O7 or Y2TiO5) which provide high
temperature tensile and creep strength[7,8]. In addition to high temperature strength, oxide particles act as a sink
sites for point defects thus improving swelling resistance[9,10].

2214-7853 © 2018 Elsevier Ltd. All rights reserved.

Selection and/or Peer-review under responsibility of Advances in Materials & Processing: Challenges & Opportunities (AMPCO-2017).
2 Author name / Materials Today: Proceedings 00 (2018) 0000–0000

ODS steels with 0.35 wt% Y2O3 as dispersant are the most commonly produced ODS steels and addition of
Y2O3 content was limited to 0.5 wt% due to the decrease in ductility at high yttria levels [11,12]. Several studies are
available on the mechanical alloying of ODS steels where changes occurring due to change in atmosphere, speed,
time and types of mills have been addressed[13–15]. The fundamental studies on the microstructural changes
occurring in steel powders during mechanical alloying and post mechanical alloying treatments (heat treatments or
consolidation by various routes) with respect to Y 2O3 are very limited. The main problem in characterizing in this
regard is the small volume fractions of Y2O3 in general ODS steels. The main motivation of the present study is to
understand the crystallite changes occurring in Fe and yttria during mechanical alloying and subsequent heat
treatment at high temperatures (1200 oC and 1060oC). These temperatures were selected since they are the
consolidation temperature (1200oC) and heat treatment temperature (1060oC) of commercial ODS (9Cr)
Ferritic/Martensitic steel. In the present study, Fe with 25 wt% Y 2O3 was mechanically alloyed followed with heat
treatments of MA powders. X-Ray diffraction is used as a major characterizing tool to determine microstructural
changes during mechanical alloying and heat treatment. The peak shifts in XRD profile are the good indications for
lattice parameter variation. The study of XRD line profile analysis reveals information on the kind of deformation
the material has undergone. A perfect crystal would have its extent in all directions up to infinity which would give
a peak at exactly Bragg angle. But the mechanically deformed materials will have finite crystallite size, this leads to
the broadening of the diffraction peak. The two factors which result in peak broadening are crystallite size and micro
strain.

2. Experimental Procedure:

2.1 Materials:

Elemental Fe with average particle size of -325 mesh (~45μm) and 99.95 purity procured from NMDC,
Hyderabad and Y2O3 with average particle size of ~4μm and 99.995 purity procured from Alfa Aeser, Hyderabad
were used as raw materials.

2.2 Mechanical Alloying:

Elemental powders of Fe and Y2O3 were mixed using mortar pestle for 10 min to obtain a nominal
composition of Fe-25wt% Y2O3. The powder mix was mechanically alloyed in a Retsch PM100 Planetary Mill
having WC-Co vessel as grinding unit and WC balls of 5mm dia as grinding media. MA was carried out for 10
hours with ball to powder ratio of 10:1 at 200rpm.

2.3 Heat Treatment:

The MA powders of Fe-25 Y2O3 were heated to 1200oC at a heating rate of 15oC per min with flowing H2
gas, which prevents oxidation, holding time given was 30 min and cooled down to room temperature in air. In the
second heat treatment, powders treated at 1200 oC were reheated to 1060oC and cooled to room temperature in air.
The heating rate and holding time maintained was same as previous treatment.

2.4 X-Ray Diffraction Analysis:

Standard Si powder ~20 %Vol was added as an internal standard in as milled (AM) and heat treated at
1200oC (1200) powder samples. Si powder was well mixed with the alloy powder samples using mortar pestle for
10 min and then in an ultrasonic bath for 15min with ethanol as solvent. The powder was allowed to dry and placed
in the cavity of glass slide for XRD analysis. The excess powder was removed using thin glass slide.

XRD measurements were carried out in a Rigaku X-ray Diffractometer using CoKα radiation with a wave
length of 1.78901 A0. Co target is preferred over Cu in order to avoid fluorescence. The powders were scanned in a
2θ range of 30-110o, speed 1o/min and step size of 0.02o. PANalytical Xpert High Score was used to analyse the
powder diffraction data to identify the phases, diffraction angles (2θ) and d-spacing values. To determine lattice
 Author name / Materials Today: Proceedings 00 (2018) 0000–0000 3

parameter, Nelson-Riley ( ) extrapolation function was used. Si was added as an internal standard to
determine instrumental error (shift). The diffraction angles (2θ) of Si were calculate theoretically using Bragg’s
equation (λ = 2dSinθ), having known values of λ (Co Kα1), a (lattice parameter of Si) and (hkl) values, we can
calculate 2θ values. The peak shift of experimentally recorded 2θ values of standard Si powder mixed in AM and
1200 samples with respect to theoretical 2θ values were determined. The error at each diffraction angles (Y-axis)
were plotted against 2θ (X-axis) and the data points were fit to 2 nd order polynomial fitting. The instrumental peak
shift of Fe and yttria were determined by the corresponding error values on polynomial fit. The peak shift at each 2θ
value of ferrite and yttria were adjusted and accurate diffraction angle (2θ) was determined and used in further
procedure to determine precise lattice parameter.
Crystallite size and Micro strain were determined by using Williamson-Hall method mentioned in
Equations 3 and 4. The experimental broadening (βo) observed in diffraction profile is the combination of various
components like instrumental (βi), crystallite size (βc) and micro strain (βst). It is very important to correct
instrumental broadening in order to evaluate accurate crystallite size and strain. The equation 4, resembles equation
of straight line with 4sinθ as x-variable and βrCosθ as y-variable where, η is slope and is y-intercept.
(1)
(2)
Where,
– Experimental Broadening
– Instrumental Broadening
– Broadening due to crystallite size
– Broadening due to micro strain
– Net broadening
(3)
(4)
Where,
L- Crystallite Size and η- micro strain.
Standard Si powder having a negligible micro strain and very high crystallites was used to determine
instrumental broadening. XRD measurements were recorded for standard Si powder and the broadening at each
diffraction (2θ) angle was determined. The Kα1 and Kα2 components were deconvoluted using Pseudo-voigt
function and the peak broadening of Kα1 was considered. Peak broadening values of Kα1 (Y-axis) were against 2θ
(X-axis) values and the data points were fit to 3rd degree polynomial fitting. The instrumental broadening of ferrite
and yttria in AM, 1200 and 1060 samples were determined by the corresponding Y-value of the polynomial fit.
Having determined instrumental broadening (βi), Now net broadening was determined by the expression,
.

3. Results and Discussion

3.1 XRD Phase Analysis

The powder samples are referred as AM- as milled, 1200 – heat treated at 1200oC and 1060 – heat treated at
1060oC. The XRD profiles were analysed using PANalytical Xpert High Score plus software to determine phases
which are shown in Fig. 1. XRD profiles of AM, 1200 and 1060 showed strong reflections of Fe (JCPDS Ref code
00-006-0696) and yttria (JCPDS Ref code 00-041-1105). Si is added as internal standard in AM and 1200 conditions
while 1060 was without Si addition and thus, Si reflections were observed in AM and 1200. It can be observed that
the diffraction profiles of Fe in AM are less in intensity and broader compared to 1200 and 1060. Yttria peaks also
showed similar profile as that of Fe. In 1200 and 1060 profiles, Fe and yttria peaks appeared to be very sharp,
indicating the growth in the crystals. Yttria peaks having very low intensities were not indexed in case of 1200 and
1060 samples. It can be observed that some of the lower intensity peaks (relative intensity <10) of yttria had
disappeared in AM condition.
4 Author name / Materials Today: Proceedings 00 (2018) 0000–0000

Fig. 1: XRD profiles of (a) as milled (AM) and heat treated at 1200 oC (1200) with Si addition and (b) heat treated at 1060oC (1060).
Mechanical alloying is a mechanism where the powder particles are flattened, cold welded, fractured and
rewelded repeatedly. There are three different components in mechanical alloying; ductile - ductile components,
ductile – brittle components and brittle – brittle components[16]. In mechanical alloying there is a possibility to
form an alloy of insoluble components due to high deformation and repeated welding and fragmentation of powder
particles. The alloy formation is easier in case of ductile – ductile component system where repeated welding and
fracture process form composite lamellar structure of constituent elements which further form an alloy. Mechanical
alloying of typical ODS steel containing Fe, Cr and other alloying elements with yttria is an example of this
type[17]. Present alloy system (ODS steels) fall in ductile – brittle component system where in the initial stages of
milling, ductile Fe gets flattened while brittle yttria get fragmented. In the later stages of milling yttria get trapped
and further dispersed uniformly in the Fe matrix. There is no indication of iron oxides or Fe-Y intermetallic phases
in XRD profile of AM sample (Fig. 1a) which would be possible if yttria is soluble and alloyed with Fe during
mechanical alloying.

3.2 Lattice Parameter variation

Si was added as internal standard to determine instrumental peak shifts. Polynomial fit of error Vs 2θ in case of
AM condition is shown in Fig. 2. The instrumental shift of Fe and Y2O3 was calculated by corresponding value on
polynomial fit. Lattice parameter was calculated using Nelson-Riley ( ) extrapolation function. The
values of Lattice parameter of ferrite and yttria calculated by Nelson-Riley function are shown Table-1.
The lattice parameter of pure iron is 2.8664Ao and yttria is 10.6041Ao. A slight increase in lattice parameter of
Fe was observed after milling Table-1. Some researchers worked on the mechanical milling of pure Fe also found
increase of lattice parameter of pure Fe with increased milling. This can be attributed to increased surface energy
and defect density during milling which causes cell expansion in Fe [18,19]. There is no significant change in lattice
parameter of Fe after heat treatment. There is no significant variation of lattice parameter of yttria during mechanical
alloying (AM) and after heat treatment (Table-1). From the lattice parameter values it is evident that there is no
significant influence of yttria on the lattice parameter of Fe during mechanical alloying and heat treatment. Lattice
parameter values of 1060 samples were not mentioned because it was assumed that there would be no change in
lattice parameter of Fe since both the heat treatment temperatures (1200 oC and 1060oC) are above the austenitizing
(900oC) temperature of Fe and there was no effect of heat treatment on lattice parameter of Fe.
 Author name / Materials Today: Proceedings 00 (2018) 0000–0000 5

Fig. 2: Polynomial fit of Si peak position error in AM condition for instrumental peak shift correction.

Table-1: Lattice parameter values of pure Fe, pure Y2O3, Fe and Y2O3 in AM and 1200 conditions.
Element Pure (Initial) (nm) AM (nm) 1200 (nm)
Fe (Iron) 2.8664 2.8677 2.8676
Y2O3 10.6014 10.60 10.6018

3.3 Crystallite size and strain Variation

The polynomial fit of FWHM of Si Vs 2θ is shown in Fig. 3. This was used to determine instrumental
broadening of Fe and yttria. Voigt, Pseudo-Voigt and Pearson IV are the generally used functions for fitting of XRD
profile. In the present system Pseudo-Voigt function was used for fitting XRD profile and also for deconvolution of
Kα1 and Kα2 components. An example showing the deconvolution of Kα1 and Kα2 for (211) peaks of Fe in 1200
condition is shown in Fig. 4. Generally Kα2 component has half the intensity and same FWHM as of Kα1. For
determining crystallite size and micro strain values, FWHM of Kα1 component was considered for AM, 1200 and
1060 samples. Having determined experimental and instrumental broadening crystallite size and strain were
calculated by Williamson – hall method. The values of crystallite size and micro strain are shown Table-2.
6 Author name / Materials Today: Proceedings 00 (2018) 0000–0000

Fig. 3: Polynomial fit of FWHM values of standard Si to determine instrumental broadening.

Fig. 4: Deconvolution of Kα1 and Kα2 using Lorentz function in (211) plane of Fe in 1200 profile.
It can be observed that the crystallite size of Fe is very large compared to yttria in all the conditions (Table-2).
Fe showed a significant increase in crystallite size from as milled condition (89.45 nm) to heat treatment at 1200 oC
 Author name / Materials Today: Proceedings 00 (2018) 0000–0000 7

(988 nm) and significant drop in crystallite size after heat treatment at 1060 oC (232 nm) (Table-2). Yttria showed a
significant increase in crystallite size from AM (26.39 nm) to 1200 (50.30) condition and no significant variation
was observed after heat treatment at 1060 oC (48.9 nm) (Table-2). Micro strain values of Fe and yttria are higher in
AM condition followed by heat treatment at 1060 oC and 1200oC respectively. However highest micro strain was
observed in yttria AM condition (1.24%).
Table-2: Crystallite size values of Fe and Y2O3 in AM, heat treated at 1200oC and heat treated at 1060oC.
Crystallite Size Micro Strain
Condition
(nm) (%)
AM 89.45 0.5
Iron 1200 988 0.16
1060 232 0.19
AM 26.39 1.24
Y2O3 1200 50.30 0.65
1060 48.9 0.7
MA is a very complex process in which great energy and heavy deformation is introduced to the powder
particles which cause crystal defects and reduce the crystallite size. Many studies on mechanical alloying of ODS
steels showed the decrease in the crystallite size and increase in strain during mechanical alloying and the decrease
in crystallite size is sharp initially and stabilizes on further milling[14,20,21]. A significant increase in crystallite
size of Fe in 1200 condition can be attributed to recrystallization and significant growth of Fe crystal. This suggests
that there was no significant influence of yttria in restricting the growth of Fe crystal during heat treatment which
would have happened if yttria get in to the Fe lattice. The decrease in crystallite size in 1060 condition can be
attributed to smaller austenite grain size at 1060 oC. It was observed that there was significant growth of yttria after
heat treatment at 1200oC suggesting re-precipitation of yttria during heat treatment. Yttria is highly stable oxide at
higher temperatures; but, due to high amount of defect density created by mechanical alloying, yttria would
dissociate in to Y and O and during heat treatment a new crystals nucleate and grow. Some researchers showed the
precipitation of new complex oxides in ODS steels with small addition of Ti where Y 2O3 combines with TiO2 and
forms complex oxides[7,8]. These oxides are very stable at the working conditions (700-800oC) of these alloys. No
significant change in crystallite size of yttria at 1060 condition can also suggest that the re-precipitated Y2O3
particles are stable.

4. Conclusions

 The important conclusion drawn from the study is that there is no significant effect of yttria on the
crystallite changes of ferrite.
 XRD profile showed strong reflections of ferrite and yttria in all the conditions and the intensities of peaks
were less in as milled condition than heat treated conditions.
 No peaks other than ferrite and yttria were observed in as milled XRD profile suggesting no alloy (solid
solution) formation during mechanical alloying.
 There was a slight increase in lattice parameter of ferrite after milling and there is no significant change in
lattice parameter of Yttria.
 Crystallite size was lower in as milled condition for both ferrite and yttria while a significant raise in
crystallite size was observed in ferrite and yttria after heat treatment at 1200 oC.
 The lower crystallite size value of ferrite after heat treatment at 1060 oC compared to heat treatment at
1200oC can be attributed to the smaller austenite grain size at 1060 oC.

Acknowledgements
The authors would like to acknowledge and thank Dr. Vivek K. Malik and other staff of physics
department, IIT Roorkee for their help in carrying out mechanical alloying. Authors would also like to thank
Sudheer Guntaka and Vamshi (B.Tech students of academic year 2013-14) for their valuable help in this study.

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