Abstract ICAS All220916

ICAS 2022
The 7th International Conference on Advanced Steels
Proceedings
May 29 - June 1, 2022· in Tsukuba, Japan

Symp
No page session name title
osium
001 1-4 Plenary Lecture 1 Sung-Joon Kim Role of Interstitials in Austenitic Stainless Steels: C vs N
002 5-7 1 Phase transformation Tadashi Furuhara Interface engineering in controlling microstructure and properties of steels
003 8-11 1 Phase transformation Yasunobu Nagataki State-of-the-art ultra-high-strength steel sheets for automobile application
006 12-15 1 Phase transformation Mahesh Chandra Somani Recent Advances in Design and Processing of Novel Ultrahigh Strength Steels for Arctic Applications
007 16-18 1 Grain structure control Munekazu Ohno Formation of coarse columnar austenite grains during solidification of peritectic steels
008 19-20 1 Grain structure control Shuang Xia The effects of grain boundary character distribution on the mechanical properties of a 316L stainless steel
009 21-22 1 Grain structure control Toshio Ogawa Characterization of recrystallization behavior in pure iron and low-carbon steel by three-dimensional microstructural analysis
010 23-25 1 Grain structure control YongJie Yang Primary recrystallization texture development in grain-oriented silicon steel
011 26-29 1 Second phase particle control Yutaka Neishi Higher performance of special steel bars & wire rods by inclusion morphology control
012 30-33 1 Second phase particle control Ling Zhang Mechanical property of a low carbon steel containing 2 wt%Nb
013 34-37 1 Second phase particle control Wei Wang Obtaining the Solubility Product of TiN in Austenite by Measuring the Grain Growth at Elevated Temperatures
015 38-40 2 Strength & Deformation 1 Nobuhiro Tsuji Possibility of Fully Recrystallized Ultrafine Grained Steels Managing Both High Strength and Large Ductility
016 41-43 2 Strength & Deformation 1 Elena Pereloma Uncovering the relationships between processing parameters, interphase precipitation and strengthening of ferritic high strength low alloy steels
017 44-47 2 Strength & Deformation 1 Genichi Shigesato Microstructure control in high toughness steel plate
018 48-50 2 Strength & Deformation 1 Norimitsu Koga Low-temperature tensile properties of aged ultra-low carbon steels
019 51-54 2 Strength & Deformation 1 Myeong-heom Park Local deformation behavior of ferrite + martensite dual-phase steels with different martensite hardness
020 55-57 2 Strength & Deformation 2 Noriyuki Tsuchida Improvement of mechanical properties from the viewpoint of stress partitioning
021 58 2 Strength & Deformation 2 Stefanus Harjo Observation of deformation behavior of steels using pulsed neutron diffraction
022 59 2 Strength & Deformation 2 Si Gao Effect of grain size on the tensile properties of 304 stainless steel studied by in situ neutron diffraction
023 60 2 Advanced steels 1 Jungho Han The possibility of improved cryogenic toughness of medium-Mn steelfriction stir welding
024 61 2 Advanced steels 1 Hongliang Yi Carbon enrichment at coating/substrate interface and its effect on bendability of Al-Si coated press hardening steel
027 62-65 2 Advanced steels 1 Dirk Ponge Hydrogen embrittlement in high-strength medium- and high-Mn steels: from fundamental understanding to new H-resistant microstructure design
028 66-69 3 Hydrogen embrittlement Young-Kook Lee Effects of microstructure and deformation on the hydrogen embrittlement of a pearlitic steel
029 70 3 Hydrogen embrittlement Hong Luo Environment-induced degradation of iron based multicomponent alloys
030 71-73 3 Hydrogen embrittlement Shusaku Takagi Issue of hydrogen embrittlement evaluation
031 74-76 3 Hydrogen embrittlement Akinobu Shibata Hydrogen-related crack propagation behavior in martensitic steel
032 77-78 3 Hydrogen embrittlement Tomohiko Hojo Evaluation of hydrogen embrittlement properties of ultrahigh-strength TRIP-aided steels
033 79 3 Design of heat resistant steels Satoru Kobayashi Design of ferritic heat resistant steels with improved long term structural stability
034 80 3 Design of heat resistant steels Shigeto Yamasaki Effect of Co addition on creep strength and magnetic properties of high chromium ferritic steel
035 81-84 3 Design of heat resistant steels Nobuaki Sekido Nano-SIMS observation on the boron segregation evolution during tempering of a hear resistant ferritic steel
036 85-88 3 Design of heat resistant steels Yoshiaki Toda Improvement in Creep Strength of Precipitation Strengthened Ferritic Steels
037 89-92 3 Evaluation of heat resistant steels Masatsugu Yaguchi Microstructure and creep strength of grade 91 steel under long-term service condition
038 93 3 Evaluation of heat resistant steels Masatoshi Mitsuhara Effect of grain boundary characters on growth of M23C6 carbides in 9Cr ferritic heat-resistant steel
039 94-97 3 Evaluation of heat resistant steels Tomotaka Hatakeyama Effect of microstructure change on the creep deformation behavior of 18Cr 9Ni 3Cu Nb N steel
040 98-101 3 Evaluation of heat resistant steels Shengde Zhang Microstructure and Mechanical Properties of Long-term Used Super 304H Steel Boiler Tubes
041 102 Plenary Lecture 2 Chengjia Shang The insights from crystallography into the effect of boundaries on the toughness in a heavy gauge high strength low alloy steel
042 103-104 1 Advanced-characterization Naoya Shibata Development of atomic resolution electron microscope for magnetic materials and steels
043 105-106 1 Advanced-characterization Jae Hoon Jang Atomistic investigation of clustering and precipitation in Nb-microalloyed steel
044 107-110 1 Advanced-characterization Wu Gong In situ neutron diffraction study on lattice parameter changes of austenite and martensite during transformation in Fe-18Ni alloy
045 111 1 Advanced-characterization Alexander Bright Automated sample preparation and precipitate characterization in TEM for HSLA steel
046 112-115 1 Advanced-characterization Yuya Murata A precise measurement of grain boundary segregation in steel by STEM-EDS and ζ-factor method
047 116-118 1 Control of austenite Christopher Hutchinson Mechanical stability of austenite in advanced high strength steels
048 119-120 1 Control of austenite Hao Chen Mechanism of Austenite reversion in additive manufactured ultra high strength steels
049 121-124 1 Control of austenite Hui Guo Enhanced carbon enrichment in austenite through introducing pre-existing austenite as a ‘carbon container’ in 0.2C-2Mn steel: the significant impact on microstructure and mechanical properties
050 125-126 1 Martensite/bainite Dong-Woo Suh Heterogeneity driven enhanced tensile properties in martensitic steels
The full program is available at the following website
https://www.nims.go.jp/group/sdg/icas2022/program/
Symp
No page session name title
osium
051 127-128 1 Martensite/bainite Hideyuki Ohtsuka First-principles calculation of the atomic interaction and tetragonality in an Fe-C system
052 129-131 1 Martensite/bainite Maria J. Santofimia Navarro Investigating the formation of bainite in the presence of martensite
053 132 2 Advanced steels 2 Mingxin Huang Negative strain rate sensitivity in steels
055 133 2 Advanced steels 2 Jae-Bok Seol Near atomic-scale comparison of passive film on a high-Cr high-Mn steel with those on typical stainless steels
056 134 2 Advanced steels 2 Shiro Torizuka MECHANICAL PROPERTUES of SINGLE VARIANT MARTENSITE from FERRITE + Mn-RICH CEMENTITE STRUCTURE in 0.1C-2Si-5Mn STEELS
057 135-136 2 Fracture Masaki Tanaka Delamination in wire-drawn pearlitic steels
058 137 2 Fracture Kazuki Shibanuma Fatigue life prediction of steels based on multiscale model synthesis
059 138-141 2 Fracture Yuuji Kimura Delayed Fracture Behavior of Ultrahigh-Strength Low-Alloy Steel Processed by Warm Tempforming
060 142 2 Fracture Yoshikazu Todaka Hydrogen Embrittlement Behavior of Nanostructured SUS316LN Austenitic Stainless Steel Produced by Heavy Cold-rolling and High-pressure Torsion Straining
061 143-144 2 Martensite Nobuo Nakada Heterogeneous cleavage fracture of lath martensite induced by Bain strain
062 145 2 Martensite Shimpei Yoshioka Formation of inhomogeneous microstructure in martensitic steel during cooling and its effect on yield strength
063 146-149 2 Martensite Osamu Idohara Estimation of true hardness of as-quenched martensite without auto-tempering
064 150-153 2 Martensite Hiroyuki Kawata Grain refinement strengthening on Fe?18Ni low carbon lath martensite
065 154-157 3 Fundamentals of Corrosion Masatoshi Sakairi Effects of metal cation on corrosion of structural metals in aqueous environments
066 158 3 Fundamentals of Corrosion Yoshinao Hoshi 3D Impedance Spectroscopy to Investigate Film Growth Rate of Chromate Film Formed on Steel
068 159-160 3 Fundamentals of Corrosion Mariko Kadowaki Roles of Interstitial Elements in Anodic Dissolution Resistance of Martensitic Steels
070 161-163 3 Corrosion resistant materials / evaluation methods Fumio Yuse Corrosion resistant steel for bridges and life cycle cost
071 164-167 3 Corrosion resistant materials / evaluation methods Yusuke Tsutsumi Fundamentals of corrosion engineering of metallic materials and development of ultrahigh corrosion resistant stainless steels by novel laser techniques
072 168-169 3 Corrosion resistant materials / evaluation methods Kotaro Doi Corrosion Behavior of Steel Rebar in Concrete Studied with Hyperbaric-oxygen Accelerated Corrosion Test
074 170-172 1 High alloyed steels Kyung-Tae Park Tensile Fracture of High Mn TWIP steel
075 173 1 High alloyed steels Hung-Wei (Homer) Yen Nano/microstructural engineering in lightweight high-entropy steel with multiple characteristics
076 174 1 High alloyed steels Ivan Gutierrez-Urrutia Study of microbanding in a Fe-30Mn-6.5Al-0.3C low-density steel deformed at cryogenic temperatures: Mechanisms and contribution to the mechanical behavior
077 175 1 High alloyed steels Mei Zhang Manufacturing superior property medium Mn TRIP steel free of Luders bands by warm deformation + IA process
078 176-178 2 Strength & Deformation 3 Heung Nam Han Mechanistic view on electric current induced kinetic enhancement and its various examples in steels
079 179-182 2 Strength & Deformation 3 Emmanuel De Moor Double Soaking of Medium Manganese Steels
080 183- 2 Strength & Deformation 3 Masato Wakeda Atomistic modeling and analysis of dislocation behaviors near grain boundary in iron
082 184-187 3 Fatigue Takashi Nakamura In situ observation of small fatigue cracks in high-strength metals using synchrotron radiation micro and nano computed tomography
083 188-190 3 Fatigue Hisao Matsunaga Various strength properties of low-alloy steels in high-pressure hydrogen gas and their hydrogen compatibility
084 191 3 Fatigue Motomichi Koyama Plastic deformation and dislocation motion at a fatigue crack tip of a bi-modal Ti-6Al-4V alloy during dwell loading
085 192-195 3 Fatigue Hideaki Nishikawa Understanding the effect of microstructure on fatigue properties of weld heat affected zone of low carbon steel based on microscopic fatigue crack initiation and growth behavior
086 196-199 Plenary Lecture 3 Setsuo Takaki (Japan) Yielding mechanism in polycrystalline ferritic steel
The full program is available at the following website
https://www.nims.go.jp/group/sdg/icas2022/program/
Role of Interstitials in Austenitic Stainless Steels: C vs N
Sung-Joon Kim1,*, Kyung-Shik Kim1 and Jee-Hyun Kang2
1
Graduate Institute of Ferrous and Energy Materials Technology, POSTECH, Pohang, 36763, Korea
2
School of Material Science and Engineering, Yeungnam University, Gyeongsan 35481, Korea
*email: sjkim1@postech.ac.kr
Keywords: carbon, nitrogen, stainless steel, deformation behavior, hydrogen embrittlement
Austenitic stainless steels are known for their excellent corrosion resistance, toughness, and formability.
Furthermore, they are resistant to hydrogen embrittlement, which enables their application in hydrogen environment.
However, their strength is low; yield and tensile strengths are approximately 250 MPa and 600 MPa, respectively. To enhance
their strengths, interstitial alloying elements, such as carbon and nitrogen, are added.
The different behavior of C and N in austenitic stainless steels has been studied extensively. Gavriljuk et al. claimed
that different properties brought by the interstitials is attributed to their different influences on the electronic structure of the
steels. Because N and C change the distribution of density of states differently, free electron concentration is increased more
effectively by N than by C. Thus, nitrogen is known to promote metallic interatomic bonding while carbon induces covalent
bonding 1). Consequently, for neighboring carbon atoms, nearest interstitial sites are preferred, which results in short-range
clustering. On the other hand, nitrogen atoms tend to occupy second nearest interstices which would generate short-range
ordering 2).
Accordingly, various properties of austenitic stainless steels are altered in different ways. Precipitation of either
M23C6 or Cr2N was less likely to occur in N bearing steels than in C containing steels 3). Moreover, more lattice distortion was
caused by nitrogen, which resulted in higher strengthening effect than by the same concentration of carbon 4,5). Another
difference was the segregation tendency at grain boundaries. Carbon segregated to grain boundaries which would contribute
to intergranular corrosion.
Recently, different effects by C and N on austenite stability and staking fault energy (SFE) of austenitic stainless
steels have been intensively investigated. Masumura et al. reported that the effects by C and N on austenite stability depended
on the type of stability. When the steels are quenched to form athermal α'-martensite, nitrogen was more effective in
stabilizing austenite than carbon. On the other hand, a N containing steel induced less fraction of α'-martensite during
deformation 6). The trend of SFE alteration is controversial. It was reported that carbon increased 6-9), or did not affect 10-12) SFE,
while nitrogen increased 6,7), decreased 13-15), or non-monotonously affected 12-,16) SFE. This suggests that SFE variation may
depend on alloy systems.
Although different effects of C and N on austenite have been continuously studied, they were rarely investigated in
the same base alloy system. Inspired by this fact, the present study dealt with the austenitic stainless steels which only varies
with the type of interstitials while the concentrations of other alloying elements were equivalent. Deformation behavior at
room temperature and at high temperature as well as hydrogen embrittlement were studied by focusing on the different effects
of carbon and nitrogen.
Alloys were designed so that up to 0.3 wt% of either C or N is soluble. By using ThermoCalc with TCFE7
database, the suitable base alloy that satisfied the solubility condition was acquired to be Fe-15Cr-15Mn-4Ni-0.3Si (wt%).
The alloys with 0.1, 0.2, 0.3 wt% C were called as C1, C2, and C3, respectively, and their nitrogen counterpart was named as
N1, N2, and N3 (Table 1). All alloys were hot-rolled to 13 mm-thick sheets. For the room temperature deformation study, the
alloys were machined into tensile specimens, gauge dimension of which was 33×10×1.5 mm3. They were all annealed at
1100°C for 15 or 30 min so that the resulting grain size was ~50 μm. SFE values were obtained by thermodynamic
calculation and XRD (Table 1). Tensile tests were conducted with a constant crosshead speed of 1.5 mm min-1. For the
Hall-Petch relationship study, hot-rolled sheets were cold-rolled to either 1.4 or 2.3 mm, and solution-treated for 1-180 min at
1000 or 1200°C. Yield strength was obtained with tensile testing at a constant crosshead speed of 0.1 mm min-1. The gauge
dimension of tensile samples was 25×6×1 mm3. For the high temperature deformation study, hot compression testing was
performed. Cylindrical samples were prepared from hot-rolled sheets. They were annealed at 1200°C for either 1.5 or 5 min,
ICAS 2022 The 7th International Conference on Advanced Steels -1-

and compression testing was carried out at 800-1100°C with the strain rates of 0.01, 0.1, or 1 s-1. For hydrogen embrittlement
study, the alloys were machined into tensile samples, the dimension of which was 25×6×1.5 mm3, and were solution-treated at
1100°C for 10-15 min. Hydrogen was charged in an aqueous solution of 30 g L-1 NaCl and 3 g L-1 NH4SCN under 50 A m-2
for 48 h at 90°C. Afterwards, slow strain-rate tensile testing was conducted at room temperature under a constant crosshead
speed which yielded the initial strain rate of 6.67×10-5 s-1. Hydrogen permeation testing was carried out according to ISO
17081 standard, and thermal desorption analysis (TDA) was performed under the heating rate of 100°C h-1. The details of
experimental procedures are available elsewhere 5,17-20).
Table 1: Alloy compositions and stacking fault energy (SFE) values.

SFEcalc / SFEexp /
Alloy Cr / wt% Mn / wt% Ni / wt% Si / wt% C / wt% N / wt% Fe
mJ m-2 mJ m-2
Base 15.4 14.8 4.1 0.33 0.01 0.01 Balance -2 9±1
C1 15.1 14.8 4.0 0.33 0.10 0.01 Balance 9 12 ± 1
C2 14.9 15.0 4.0 0.29 0.21 0.01 Balance 7 15 ± 1
C3 15.2 15.1 4.0 0.32 0.30 0.01 Balance 14 22 ± 1
N1 15.4 15.3 4.0 0.28 0.02 0.11 Balance 8 14 ± 1
N2 15.0 15.2 4.1 0.26 0.02 0.19 Balance 18 19 ± 2
N3 14.9 14.9 4.0 0.27 0.01 0.31 Balance 30 25 ± 5
The interstitial effect on the tensile behavior at room temperature was most prominent in yield strength while it was
insignificant in strain hardening. The effect on yield strength was larger with N addition than C addition possibly due to higher
interstitial-dislocation binding energy for nitrogen 21). The difference was also noticeable in austenite stability. Although
ε-martensite was fully suppressed in the N containing steels on quenching, it appeared in the C containing steels and Base.
Moreover, the fractions of deformation-induced martensites were higher for the carbon bearing steels than for their
counterpart containing the equivalent concentrations of nitrogen. In other words, nitrogen was more effective for suppressing
both athermal and deformation-induced martensites, which was consistent with the variation in SFE (Table 1). Although the
martensites fractions were different, the morphologies were similar in both C and N containing steels. In all interstitial
containing steels, not only martensite but also mechanical twinning formed, and α'-martensite formed at the intersections of
ε-martensite. The different effects of the interstitials also appeared in dislocation structure. While the C bearing steels exhibited
wavy slip, N bearing steels showed planar slip. However, such difference insignificantly affected strain hardening.
To study Hall-Peth relationship, effective grain size was estimated by considering the number of twin boundaries
per grain. The effective grain size depended on the correction factor which implied the effectiveness of a twin boundary to act
as a dislocation barrier. When the steels were annealed at different temperatures and times to obtain various grain sizes, the
number of twin boundaries per grain was higher in N3 than in C3, which resulted in smaller effective grain size in N3. Both
C3 and N3 followed Hall-Petch relationship. For all values of the correction factor from 0 to 1, Hall-Petch slope was higher
for N3 than for C3. Hall-Petch slope is known to depend on Taylor factor, Burgers vector, shear modulus, Poisson ration, and
the stress τc required to activate dislocation source. Because all the factors except τc was similar, it is concluded that τc/G was
smaller for C3 than for N3. τc/G was suggested to be related to dislocation glide behavior. Because slip planarity tendency was
higher in N3, which implied the difficulty in cross slip, slip transmission would be suppressed which resulted in higher τc/G.
From high temperature compression, it was found that both C and N bearing steels followed the general trend; flow
stress was lowered by increasing temperature and decreasing strain rate. As the interstitial concentration increased, flow stress
increased accordingly; this trend appeared more strongly by N addition than by C addition. Moreover, activation energy for
deformation was higher for nitrogen containing steels. These suggested that deformation became more difficult by N addition
than by C addition. At the temperature ≥ 1000°C, strain hardening became negligible owing to dynamic softening. Especially,
dynamic recovery rate was revealed to be lower for N bearing steels, which was caused by suppression of cross slip, i.e.,
promotion of slip planarity by short-range ordering. The microstructure after the hot compression testing contained
recrystallized grains which nucleated along elongated grains. It was revealed that the size of the recrystallized grains increased
with increasing temperature and decreasing strain rate. Moreover, the size decreased with increasing interstitial concentration;

such size decrease was higher for N containing steels that their C containing counterparts. This implied that the solute drag
effect during hot deformation was stronger by N than by C.
Slow strain-rate testing revealed that the addition of either C or N enhanced resistance to hydrogen embrittlement.
During deformation, the formation of ε-martensite occurred, and it was promoted by hydrogen precharging. α'-martensite also
formed; however, its fraction was smaller than that of ε-martensite, and was suppressed by hydrogen precharging. The
different effects of C and N on hydrogen embrittlement were noticeable in strain hardening rate (SHR). After hydrogen
precharging, SHR values deviated from the SHR curves of the non-charged samples. With C addition, the deviation started in
the middle of deformation while in N added steels, it occurred immediately after yielding. Such tendency was attributed to
surface cracking during deformation. It was found that the surface cracks initiated and propagated from the beginning of
deformation for N containing steels. Moreover, fractography analysis revealed brittle fracture at the edge of all samples
because hydrogen could not penetrate through the samples. Especially for C added steels, transgranular fracture was observed
and the depths showing brittle fracture were similar for all C1, C2, and C3. On the other hand, intergranular fracture appeared
in N bearing steels, and the depth of brittle fracture region was reduced with increasing the N content. TDA and permeation
test results showed that hydrogen diffusivity as well as hydrogen content in the steels were similar for C1, C2, and C3 while
these decreased with increasing N concentration, which was consistent with the fractography. In addition, crack initiation and
propagation behavior in the hydrogen affected regions depended on the interstitial types. In C containing steels, cracks
propagated through the grains and suspended at the grain boundaries while in N added steels, cracks initiated and propagated
along the grain boundaries. Such observation was consistent with different types of brittle fracture observed on the fracture
surfaces.
In summary, different roles of C and N in austenitic stainless steels were investigated in their deformation behavior
at room and high temperatures and hydrogen embrittlement. It was found that nitrogen was more effective in enhancing yield
strength and stabilizing austenite. Also, it promoted planar glide of dislocation and suppressed cross slip. Moreover,
Hall-Petch slope was higher in N containing steels than in C containing counterparts because nitrogen suppressed slip
transmission to an adjacent grain. Furthermore, dynamic recovery and recrystallization during high temperature deformation
was delayed and yield strength increased more effectively by N addition than by C addition because the solute drag effect was
stronger and deformation activation energy was higher in N added steels. Moreover, both C and N additions suppressed
susceptibility to hydrogen embrittlement. Although both C and N considerably stabilized austenite, hydrogen induced
phenomena in the steels depended on the interstitial type. The carbon concentration in the steels hardly affected permeation
behavior of hydrogen while hydrogen diffusivity and charged content were reduced with increasing N content. Besides,
cracks propagated along martensite/austenite interfaces to cause transgranular fracture in C added steels while they propagated
along austenitic grain boundaries resulting in intergranular fracture for N steels. It was also found that crack on the sample
surface was facilitated in N added steels which caused the deviation of strain hardening rate to appear from the beginning of
deformation. In conclusion, although C and N share common characteristics that both strengthen the steel, stabilize austenite,
and enhance the resistance to hydrogen embrittlement, the extents of such effects are different. Strengthening and austenite
stabilizing effects were more effective by N addition while surface cracks are less prevalent and intergranular fracture is
suppressed by C addition.
Acknowledgement
The authors are thankful for the financial support by National Research Foundation of Korea (NRF-2020R1A2B5B01001900).
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Interface Engineering in Controlling Microstructure and Properties of Steels
Tadashi Furuhara1,2, Yongjie Zhang1, Mitsutaka Sato1, and Goro Miyamoto1,3

1
Institute for Materials Research, Tohoku University, Sendai, Miyagi 980-8577, Japan
2
Core Research Clusters for Materials Science, Tohoku University, Sendai, Miyagi 980-8577, Japan
3
Research Center for Structural Materials, National Institute for Materials Science, Tsukuba, Ibaraki 305-0047, Japan
*email: tadashi.furuhara.c3@tohoku.ac.jp
Keywords: steel, phase transformation, precipitation, crystallography, interface, alloying element
In modern high strength steel, sophisticated control of transformation microstructure is required for better strength and
ductility/toughness balance. In addition to fraction, size and distribution of constituent phases, a degree of local partitioning of
carbon (C) and substitutional alloying elements (M) during phase transformations is an important factor in development of dual
phase and TRIP steels which are typical advanced high strength steels. Therefore, quantitative understanding of alloying effects
on phase transformation kinetics in Fe–C system becomes increasingly important. Recently, our group has been carrying out the
research on the effects of hetero-phase interface (i.e., interphase boundary) in various phase transformations and precipitation
mainly in low alloy steels1-4) . In this presentation, alloy partitioning and precipitation during austenite/ferrite interphase boundary
migration are discussed.
Interphase boundary nature has a direct impact on the transformation kinetics. The growth of grain boundary ferrite
in Fe-C alloys is contolled by volume diffusion of carbon in austenite by local equilibrium, but is slower than the expected from
calculation assuming the migration of incoherent boundaries The reason for this was considered to be effects of the boundary
structures mixed by partly coherent and incoherent ones. Boundary velocity (V) is proportional to driving force (ΔG) to move
the boundary forward as described below.
V = M･ΔG
where M is boundary mobility. If the interphase boundary can move freely, the entire chemical driving force is available for
boundary migration. However, there are various ‘frictions’ on the interphase boundary migration exerted from various
components of the microstructure as represented in Fig. 1(a). Atomic displacement at the boundary causes intrinsic friction. Solute
atoms segregated at the boundary provide another friction known as 'solute drag'. Dislocations or fine second-phase particles may
add further barriers for boundary migration. These kinds of friction or barrier result in the energy dissipation during boundary
migration and decrease in the net driving force ΔG. Fig. 1(b) shows the effect of such energy dissipations in boundary migration
on partitioning of carbon in the Fe-C binary system. The same situation can be imagined for the (Fe, M)-C pseudo-binary case
with para-equilibrium. Total energy dissipation caused from various sources is balanced by driving force (ΔGdvr) at migrating
Fig. 1: (a) Schematic illustration of microstructure components causing energy dissipation in boundary migration. (b) Deviation of
carbon partitioning from local equilibrium due to energy dissipation at a migrating boundary for γ→α forward transformation. (c)
Energy dissipation for BF and WF transformations with respect to para equilibrium 2, 3).

interphase boundary. ΔGdvr corresponds to the gap between the chemical potentials of iron for the two different carbon content at
the boundary and is determined by carbon concentrations in α and γ near the boundary. When some friction accompanies
boundary migration, an extra driving force to make the boundary move forward is necessary and a deviation from local
equilibrium occurs as shift of the boundary concentration from the black open circles to red open circles. Such energy dissipation
leads to lower carbon content in austenite for ferrite transformation. By measuring the chemical composition, in particular the
carbon content across the boundary, it is possible to estimate the amount of such dissipation.
Proeutectoid ferrite changes its morphology from allotriomorhic ferrite (AF) to Widmanstatten ferrite (WF) as
temperature decreases. Ferrite growth takes place via preferential migration of 'incoherent' boundary without well-known K-S
orientation relationship (OR) for AF and more 'coherent' boundary with near K-S OR for WF. The energy dissipation is larger as
transformation temperature is lower for each type of boundary. Also, dissipation is much larger for the WF/γ boundary than the
AF/γ boundary. This can be attributed to low mobility of partially coherent near K-S boundary causing larger interface friction.
When the transformation temperature further decreases typically below 600℃, bainitic ferrite (BF) with high boundary coherency,
similarly to WF, starts to form both at austenite grain boundaries but also by frequent intragranular nucleation.
In alloyed steel, AF grows more slowly than the Fe-C case with carbon partitioning. There are three distinctive local
equilibrium growth modes in Fe-C-M (M: substitutional alloying element) system. These are para-equilibrium (PE), negligible-
partitioning local equilibrium (NPLE) and partitioning local equilibrium (PLE). PE and NPLE are essentially C diffusion-
controlled modes without macroscopic partitioning of substitutional alloying element M. Fig. 1(c) summarizes the energy
dissipation from Ae3 temperature of PE for WF and BF formation including Fe–C and Fe-C-Mn alloys as well as and some other
multi-component steels, plotted as a function of transformation temperature 2). It also contains the recent evaluation of ferrite
transformation in Fe-N binary alloy 3). Even with a wide range of alloying element and composition, energy dissipation almost
follows a universal line and increases rapidly with lowering transformation temperature. Large energy dissipation at low
temperature is probably originated from elastic strain energy. Although plastic accommodation provides another friction for
displacive motion of interphase boundary, the variation of strain energy with transformation conditions is very useful in novel
and sophisticated design of high strength steel using ferrite and bainite transformations.
Multiphase advanced high strength steels such as DP or TRIP steels show good uniform elongation but are with
relatively poor local elongation. For automobile parts requiring more local elongation, ferritic steel strengthened by nano-sized
precipitation is preferably used. Interphase precipitation of alloy carbides during ferrite transformation establishes high yield
strength and good elongation in low-carbon ferritic steels. Nano-sized carbide dispersion obtained in this phenomenon increases
yield strength and work hardening in the early stage of deformation. But, later, uniformly introduced dislocations interact each
other and dynamic recovery is enhanced, resulting in suppression of inhomogeneous deformation and large local elongation.
In the interphase precipitation, crystallographic relationship between ferrite (α), austenite (γ) and carbide plays a major
role to determine the carbide dispersion and corresponding strength. Recently, we have demonstrated that a larger driving force
for precipitation results in a finer carbide dispersion with incoherent α/γ boundary 4).. Fig. 2 shows the effect of boundary coherency
(here represented as deviation angle from the K-S OR, i.e., Δθ) on the VC particle dispersion and corresponding nano-hardness.
V is thought to have an attractive interaction to α/γ boundary and exert solute drag effect as in the case of Nb addition. More V
atoms segregate at non K-S boundary (Fig. 2(d)) and such a situation is advantageous for carbide precipitation thermodynamically
and kinetically. As the deviation angle becomes larger, which means that the α/γ boundary becomes less coherent, the number
density of VC particles increases drastically (Fig. 2(e)). Fig. 2(f) clearly shows that the increase of particle density leads to higher
hardness through the Orowan-type dispersion hardening.
It is important to make incoherent α/γ boundaries to obtain high strength through interphase precipitation. Although
this is rather challenging, one possible way is use of ferrite transformation from deformed austenite. Fine-grained austenite
structure inhibits formation of Widmanstätten ferrite so that recrystallization of austenite can be effective to obtain granular ferrite
structure. Ferrite transformation in unrecrystallized austenite can be promising since local orientation fluctuation in the deformed
austenite will accomplish loss of interfacial coherency during growth even though initial nucleus had near K-S OR with austenite.
Use of nucleation at particles is also a good way 5, 6). Nucleation at grain boundary precipitate or intragranular inclusion effectively

enhances the formation of granular ferrite grains with non K-S OR, rather than WF or BF without nanosized VC precipitation in
as-transformed condition. This ferrite morphology change results in the significant increase of overall strength or hardness.
Here, the alloy partitioning/segregation and nanoscale precipitation at migrating interfaces, in design of advanced high
strength steels with good ductility was summarized. In conclusion, it is clear that interfacial coherency plays major roles in the
control of microstructure and mechanical properties of steels. By controlling crystallographic constraints in phase transformations,
a variety of alloy design and thermomechanical processing is expected to contribute to further advances in the development of
novel high strength steels.
Acknowledgement
The authors gratefully acknowledge financial supports by the Innovative Structural Materials Project funded by the New Energy and
Industrial Technology Development Organization, CREST Basic Research Program “Creation of Innovative Functions of Intelligent
Materials on the Basis of Element Strategy” funded by Japan Science and Technology Agency, Grant-in-Aid for Scientific Research (B)
No. 23360316 (2011–2013) and (A) No. 17H01330 (2017-2019) funded by Japan Society for the Promotion of Science.
References
1) T. Furuhara:, Y. -J. Zhang, G. Miyamoto: IOP Conf Series: Mater Sci Engng, 580(2019), 012005.
2) G. Miyamoto, T. Furuhara: ISIJ International, 60(2020), pp. 2942–2953.
3) M. Sato, G. Miyamoto, T. Furuhara: Netsu Shori (J. Jpn. Soc. Heat Treat.), 61(2021), pp. 82-85.
4) Y. -J. Zhang, E. Chandiran, H. -K. Dong, N. Kamikawa, G. Miyamoto, T. Furuhara: JOM, 73(2021), pp. 3214-3227.
5) Y. -J. Zhang, G. Miyamoto, K. Shinbo, T. Furuhara: Acta Mater., 128(2017), pp. 166-175.
6) G. Miyamoto, R. Hor, B. Poorganji, T. Furuhara: Metall. Mater. Trans. A, 44(2013), pp. 3436-3443.
Fig. 2: (a) Ferrite orientation maps of the Fe–0.1C–1.5Mn–0.4V alloy transformed at 923 K. Circles represent near K-S boundaries
and triangles indicate non K-S boundaries. (b) Schematic illustration describing angular deviation from K-S OR. 1D concentration
profiles of V and C obtained by 3DAP analyses of (c) near K-S and (d) non K-S boundaries. Variations in (e) number density of VC
precipitate and (f) nanohardness of α grains with Δθ in Fe-0.1C-1.5Mn-0.4V 1,4).

State-of-the-art ultra-high-strength steel sheets for automobile application
Yasunobu Nagataki1,*
1
Steel Research Laboratory, JFE Steel Corporation, 1-Kawasaki-cho, Chuo-ku, Chiba 260-0835, Japan
*email: y-nagataki@jfe-steel.co.jp
Keywords: ultra-high-strength steel sheet, multiphase microstructure, ductility, stretch-flangeability, carbon mapping, spring back,
Bauschinger effect
1. Introduction
Due to the strong demand for minimization of global climate change, carbon dioxide (CO2) emission in automobile
industry has been required to be reduced drastically. Not only conventional countermeasures for energy consumption
reduction but also transition from gasoline to electric power train such as EV will be necessary for the challenging target of
CO2 emission reduction. However, even in EV, weight reduction of body weight is still a major issue to compensate the large
weight gain by pretty heavy battery. Thus, although weight reduction in automotive body has been the continuous
technological trend for these 30 years originating from corporate average fuel economy (CAFE)1) regulation, this trend will
continue in the coming century.
From the view point of material selection, non-ferrous light materials such as aluminum, magnesium, carbon fiber
reinforced plastic (CFRP) and so on might have been also considered. However, the major material for the weight reduction in
automobile would be steels taking into consideration of the stable and economical supply for the growing number of vehicles.
Without doubt, application of high-strength steel sheets has been an effective way in the past few decades and
would have been the same in the coming decades by thinning the automotive parts with maintaining or increasing crash
strength of vehicles. Especially, ultra-high-strength steels (UHSSs) with tensile strength over 980MPa have been widely used
for the structural automotive parts.
Due to the increasing demand of automobile weight reduction, maximization of strength of all the structural
automotive parts has been accelerated through the stronger collaboration than ever between steel makers and automobile
manufacturers.
2. Required properties of UHSSs for automobile application

As well known, automotive body weight and the amount of CO2 emission are in good relationship2). Weight
reduction is the effective countermeasure for the decrease of CO2 emission. At the same time, automotive body is required to
have enough crashworthiness even in the reduced body weight. Furthermore, regulations in the passenger safety have become
more and more severe. In respond to these social requirement, UHSSs have been applied to the automotive body parts.
Especially in the cabin area, hot stamping steels with tensile strength over 1500MPa are widely used. Regarding the cost and
CO2 emission reduction, UHSSs for cold stamping with tensile strength of 1500MPa (1.5G UHSS) has been developed and
applied for several automotive body parts in Japan3).
In higher tensile strength of steel sheets, formability
inevitably deteriorates. Although ductility is the major index of
formability, other indexes such as bendability and
stretch-flangeability are quite important especially in the application
of UHSSs for the complicated automotive body parts. Figure 1
shows the typical example of automotive body part in which
stretch-flangeability is necessary for the stamping.
To improve ductility, introduction of multiphase structure
is effective and especially increase of volume fraction of retained
austenite will lead to better ductility4). However, the interface
between different composed phases may become the initiation site Fig. 1. Example of stretch flange cracking
5)
of crack in heavy and local deformation . So, control of hardness in an automotive body part.

Table 1. Line-up of JFE‘s ultra-high-strength steel sheets (over 980MPa).
■︓Commercial production,●︓Developed
TS grade (MPa)
Product type Steel type Type
980 1180 1320 1470
MS High λ/super high TS ■ ■ ■ ■
Low YR ■ ■
Cold-Rolled Steel DP
High El ■ ■
Sheets (CR)
DH High El - high λ ● ●
TRIP Super high El ■ ■
MS Super high TS ● ●
Galvannealed Steel Low YR ■ ■
DP
Sheets (GA) High El ■ ■
DH high El - high λ ■
MS: Martensite, DP: Dual phase, DH: DP with high ductility, TRIP: Transformation induced plasticity
difference and distribution of each composed phase such

as ferrite, martensite, bainite and retained austenite is the
key technique for the improvement of bendability and
stretch-flangeability dominated by the local ductility.
These precise microstructure control can be
achieved by the assist of advanced analyzing techniques
such as SEM, TEM, atom probe tomography, neutron
scattering6) and so on. Because carbon content in each
phase seriously affects the kinetics of phase
transformation, stability of each phase during heat
treatment and hardness of each phase in the final
microstructure, precise information of the carbon content
will help us to discuss the relationship between
microstructure and mechanical properties and also to
construct advanced material designs. This latest technique
of quantification of carbon content will be mentioned in
the next section.
ICAS 2022 The 7th International Conference on Advanced Steels
Fig. 2. Press forming result of B-pillar. (a) Whole
Table 1 is the variation of UHSSs for cold image of press formed part (Closing lined part is
stamping in JFE Steel. Several types of UHSSs are magnified), (b) High El type 980GA,
developed with various balance of formability. Figure 2 (c) Conventional 980GA (for comparison).
shows an example of press forming results of B-pillar
applying high El type 980GA. Accompanied by the
advanced forming techniques, these UHSSs will greatly help automobile manufacturer to introduce a lighter and stronger
automotive body.
3. Advanced analyzing technique of microstructure of UHSSs

As mentioned above, multiphase microstructure design is the basic philosophy in the development of UHSSs with
superior formability. In a simple multiphase microstructure of ferrite and martensite dual-phase structure, quantification of
volume fraction, hardness and element distribution of each phase is relatively easy. But in case of more complex multiphase
microstructure with higher volume fraction of hard phases, identification of martensite, bainite and retained austenite becomes
more and more difficult. Furthermore, element distribution such as carbon, manganese, silicon and so on will be also complex
especially in the complicated heat treatment cycles applied for such as third generation high strength steels7).
-9-
Quantification of elemental distribution is
one of the key factor for understanding the FE-Gun
microstructure formation or physical properties such as
hardness. Solid solution elements such as manganese Electron beam
and silicon can be quantified by the conventional
electron probe micro analyzer (EPMA). But Plasma cleaner
quantification of carbon by EPMA technique is quite 3 carbon detectors
difficult because of the rapid formation of Liquid N2 trap
hydrocarbon contamination on specimen surface X-ray
during measurement. Sample preparation Sample
Figure 3 shows the schematic diagram of the chamber
8)
Plasma cleaner Detector
developed instrument for carbon mapping in steels . Heating stage
This new field emission (FE) EPMA can drastically
eliminates the carbon contamination of the steel
specimens by the combination of plasma cleaners in the
specimen chamber and preparation chamber, a Fig. 3. Schematic diagram of developed instrument
for carbon mapping in steels.
heating-type sample stage in the specimen chamber
and three carbon detectors. Figure 4 shows an example
of carbon mapping measurement results of a dual phase steel annealed at 950 oC then cooled to 750 oC and held for 15s
followed by water quenching9). It can be seen that the carbon concentration in the central area of the martensite is
close to that in the bulk (0.15 mass%), and carbon is enriched in front of some interfaces, which indicates the
interfaces moved during holding at 750 oC. This new technique can detect the carbon distribution in the
microstructure such as figure 4 quantitatively, which contributes to the development of advanced UHSSs.
(a) SEM image (b) C mapping

C cont.
0.8%
Ferrite
0%
Martensite
5µm
0.4
(c) C line profile 0.3

C contents /mass%
0.2
0.1
0.0
0 10 20 30 40
Distance /μｍ
Fig. 4. Example of carbon quantitative mapping of a dual phase steel (a,b) and
line analysis (c) along the yellow line in b) using the developed FE-EPMA.

4. Advanced forming technique in the application of UHSSs for automotive body parts
In the press forming of UHSSs into automotive
body parts, several defects besides fracture due to the poor
formability will appear such as surface distortion, wrinkle and
spring back. In Japan, steel makers have played an important
role as solution suppliers for the automotive manufacturers to
suppress these defects on the basis of material physical
properties. Fig. 5. Example of the application of 1.5G
Figure 5 shows an example of the application of UHSS for a roof center reinforcement with
1.5G UHSS for a roof center reinforcement with assist of assist of stress reverse press forming
10)
stress reverse press forming technique . In this application, technology.
the bottleneck to the actual adoption of UHSS is shape
(a)
accuracy. In manufacturing of 1.5G UHSS, the scattering of
Product shape
tensile strength sometimes becomes larger compared to steel
sheets with lower tensile strength. In such case, degree of
spring back becomes larger than the correction range thorough
a press forming process. Stress reverse press forming
technique is a countermeasure by suppressing the 1st process shape
susceptibility of tensile strength utilizing the Bauschinger (b)
effect. Product shape
Figure 6 shows the press forming steps of this
method. In the 1st process, a blank is formed with a small
radius curvature compared to a target radius curvature in the
2nd process. Due to the Bauschinger effect, press formed blank
1st process shape
after 1st process deforms with smaller stress into target radius
curvature in 2nd process like HSSs with lower tensile strength. Fig. 6. Newly developed 2-step press forming
This decrease in deformation stress will result in a small spring method, (a) 1st process, and (b) 2nd process.
back compared to conventional press forming processes.
5. Summary
Demand for the application of UHSSs will become more and more aggressive in a carbon neutral society. At the
same time, not only advanced material design but also microstructural analyzing techniques and solution techniques in press
forming and welding will be required to be continuously developed. Furthermore, computational materials science and data
science will become essential for promoting the development of advanced UHSSs.
Acknowledgement
New FE-EPMA for quantitative carbon analysis was developed under a project of the Innovative Structural Materials
Association (ISMA) supported by the New Energy and Industrial Technology Development Organization (NEDO) in Japan.
References
1) https://www.nhtsa.gov/laws-regulations/corporate-average-fuel-economy.
2) https://www.mlit.go.jp/jidosha/content/001337988.pdf
3) https://www.jfe-steel.co.jp/en/release/2020/201223.html
4) T. Nakagaito, H. Matsuda, Y. Nagataki and K. Seto: ISIJ Int., 57 (2017), pp.380-387.
5) K. Hasegawa, K. Kawamura, T. Urabe and Y. Hosoya: ISIJ Int., 44 (2004), pp.603-609.
6) N. Tsuchida, T. Tanaka and Y. Toji: ISIJ Int., 60 (2020), pp.1349-1357.
7) D. K. Matlock and J. Speer: Proc. The 3rd ICASS, Gyeongju Korea (2006), pp.774-781.
8) T. Yamashita, Y. Tanaka, M. Nagoshi and K. Ishida: Sci. Rep., 6 (2016), Srep29825.
9) T. Yamashita, M. Enomoto, Y. Tanaka, H. Matsuda and M. Nagoshi: ISIJ Int., 58 (2018), pp.1079-1085.
10) S. Tobita, T. Shimmiya, Y. Yamasaki and J. Hiramoto: Mater. Trans., 62 (2021), pp.1750-1756.

Recent Advances in Design and Processing of Novel Ultrahigh Strength Steels
for Arctic Applications
M.C. Somani, S. Ghosh, P. Kaikkonen, S. Pallaspuro, S. Sadeghpour, and J. I. Kömi
University of Oulu, Faculty of Technology, Centre for Advanced Steels Research, P.O. Box 4200, 90014 Oulu,
Finland; contact: mahesh.somani@oulu.fi
Keywords: Quenched & partitioned/nanostructured bainitic/medium-Mn steels, C/Mn partitioning.

In pursuance of one of its scientific profiling areas to create sustainability by materials and
systems, the University of Oulu has embarked on a comprehensive plan to employ physics-based
physical metallurgy concepts for the research, development, design, and processing of novel
ultrahigh strength steel concepts with excellent combinations of properties. Themes identified for
the research activities include novel 3rd generation steel concepts, such as (direct) quenched and
partitioned (D(Q&P)) steels, nanostructured bainitic steels and medium-Mn steels [1,2].
Microstructures engineered in these advanced steel concepts normally comprise two or more
phases with the constituents often finely divided to nanometre/submicron level with various
functionalities and require advanced physical simulation and modelling for optimized processing
and predicting structure-property relationships. The key identified areas for the novel steel
concepts include studying extensive structural refinement, distribution and morphology of phase
constituents, phase transformation characteristics and kinetics, and accompanying structural
mechanisms using advanced metallography as well as analytical techniques including atom probe
tomography. The accomplishment of reasonable ductility and high toughness in these complex
microstructures have been characterized in respect of associated deformation and fracture
mechanisms.
As regards Q&P studies, the effects of Si alloying on carbon partitioning, carbide formation
and austenite decomposition during Q&P treatment in 0.4 wt.% carbon steels with tailored Si
content have been examined using in-situ dilatometric analysis and qualitative and quantitative
microstructural characterization [3,4]. Based on the results of Q&P simulations, an innovative
processing route comprising multi-pass, thermomechanical rolling followed by direct quenching
and partitioning (DQ&P) was designed for the 0.4 wt.% C steels resulting in tough, ultrahigh-
strength steels with high uniform and total elongations. The results revealed an excellent
combination of mechanical properties comprising high yield (~1000 - 1200 MPa) and tensile
(~2100 - 2300 MPa) strengths, good elongation (~11 - 13%), and moderate 28J impact toughness
transition temperature (T28J) (- 5 to +12°C) [5,6]. Straining of austenite prior to DQ&P led to an
extensive refinement of the final martensitic-austenitic structure. Formation of nanoscale lath-
martensite and fine film-like retained austenite structures (as shown in Figs. 1a,b) enabled the
observed improvement of mechanical properties. Besides the formation of nano-twinned
martensite, inter-lath austenite and transition carbides were comprehensively characterized. 3D
Atom probe tomography (APT) and high-resolution transmission electron microscopy (HR-TEM)
were employed to study the carbide precipitation associated with quenching and partitioning
treatment. Different types of carbides resulting mainly from tempering of martensite and/or partial
decomposition of carbon-enriched austenite have been characterized. The results revealed
formation of transition carbides h (Fe2C) that were stable even at high partitioning temperatures
(300 °C) in the case of steel with 1.5 wt. % Si. However, these h carbides formed in the steel with
1
0.75 wt. % Si were only partially stable, as a fraction of h carbides decomposed to q (Fe3C) (Figs.
1d-f). In the case of steel with 0.25 wt. % Si, only the existence of q precipitates was evident [3].
Fig. 1: TEM BF (a,d,e), DF (b,f) images and corresponding SADP of RA (c) of 0.75 wt. % steel.
Furthermore, the size of q precipitates was found to be relatively large compared to h
carbides, suggesting that the growth of cementite occurred during partitioning at 300 °C. The
carbon atom map in Fig. 2a shows some carbon agglomerated regions in the 0.75 wt. % Si steel
specimen. Owing to the respective stoichiometries of different carbides, a carbide with a carbon
content of about 25 at. % can be claimed as q and the other one with a carbon content of about 31
at. % can be claimed as h-carbide. Apart from carbides, segregation of carbon clusters in
martensite lath boundaries was clearly revealed by APT.
Fig. 2: (a,b) Iso-concentration surfaces & (c,d) corresponding proxigrams of 0.75 wt. % Si steel.
Additionally, an attempt has been made to detect the possible formation of a metastable,
hexagonal omega (w) phase within the boundaries of nano-twinned high carbon martensite. Fig.
3a represents a magnified image of twinned martensite structure in 1.5 wt. % Si steel. The selected
area diffraction pattern (SAED) on [011]BCC zone axis (inset in Fig. 3b) shows the twinned regions
having a (211) twin plane aligned in [111] twinning direction. In addition, there are two other spots
found to be present along with the (211) plane. The dark field image from one of the extra spots
showed the existence of nanosized thin plates in between the twinning planes (Fig. 3b). The
crystals in this twinned martensite most likely correspond to ω phase [7].
2
Fig. 3: (a) TEM bright, and (b) dark field images of DQ&P processed 1.5 wt. % Si steel.
Fig. 4: SEM micrographs of non-deformed and ausformed medium C steel specimens.

Our second study focussed on developments of medium C nanostructured bainitic steels
consisting of extremely fine bainite plates (<50 nm) together with fine interlath films of RA,
through specific composition and process designs with the primary aim to accelerate the bainitic
transformation kinetics. Among different methodologies, one approach to greatly refine the
bainitic ferrite plates is to apply isothermal bainite transformation below Ms in steels, which has
been explored with various carbon contents. In a recent study, we systematically investigated the
characteristics of nanostructured bainite formed via isothermal holding above and below Ms (Ms =
280 °C) following ausforming. A series of experiments combining ausforming (~ 0.5 true strain)
and isothermal holding at the same temperature were conducted at five different temperatures in
the range 235 - 325°C. The results suggest that ausforming above Ms reduced the time for onset of
bainite transformation, whereas the effect was just the opposite below Ms with the onset times
delayed by introducing prior ausforming (Fig. 4). However, significant refinement of bainitic
ferrite plates and retained austenite films was observed in the ausformed samples below Ms,
besides noticeable increase in hardness. Lab rolling experiments comprising multi-pass
thermomechanical rolling followed by ausforming below Ms resulted in an excellent combination
of mechanical properties (yield strength of ~900 - 1150 MPa and tensile strength ~1600 - 1800
MPa, elongation ~16 - 18%), comparable to 0.4C DQ&P steels.
As a potential candidate for automotive applications, medium Mn steels have received
considerable interest among the 3rd generation AHSS owing to their excellent combination of high
3
strength and good ductility. The key factor in governing a good combination of strength and
ductility, however, lies in properly controlling the volume fraction and stability of RA that must
be finely divided in the matrix and hence, becomes a challenging objective in designing new
processing routes. Though the effects of different methods such as pre-existing austenite,
deformation and high temperature partitioning have been studied individually, a combination of
these process parameters on the processing and intercritical annealing of medium Mn steels has
still not been systematically investigated. A new combination of factors enhancing the stabilization
of austenite, including pre-existed austenite among quenched martensite, prior deformation, and
partitioning at high temperatures was employed to create a multi-component refined
microstructure in Fe-4Mn-0.31C-2Ni-0.5Al-0.2Mo steel [8]. The results demonstrated that the
combinatorial approach will be beneficial in accelerating austenite stabilization and microstructure
refinement. The final microstructure of the specimen after 0.4 strain deformation of 73%
martensite–27% austenite at 250 °C and subsequent partition-annealing at 650 °C for 20 min was
composed of ultrafine-grained equiaxed ferrite, 32% RA (avg. grain size of 250 nm) along with
some fresh martensite during final cooling and few carbide precipitates, as shown in Fig. 5.
(a) (b)
Fig. 5: EBSD IQ & Phase maps of the deformed & partition-annealed medium-Mn steel sample.
Acknowledgement
This funding of this research activity under the auspices of Genome of Steel (Profi3) project by
the Academy of Finland through grant # 311934 is gratefully acknowledged.
References
1) M.C. Somani, D.A. Porter, L.P. Karjalainen, D.K. Misra, Evaluation of DQ&P Processing Route for the
Development of Ultra-high Strength Tough Ductile Steels, Int. J. Metall. Eng. (2013)154–160.
2) Raabe, D., Sun, B., Kwiatkowski Da Silva, A. et al. Current Challenges and Opportunities in Microstructure-
Related Properties of Advanced High-Strength Steels. Metall Mater Trans A 51, 5517–5586 (2020).
3) I. Miettunen, S. Ghosh, M.C. Somani, S. Pallaspuro, J. Kömi, Competitive mechanisms occurring during Q&P of
three silicon variants of 0.4 wt.% carbon steels, J. Mater. Res. Technol 11 (2021) 1045-1060.
4) I. Miettunen, S. Ghosh, M.C. Somani, S. Pallaspuro, D. Porter, J. Kömi, Effect of Si content on the decomposition
of austenite in 0.4C steel during Q&P treatment. Mater. Sci. Forum 1016 (2020) 1361-1367.
5) S. Ghosh, I. Miettunen, M.C. Somani, J. Kömi, D. Porter, Nanolath martensite-austenite structures engineered
through DQ&P for developing tough, ultrahigh strength steels, Mater. Today Proceed. 46 (2021) 2131-2134,
6) S Ghosh, P Kaikkonen, V Javaheri, A Kaijalainen, I Miettunen, M Somani, J Kömi, S Pallaspuro, Design of tough,
ductile DQ&P AHSS with tailored Si content, J Mater. Res. Technol., 17, 2022, 1390-1407.
7) T. Liu, D. Zhang, Q. Liu, Y. Zheng, Y. Su, X. Zhao, J. Yin, M. Song, D. Ping. A new nanoscale metastable iron
phase in carbon steels, Sci. Rep. 5 (2015) 15331
8) S. Sadeghpour, M.C. Somani, J. Komi, L.P. Karjalainen, A new combinatorial processing route to achieve an
ultrafine-grained, multiphase microstructure in a medium Mn steel, J. Mater. Res. Tech. 15 (2021) 3426-3446.
4
Formation of coarse columnar austenite grains during solidification of peritectic steels
Munekazu Ohno1,*
1
Division of Material Science and Engineering, Hokkaido University, Sapporo, Hokkaido 060-8628, Japan
*email: mohno@eng.hokudai.ac.jp
Keywords: peritectic solidification, continuous casting, coarse columnar grains, phase-field simulations, directional solidification
Coarse columnar γ grain (CCG) structure is formed in the vicinity of continuously cast (CC) slab surface of peritectic
solidified carbon steels. Formation of the CCG structure is a serious problem, because it causes occurrence of surface cracking of
CC slabs1,2). Elucidation of formation mechanism of the CCG structure and also its kinetics is of great importance for production
of high-quality CC slabs.
It was found by means of a rapid unidirectional solidification experiment that
the formation of CCG structure is ascribed to a discontinuous grain growth3,4). The
microstructure during the solidification is schematically shown in Fig. 1. This was
drawn based on the microstructure observed in a sample quenched during rapid
directional solidification experiment3), the cooling condition of which is close to that in
continuous casting. The columnar dendrite of δ phase grows in the direction of
temperature gradient, which is followed by the formation of γ grain structure in δ
dendrite. Fine columnar γ grains (FCG) are formed ahead of CCGs. Importantly, the
change from FCG to CCG structures is discontinuous. In other words, there is a clear
distinction between FCG and CCG regions and, hence, the boundary between these
regions, called FCG/CCG region boundary (FCRB), can be identified. The temperature
at FCRB is close to the equilibrium temperature Tγ below which γ single phase is stable.
Namely, in the case of hyperperitectic steels, the liquid phase exists around FCG,
suppressing the coarsening of FCG. The liquid phase in FCG region also pin the motion
of FCRB in the direction of temperature gradient. As the cooling proceeds, FCRB
moves upward immediately after the liquid ahead of CCG vanishes, finally yielding Fig. 1 Schematic illustration of
the CCG structure. CCG formation process3).
Prevention of the formation of CCG structure in the CC slabs requires
understanding the kinetics of discontinuous grain growth process. It is especially important to quantitatively ascertain the critical
condition of the occurrence of the discontinuous grain growth. The purpose of this study is to elucidate the critical condition of
formation of CCG structure. To this end, the discontinuous grain growth process from FCG structure was systematically
investigated by means of phase-field simulations, mold casting experiment and directional solidification experiment.
The phase-field model is a diffuse interface model in which the entity of boundary is described by the spatial
distribution of phase-field variable. It enables description of moving boundary without explicit tracking of the position of boundary.
In this study, we utilized the multi-phase-field model proposed by Steinbach and Pezzola5) and further developed for the case of
grain growth by Kim et al.6). In this model, the grain structure is characterized by the spatial distribution of a set of phase field
variables {𝜙𝜙𝑖𝑖 (𝒓𝒓, 𝑡𝑡)}. 𝜙𝜙𝑖𝑖 represents a probability of finding a grain having a crystallographic orientation i (i = 1, 2, …, N). Here,
𝒓𝒓 is the spatial coordinates, t is the time and N is the total number of grain orientations considered in the simulation. The time
evolution of 𝜙𝜙𝑖𝑖 is described by the following equation
𝑁𝑁
𝜕𝜕𝜙𝜙𝑖𝑖 2𝐿𝐿 𝛿𝛿𝛿𝛿 𝛿𝛿𝛿𝛿
= − � 𝑠𝑠𝑖𝑖 𝑠𝑠𝑗𝑗 � − �
𝜕𝜕𝜕𝜕 𝑛𝑛 𝛿𝛿𝜙𝜙𝑖𝑖 𝛿𝛿𝜙𝜙𝑗𝑗
𝑗𝑗≠𝑖𝑖
where 𝐿𝐿 is the phase-field mobility, 𝑠𝑠𝑖𝑖 is a step function with 𝑠𝑠𝑖𝑖 = 1 for 𝜙𝜙𝑖𝑖 > 0 and 𝑠𝑠𝑖𝑖 = 0 otherwise and 𝑛𝑛 =
∑𝑁𝑁
𝑖𝑖 𝑠𝑠𝑖𝑖 (𝒓𝒓, 𝑡𝑡). The functional derivative on the right-hand side is given as,

𝑁𝑁
𝛿𝛿𝛿𝛿 𝜖𝜖 2
= � � ∇2 𝜙𝜙𝑘𝑘 + 𝜔𝜔𝜙𝜙𝑘𝑘 �
𝛿𝛿𝜙𝜙𝑖𝑖 2
𝑘𝑘≠𝑖𝑖
where 𝜖𝜖 is the gradient energy coefficient and 𝜔𝜔 represents the height of the parabolic potential for the energy barrier between
different grains. These parameters are related the grain boundary thickness 𝑊𝑊, and the grain boundary energy 𝜎𝜎, as given by
𝜖𝜖 = 2√𝑊𝑊𝑊𝑊 ⁄𝜋𝜋 and 𝜔𝜔 = 4𝜎𝜎⁄𝑊𝑊 . In this model, the anisotropy of the grain boundary energy and mobility is not taken into
account. The above-mentioned equation reproduces the curvature-driven motion given as 𝑣𝑣 = −𝑚𝑚𝑚𝑚𝑚𝑚 where 𝑣𝑣 is the local
velocity of grain boundary, 𝑚𝑚 is the grain boundary mobility and 𝜅𝜅 is the local curvature of grain boundary. The phase-field
mobility 𝐿𝐿 is given as 𝐿𝐿 = 𝑚𝑚𝑚𝑚⁄𝜖𝜖 2 .
We employed the active parameter tracking (APT) algorithm6) to perform simulations of coalescence-free grain growth.
Two-dimensional (2D) system was divided into 1000 × 500 grid points for x- and y-directions with the grid spacing of 1 mm,
respectively, and the periodic boundary condition was set to x-direction. The initial system consists of FCGs that are surrounded
by the liquid phase above 𝑇𝑇𝛾𝛾 . The simulations were performed for different cooling conditions specified by the temperature
gradient 𝐺𝐺 in y-direction and the cooling rate 𝑇𝑇̇. Also, three-dimensional computations were performed for some set of 𝐺𝐺 and
𝑇𝑇̇.
Figure 2(a) and (b) shows the grain structures simulated for 𝐺𝐺 = 1.4 × 104 and 6.0 × 103 K/m, respectively7).
The initial FCG structure is the same and the cooling rate was set to 𝑇𝑇̇ = 1 K/s in both cases. 𝑇𝑇𝛾𝛾 is located at around the center
height in both cases. In Fig. 2(b), the grains grow from the initial FCG structure in a continuous way and the grain structure below
𝑇𝑇𝛾𝛾 consists of relatively equiaxed grains, the aspect ratio of which is smaller than the one of initial FCG. However, the FCGs
discontinuously changes to CCGs in Fig. 2(a) and this process results in the formation of the CCG structure. Therefore, the grain
growth mode and the final grain structure are largely dependent on the cooling condition. The relation between the growth mode
(final grain structure) and the cooling condition, obtained from the phase-field simulations, is summarized in Fig. 2(c). The dashed
line separates the growth mode and this line is given by the relation 𝑉𝑉𝑇𝑇 = 𝑉𝑉𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹 where 𝑉𝑉𝑇𝑇 = 𝑇𝑇̇⁄𝐺𝐺 determined by the cooling
condition and 𝑉𝑉𝐹𝐹𝐹𝐹𝐹𝐹𝐹𝐹 is the velocity of FCRB determined by the curvature-driven growth. The validity of this relation was
confirmed by 2D simulations for different initial microstructure, different composition and also by 3D phase-field simulations.
Moreover, the validity of the relation was investigated by means of mold casting experiments7) and directional solidification
experiment8). These investigations confirmed that this relation is quantitatively correct. Therefore, it is expected that the formation
of CCG structure in CC slabs of peritectic carbon steels can be avoided based on this relation9).
Fig. 2. Grain structures obtained by phase-field simulations for 𝑇𝑇̇ = 1 K/s, (a) 𝐺𝐺 = 1.4 × 104 and (b) 6.0 × 103 K/m.
(c) The relation between the grain growth mode and the cooling condition obtained from the phase-field simulations7).

Note that the above-mentioned analyses focused only on the grain growth from the FCG structure and the formation
process of FCGs was not investigated. According to time-resolved X-ray imaging studies, the δ to γ transformation in carbon
steels generally occurs not via the peritectic reaction but via massive-like transformation and, importantly, fine γ grains are
produced through the massive-like transformation10). Such fine grains should be the origin of FCG structure. Also, it was shown
that the massive-like transformation induces strains in the γ grains and the strains are released during coarsening. Therefore, the
critical condition of CCG formation must include effects of strain in the γ grain, which should lead to the improvement of
prediction accuracy of the formation condition of CCG structure.
References
1) Y. Maehara, K. Yasumoto, Y. Sugitani, K. Gunji: ISIJ Int. 25 (1985) 1045.
2) L. Schmidt, Å. Josefsson: Scand J. Metall. 3 (1974) 193.
3) S. Tsuchiya, M. Ohno, K. Matsuura, K. Isobe: Acta Mater. 59 (2011) 3334.
4) S. Tsuchiya, M. Ohno, K. Matsuura: Acta Mater. 60 (2012) 2927.
5) I. Steinbach, F. Pezzola: Physca D 134 (1999) 385.
6) S.G. Kim, D.I. Kim, W.T. Kim, Y.B Park: Phys. Rev. E 74 (2006) 061605.
7) M. Ohno, S. Tsuchiya, K. Matsuura: Acta Mater. 59 (2011) 5700.
8) M. Ohno, M. Maruyama, K. Matsuura: Acta Mater. 61 (2013) 7334.
9) M. Ohno, S. Tsuchiya, M. Matsuura: ISIJ Inter. 55 (2015) 2374.
10) H. Yasuda, T. Suga, K. Ichida, T. Narumi and K. Morishita: IOP Conf. Ser. Mater. Sci. Eng. 861 (2020) 012051.

The effects of grain boundary character distribution on the mechanical properties of a
316L stainless steel
Shuang Xia1,*, Qin Bai2, Zheng Zhuo1, Kai Liu1 and Bangxin Zhou1
1
School of Materials Science and Engineering, Shanghai University, Shanghai 200072, People’s Republic of China
2
Key Laboratory for Microstructures, Shanghai University, Shanghai 200444, People’s Republic of China
*email: xs@shu.edu.cn
Keywords: 316L stainless steel, grain boundary engineering, tensile mechanical properties, strain rate; dynamic strain aging,
dynamic recrystallization
316L stainless steel has been widely used due to a combination of good corrosion resistance and mechanical properties.
However, with the stainless steel service conditions becoming increasingly complex, the demands for its performance are
increasing in many industrial fields. Especially for stainless steel as a structural material is concerned, the need to further
improve the mechanical properties should be considered. As one of the important microstructural features of polycrystalline
materials, grain boundary (GB) has an important influence on the performance of stainless steels. Grain boundary engineering
(GBE) can enhance the grain-boundary-related properties of metal materials which have face centered cubic (FCC) structure
with low stacking fault energy (SFE) by changing the twin-induced grain boundary character distribution (GBCD). In this
work, GBE was applied to a 316L stainless steel. Subsequently, the effects of the GBCD formed during GBE on the tensile
mechanical properties at room and elevated temperatures (300 ℃ ~ 900 ℃) at different strain rates (4×10-2 s-1 ~ 4×10-5 s-1)
were investigated. The results are as follows:
The proportion of low-ΣCSL (Σ≤29, coincidence site lattice) GBs can be increased to more than 70% in the GBE
specimen. Meanwhile, the large-size highly-twinned grain-cluster microstructure was formed through the treatment of GBE.
All of the grains inside of this kind of cluster have Σ3n (n=1, 2, 3…) mutual misorientations 1). During the recrystallization
process, the Σ3n GBs are developed associating with the recrystallization nuclei growth. After full recrystallization, the
specimens were in the grain growth stage. The proportion of low-ΣCSL GBs decreased with grain growth due to being swept
away of the existing low-ΣCSL GBs.
The GBE samples with enhanced proportion of Σ3n GBs displayed increased uniform elongation during tensile test at
room temperature, and the differences in the uniform elongations between the GBE and Non-GBE specimens
(UEGBE–UENon-GBE) increase with the decreasing of strain rates 2). The Σ3 GBs are effective for improving the extent of
uniform plastic deformation of the GBE specimens under the condition of low strain rates. During the tensile deformation at
room temperature, the GBE specimen showed lower hardness and more homogeneous local strain distribution. The abundant
Σ3 GBs in the interior of the grain-clusters have weaker interaction with dislocation. Dislocation slip can easily transfer most
Σ3 twin boundaries, preventing the piling up of dislocations. The large and deep dimple structure also indicates the improved
plasticity after GBE.
The results of high temperature tensile tests show that the high proportion of Σ3n GBs of GBE samples not only
increases the elongations but also affects the dynamic strain aging (DSA) behavior in the temperature range of 300 -500C °
and dynamic recrystallization (DRX) at 900 C ° . Delayed occurrence of serrated flow as a result of DSA was observed in the
GBE samples as compared to the Non-GBE samples. The GBE samples have smaller serrations on the stress-strain curves,
especially at lower strain rate. The GBE specimen has a more homogeneous strain distribution leading to better plasticity at
lower strain rate. When the test temperature increased to 700 C ° , the total elongations of GBE samples show a greater extent
of increase. Higher dynamic recrystallization (DRX) fractions were observed in the GBE samples as compared to the
Non-GBE samples during tensile tests at 900 C ° . The grains of DRX have an obvious Goss texture inside the deformed grains,
which have <001> and <111> fiber textures. The dynamically recrystallized grains have higher values of Schmid factor,
which can facilitate further deformation. The features of the high temperature fracture surface of GBE samples also suggested
improved plasticity of GBE specimens.

Acknowledgement
This work was performed under the support of National Key Research and Development Program of China (Grant
No.2018YFE0122100) and National Natural Science Foundation of China (Grant No. 51871144)
References
1) Z. Zhuo, S. Xia, Q. Bai and B. Zhou: J. Mate. Sci. 53(2018) 2844–2858.
2) S. Xia, B. Zhou and W. Chen: Metall. Mater. Trans. A, 40A (2009)3016-3030.

Characterization of recrystallization behavior in pure iron and low-carbon steel
by three-dimensional microstructural analysis
Toshio Ogawa1,*, Kengo Horiuchi1, Zhilei Wang1 and Yoshitaka Adachi1
1
Department of Materials Design Innovation Engineering, Nagoya University, Nagoya, Aichi 464-8603, Japan
*email: ogawa.toshio@material.nagoya-u.ac.jp
Keywords: recovery, recrystallization, three-dimensional analysis, Avrami exponent
1. Introduction
Controlling recrystallization is important for controlling the mechanical properties of iron and steel. Moreover,
three-dimensional (3D) analysis of recrystallized ferrite grains is needed to precisely understand the recrystallization behavior.
It is well known that the presence of solute carbon retards recovery in iron and steel1). This means that the recovery rate in
low-carbon steel is lower than that in pure iron. However, it is unclear if the 3D morphology of recrystallized ferrite grains
varies when the presence of solute carbon retards the recovery progress. Thus, we performed a 3D analysis of recrystallized
ferrite grains in pure iron and low-carbon steel. In addition, we attempted to propose a mechanism for 3D microstructural
evolution during the recrystallization process.
2. Materials and Methods

Pure iron and low-carbon steel were used in this study. After hot-rolling, the specimens were cold-rolled at a cold
reduction rate of 80%, annealed for various durations, and then water-quenched to room temperature (298 K ± 2 K) within 2 s
of being removed from the furnace. Vickers hardness tests were conducted (n = 3) under an applied load of 9.8 N for 10 s to
estimate the recrystallized fraction.
The microstructures were observed by fully automated serial sectioning with a 3D microscope. The
serial-sectioned images were used to create 3D images. The 3D recrystallized ferrite grains were constructed using Avizo Fire
or Amira software. The length, breadth, and width of the 3D recrystallized ferrite grains could be obtained. The length
corresponds to the maximum Feret diameter, breadth corresponds to the maximum horizontal measurement (taken at right
angles to the length), and the width corresponds to the minimum Feret diameter of the 3D recrystallized ferrite grains.
3. Results and Discussion

In several materials, the Johnson–Mehl–Avrami–Kolmogorov (JMAK) theory2) has been used for the 3D analysis
of recrystallization. The JMAK equation is expressed as follows:
X = 1 – exp (–ktn) (1)
where X represents the recrystallized fraction, k represents a constant, t represents time, and n represents the JMAK exponent.
A previous study reported that the value of n in the JMAK equation corresponds to the growth direction of the recrystallized
grains2). The value of n is assumed to be between 1 and 2, 2 and 3, or 3 and 4 when the growth direction of the recrystallized
grains is 1D, 2D, or 3D, respectively. Figure 1 shows the JMAK plot of the recrystallization kinetics in pure iron3) and
low-carbon steel4). In the case of pure iron, the values of n in the early and later stages of annealing were calculated to be 1.86
and 0.37, respectively. Howver, the value of n was calculated to be 2.33 in low-carbon steel. These results indicate that the
growth directions of the recrystallized ferrite grains in pure iron and low-carbon steel are likely to be close to 1D and 2D,
respectively.
Figure 2 demonstrates a quantitative evaluation of the 3D recrystallized ferrite grains in pure iron3) and low-carbon
steel4). In the case of pure iron, the 2D and/or 3D growth of the recrystallized ferrite grains was confirmed by the 3D analysis.
In contrast, the morphology of recrystallized ferrite grains in low-carbon steel was approximately 2D. These results suggest
that the value of n does not necessarily reflect the real grain growth direction in pure iron, whereas that is consistent with the
3D morphology of recrystallized ferrite grains in low-carbon steel. It is well known that the presence of solute carbon leads to
the slow recovery in iron and steel1). Thus, it appears that the recrystallization driving force decreases due to the acceleration of
the recovery in pure iron. This leads to the inconsistency between the theoretical and experimental results in pure iron. In

contrast, the change in the recrystallization driving force due to the recovery progress can be neglected in low-carbon steel,
because the presence of solute carbon retards the recovery. As a result, the theoretical and experimental results for low-carbon
steel are consistent.
1.5 1
2D 3D
1
0.8
0.5
n = 2.33
n = 0.37
ln(-ln(1-X))
Breadth/Length
0 0.6
-0.5
-1 n = 1.86 0.4
-1.5
0.2
3)
-2 Pure iron
Low-carbon steel
4) 1D ◯Pure iron3)
● Low-carbon steel4)
-2.5 0
0 1 2 3 4 5 6 0 0.2 0.4 0.6 0.8 1
ln(t) Width/Length
Fig. 1 JMAK plot of recrystallization kinetics. Fig. 2 Growth direction of recrystallized ferrite grains.
4. Conclusions
We investigated the 3D morphology of the recrystallized ferrite grains in pure iron and low-carbon steel, and the
following results were obtained.
(1) In the case of pure iron, the Avrami exponent was 1.86 and 0.37 in the early and later annealing stages,
respectively. Whereas, Avrami exponent in low-carbon steel was 2.33.
(2) The 2D and/or 3D growth of the recrystallized ferrite grains was confirmed in pure iron. In contrast, the 2D
growth of the recrystallized ferrite grains was mainly confirmed in low-carbon steel.
(3) The interaction between the recovery and recrystallization was attributed to the inconsistency between
theoretical and experimental results for pure iron.
Acknowledgement
This study was supported in part by JSPS KAKENHI Grant Number 21K14423.
References
1) N. Sugiura, N. Yoshinaga, K. Kawasaki, Y. Yamaguchi, J. Takahashi and T. Yamada: Tetsu-to-Hagané 94 (2008) 179-187.
2) J. E. Burke and D. Turnbull: Progress in Metal Physics 3 (1952) 220-292.
3) T. Matsui, T. Ogawa and Y. Adachi: Results in Materials 1 (2019) 100002.
4) K. Horiuchi, T. Ogawa, Z. Wang and Y. Adachi: Materials 14 (2021) 4154.

Primary recrystallization texture development in grain-oriented silicon steel
Y.J. Yang1, Z.Y. Xu1,2, H.B. Zhang1, M.H. Wu1, Y.H. Sha2,*, and G.B. Li1,*
Baoshan Iron & Steel Cooperation Limited, Shanghai 201999, China
1
2
Key Laboratory forAnisotropy and Texture of Materials (Ministry of Education), Northeastern University, Shenyang 110819,
China
*email: lgb@baosteel.com; yhsha@mail.neu.edu.cn
Keywords: grain-oriented silicon steel; primary recrystallization; normalized annealing; microstructure; Goss
Grain-oriented silicon steel is the critical material for transmission and distribution transformer cores. It is well
known for long and complex manufacturing procedure with sharp secondary recrystallization Goss ({110}<001>) texture as
the final purpose1). Primary recrystallization microstructure and texture play a key role for secondary recrystallization texture.
In view of the significant inheritance of microstructure and texture2), the normalization annealing of hot bands is an effective
way to regulate primary recrystallization microstructure and texture, especially for low-temperature slab heating process.
During normalization, the occurrence of recrystallization not only improves the microstructure uniformity but also changes
the texture of hot bands. In contrast with the effect of normalization on macro-texture of primary recrystallization3-5), the
micro-texture and collaborative control of microstructure and texture have received less attention. In this study, the effect of
normalized annealing was analyzed to develop a more reasonable path for optimal control of primary recrystallization process
in grain-oriented silicon steel.
Industrial Fe-3.25 wt. % Si grain-oriented silicon steel slabs were heated at 1100 ℃ and hot rolled into 2.7 mm
bands. Then HR bands were normalized at 900 ℃ (L-NA) and 1100 ℃ (H-NA) for 5min. Cold rolled sheets with a reduction
of 87% were annealed at 830 ℃ for 3 min. Micro-texture analysis was carried out using HKL Technology Channel 5
software by EBSD on a JEOLJSM-7001F scanning electron microscope .
As shown in Figure 1, the L-NA and H-NA bands present coarse pancake grains and equiaxed grains respectively,
in contrast to fine elongated grains in HR bands. Goss texture in subsurface of L-NA bands is more enhanced than H-NA
bands, which can be attributed to the different recrystallization mechanism during normalization. Continuous recrystallization
during L-NA produces pancake grains and strong Goss texture. Discontinuous recrystallization during H-NA results in
equiaxed grains and weak Goss texture with few accurate Goss grains. The center layer in HR bands is dominated with strong
{001}<110> texture, which is sharpened and dispersed by L-NA and H-NA respectively due to the difference in
recrystallization mechanism.
Figure 1 EBSD analysis of HR (a), L-NA(b) and H-NA(c) bands

The dependence of primary recrystallization microstructure on normalization is shown in Figure 2. Fine grains are
obtained after primary recrystallization when cold rolled directly from HR bands. The primary recrystallization microstructure
is characterized by a larger grain size and dispersion width with the increasing normalization temperature. The grain size
distribution has an evident gradient through sheet thickness with coarse grains at center and subsurface layers for L-NA and
H-NA, respectively. The distinct grain size at center layer results from the the difference in grain morphology and sharpening
of {001}<110> texture between L-NA and H-NA bands. This indicates that the discontinuous recrystallization nucleation at
grain boundaries during normalization is favorable to grain refinement especially for the textures with low Taylor factors.
Figure 2 Primary recrystallization microstructure from HR (a), L-NA(b) and H-NA(c) bands
The area fraction of primary recrystallization Goss texture is closely related with HR, L-NA and H-NA bands, as
shown in Figure 3. L-NA and H-NA increases and decreases Goss texture in subsurface compared with HR bands,
respectively. Preferred nucleation at grain boundaries during H-NA tends to strengthen  fiber (<111>//ND) with higher stored
strain energy and weaken Goss texture in either small or large deviation angle ranges. Continuous recrystallization during
L-NA is evidently favorable for the nucleation and growth of Goss grains. After primary recrystallization, both L-NA and
H-NA can increase Goss texture. The coarse equiaxed grains after H-NA are responsible for the abundant shear bands in cold
rolled sheets and high nucleation rate of Goss texture during primary recrystallization. The pancake grains are not so efficient
in the formation of shear bands during cold rolling as equiaxed grains, and the increase of Goss texture after primary
recrystallization by L-NA is mainly due to the enhanced Goss texture in L-NA bands. Furthermore, the deviation angle
distribution of primary recrystallization Goss texture was statistically analyzed in Figure 5. Goss grains have a higher fraction
in small deviation angle range (0~10°) for L-NA, while the lowest fraction in small deviation angle range occurs without
normalization annealing. This suggests that shear bands formed within the normalized pancake grains can provide more
accurate Goss nuclei, resulting from the smaller deviation angle of Goss texture as well as the straight grain boundaries in
L-NAbands.
Figure 3 Fraction of Goss grains in HR, L-NAand H-NAbands and primarily recrystallized sheets

Figure 4 Deviation angle distribution of Goss grains in primary recrystallized sheets
Therefore, Goss texture at subsurface and microstructure through sheet thickness after primary recrystallization
have a strong correlation with the normalized annealing of hot rolled bands in grain-oriented silicon steel. The regulation of
hot rolled bands needs to be carried out based on the recrystallization mechanism in normalized annealing so as to optimize
the microstructure gradient through sheet thickness and enhanced Goss texture in subsurface with small deviation angle after
primary recrystallization.
Acknowledgement
This work was performed under the support of the National Key Research and Development Program of China
(No. 2016YFB0300305) and the National Natural Science Foundation of China (No. 51931002).
.
References
1) Hayakawa Y. Science and Technology ofAdvanced Materials, 2017, 18(01): 480-497.
2) Matsuo M, Sakai T, SugaY. Metallurgical TransactionsA, 1986, 17A: 1313-1322.
3) Fukagawa T,Yashiki H. Transactions of the Iron & Steel Institute of Japan, 2007, 40(4): 402-408.
4) Chang S K. Materials Science and EngineeringA, 2007, 452: 93-98.
5) Shin S M, Birosca S, Chang S K, B. C. De Cooman. Journal of Microscopy, 2010, 230(03): 414-423.

Higher Performance of Special Steel Bars and Wire Rods
by Inclusion Morphology Control
Yutaka Neishi1,*
1
High Carbon Steel Research Lab., Steel Research Lab., Nippon Steel Corporation, Futtsu, Chiba, 293-8511, Japan
*email: neishi.58e.yutaka@jp.nipponsteel.com
Keywords: Inclusion morphology, Rolling contact fatigue, Artificial defect, Micro CT imaging
Introduction
Higher fuel efficiency and less CO2 emission have become increasingly required for road vehicles in recent consideration
of conservation of the global environment. Accordingly, it is important for steel products to be energy-saving, compact and
light-weight. To realize these needs, the steel bars and wire rods must be improved to have better functional properties and
higher strength. Steel bars and wire rods undergo various manufacturing processes such as forging and cutting on the user
side. Therefore, it is also necessary to improve workability and machinability of steel.
Control technique of nonmetallic inclusion morphology in steels is one of the effective solutions to realize high
performance and high strength 1), 2). In this presentation, we mainly introduce research examples on the extension life of
bearing with a focus on the inclusion morphology control3).
Bearings are the automotive parts subjected to rolling and sliding contact under high loaded conditions. It is well
known that rolling contact fatigue (RCF) life is improved by reducing the size of nonmetallic inclusions in the steels 4).
However, there is little research regarding the morphology effect on the RCF life 1), 5). This work focused on the influence of
the inclusion shape on the RCF life. Crack initiation and propagation in the steels having two different shapes of inclusions
and artificial defects during RCF were studied using cross-section observations and SR micro-CT imaging. We found that
RCF life was well correlated with inclusion length 6), 7).
The effect of inclusion morphology on the RCF life

Since attention was paid to the influence of the inclusion shape on the RCF life, we have prepared carburized
JIS-SCM420 (SAE4320 equivalent) steels which contained two different shapes of MnS. Steel A contained stringer-type
MnS and Steel B contained spheroidized-type MnS. We produced two different steels by vacuum induction melting, and
their ingots were forged at 1523 K into 80 mm diameter bars. The forged bars were normalized at 1173 K for 3.6 ks. The
chemical compositions of both steels are given in Table 1, and the typical
shapes of MnS observed in the forged bars are shown in Fig. 1. After the Steel A Stringer type
normalized treatment, we machined forged bars for the RCF test specimen. of MnS
RCF test specimens were taken from the center of the forged bar in the
20µm
longitudinal direction.
Speroidized type
Table 1 Chemical composition of steels (mass%) of MnS
Mark C Si Mn P S Cr Mo Ca
Steel B
20µm
Steel A 0.20 0.19 0.78 0.015 0.018 1.18 0.20 －
Steel B 0.20 0.19 0.78 0.013 0.017 1.18 0.19 0.0026
Fig.1 Optical micrographs of typical shapes
of MnS inclusions
RCF specimens were gas-carburized at 1203 K for 32.4 ks in a sealed quench furnace to a surface carbon content of
0.8 %, and then directly quenched in oil from 1093 K. After quenching, all specimens were tempered at 453 K for 7.2 ks.
We measured the hardness profile in the plane which was parallel to the tangential line of the rolling track center. Hard layer
thickness is defined as the depth from the surface where hardness reaches a value of 550 HV. The surface hardness of the
specimens was around 750 HV and the hard layer thickness was 1.5 mm for each steels.
The gas-carburizing and tempering treatment develops the residual stress at the surface of the specimen. We measured
the residual stress distribution in the subsurface of specimens by X-ray diffraction method. Residual stresses of both steel

specimens showed similar distribution and the values of stress at all 99
depths were compressive. Therefore, it was concluded that, even if
Steel
A(Stringer
90 type MnS)
the shape of inclusion was different between Steel A and Steel B, the Steel
70 B(Spheroidize
effect of residual compressive stress on the initiation and the d type MnS)
Percent failed (%)

50
propagation of rolling contact fatigue crack was almost same.
Steel A Steel B
We conducted RCF tests using a thrust-type machine under the
20
constant load (maximum value of Hertzian stress was 5.3 GPa),
rotating speed of 1000 rpm and well-controlled lubricant conditions. 10
7
Surface roughness of the specimens, Ra, was about 0.02 μm. Nine 5
specimens of each steel which contained two different shapes of MnS 1.00E+05 1.00E+06 1.00E+07 1.00E+08
Life （cycle）
were tested. We defined the RCF life as the number of cycles to
failure. Figure 2 shows the Weibull distribution of the RCF lives. Fig.2 Weibull distribution of RCF lives
The Weibull distribution shows clearly that the RCF life of Steel B
containing spheroidized-type MnS was longer compared to that of
Steel A containing stringer-type MnS. L50 life of Steel B was about
three times longer than that of Steel A.
In order to identify the occurrence of RCF crack initiated from (a) Steel A（N=3.4×10 cycles） 6
(b) Steel B（N=9.2×10 cycles）
6
inclusions, we carried out SEM observation on the surface of the

Section A Section B
specimens after RCF tests. SEM images of cracks observed on the
surface of specimens are shown in Fig. 3-(a), (b). Cracks observed
on the surface of specimens were originated from MnS and these Perpendicular
Ball Rolling
Direction
Perpendicular
cracks were propagated to a direction perpendicular to the ball rolling

Ball Rolling crack
Direction crack
10μm 10μm
direction in both steels. The width of the originated MnS was 30μm
(c) Steel A 【Section A】 (d) Steel B 【Section B】
for each steel. It was well known that the local stress field was
Ball Rolling Stringer Spheroidized
developed at the inclusion during RCF test 8). Tensile stress in Direction type MnS type MnS
rolling direction was occurred near the surface of specimen, and shear Perpendicular
crack Shear crack Perpendicular
stress in rolling and depth direction was also occurred in subsurface of crack
Ball Rolling
specimen. It seems that this perpendicular crack was initiated due to Shear crack
Direction 20μm
50μm
the tensile stress in rolling direction or shear stress in depth direction.
The shape of the originated MnS must affect the initiation and Fig.3 SEM images of occurrences of
propagation behavior of these “perpendicular cracks”, since the value RCF cracks
of local stress would be changed due to the shape of inclusion. To investigate the initiation and propagation behavior of
these perpendicular cracks, we conducted the sectional observation. The results are shown in Fig. 3-(c), (d). In the section
of Steel A, it was found that the perpendicular crack was propagated along the sidewall of the stringer-shaped MnS 150μm in
length and reached to the end of the stringer-shaped MnS. While in the section of Steel B, the propagation behavior of the
perpendicular crack was different from that of Steel A. It was found that the perpendicular crack was initiated from
spheroidized MnS and propagated to the depth direction. The length of the perpendicular crack initiated from spheroidized
MnS reached 40μm in depth, but its depth was shorter than that of the perpendicular crack initiated from stringer-shaped
MnS.
Present results provided evidence suggesting a strong possibility that the propagation behavior of the perpendicular crack
is well correlated with the length of the originated MnS because the value of tensile stress in rolling direction and shear stress
in depth direction depends on the length of MnS. In other words, this result may support that the perpendicular crack grew
acceleratory in mode I and mode III as the MnS length increased.
Next, attention was focused on the shear crack in the subsurface. It was found that several shear cracks appeared
parallel to the shear stress in rolling direction and were located at equal spacing in the section of Steel A. The shear crack
located at the depth of the maximum shear stress (=100μm) was the longest. However, in the section of Steel B, it should be
noted that shear cracks in the subsurface were initiated from the tip of the perpendicular crack, not from spheroidized MnS,
and the depth of the occurrence of the subsurface crack was 40μm from the surface, which was not reached at the maximum

shear stress. These results may suggest that the shear crack in the subsurface was initiated from the perpendicular crack and
the wide-length of the perpendicular crack must dominate the initiation behavior of the shear crack in the subsurface.
Evaluation of the inclusion length effect on RCF crack behavior by using artificial defects
In order to clarify the RCF crack behavior, we evaluated RCF property of the material with artificial defects simulating
stringer type inclusions using synchrotron radiation micro-computed tomography (SR micro CT) imaging. We also carried
out RCF tests using a thrust-type machine under the constant load and well-controlled lubricant conditions. The specimens
were made of induction-hardened 0.55% carbon steel and the induction-hardened region had a Vicker’s hardness of 720 HV
and residual stress of -205 MPa. We introduced artificial defects of 15 m in diameter and between 30m and 200 m in
depth on the ball rolling track of the specimen by electro-discharge machining. The defect simulates a stringer type inclusion
(e.g. MnS) in terms of size and shape. The orientation of the defect, which is perpendicular to the rolling track, corresponds to
that of inclusions in thrust bearings.
Figure 4 shows the SEM images of artificial Ball rolling direction
Defect:φ15μm×L200μm
defect of 200 m in depth on rolling contact surface
after the RCF test. We found several small cracks
appeared due to the defect, almost perpendicular to the
rolling direction and the surface. We found that the Artificial
defect Vertical
length of the perpendicular cracks increases with the

crack
(b) N=1x105 cycles (c) N=1x106 cycles

number of cycles. (a) N=1x10 cycles
4
20μm
From the specimens used for the SEM
Fig. 4 SEM photos of artificial defect on rolling contact
observation, we took a small sample which included
surface after the RCF test. (a) N=1x104 cycles. (b) N=1x105
the artificial defect and inspected the sample by SR
cycles. (c) N=1x106 cycles.
micro CT imaging at SPring-8. The inspection region
in the sample has a square cross section, 0.5 mm x 0.5 mm. The size is (a) N =1 x 104 cycles
determined from the penetrative power of X-rays in Fe material. We
conducted CT imaging at the BL19B2 beam line of SPring-8, the most PV V
P PV depth
powerful synchrotron radiation facility in Japan. For a 3-D PV direction
SH VP H
reconstruction, a set of 900 radiographs of a sample were recorded at
Artificial
rotations of over 180 °, where each rotation angle was 0.5 °. Slice defect
Ball rolling Ball rolling
images were reconstructed from the series of the projection images by a direction direction
filtered-back projection algorithm. (b) N =1 x 106 cycles

We obtained images of the artificial defect and cracks shown in Fig.
5 by CT scanning. Two types of cracks were inspected around the PV VP PV
artificial defect. The first is a perpendicular crack, which propagates VP
SH
perpendicular to the surface along the artificial defect. The second is a SH SH Artificial
defect
shear crack in the subsurface, which propagates parallel to the surface Ball rolling Ball rolling
direction direction
from a point deep within the artificial defect. It was determined that
both perpendicular and shear cracks initiated before N= 1x104 cycles. Fig. 6 CT images of artificial defect and
A perpendicular crack propagated in the depth direction and cracks (P: perpendicular crack, H: shear
perpendicular to the rolling direction of the artificial defect from crack). (a) N= 1x104cycles. (b) N= 1x106
N=1x104 cycles to N= 1x106 cycles. Shear cracks propagated in a cycles
horizontal direction simultaneously. The propagated length of a shear crack at a depth of approximately 150 μm was the
largest. The depth was close to the region (100-170 μm) where the range of shear stress was largest according to Hertzian
theory.
For the sample interrupted at N= 1x106 cycles, the perpendicular crack was artificially opened under liquid nitrogen
cooling. Figure 6 shows a SEM micrograph of the fracture surface of the perpendicular crack. The shape of the
perpendicular crack examined by CT scanning is superimposed on the fracture surface with the line identified as the crack tip
from fractography. Both shapes of the crack almost coincide in the shallower region up to about half the depth of the

artificial defect. On the other hand, the shape obtained by CT Rolling contact surface
imaging indicates a smaller perpendicular crack in the deeper region.
The difference of crack shapes in the deeper region is due to the P P Crack shape
of CT image
estimation error of CT imaging, which should be improved by S
S
optimizing CT imaging conditions as a future task.
Crack shape
The process of RCF crack propagation is summarised in Fig. 7.
P P
deduced from
this image
First, perpendicular cracks are initiated at the region close to a surface S
along an inclusion (artificial defect) due to tension and shear stresses, ×
Rolling direction
while simultaneously, shear cracks are initiated at several points along
the inclusion (artificial defect) due to shear stress. Next, P: Perpendicular crack
20m S: Shear crack
perpendicular cracks propagate in mode III from the edges at the
Fig. 6 Comparison between CT image
surface and at intersections with shear cracks, and propagate in mode
and SEM view of crack surface
II from the edge at the bottom. Then, shear cracks propagate in
mode II at intersections with perpendicular cracks. The next process, the perpendicular cracks probably propagate in a
rolling direction and towards the surface. Finally, flaking occurs. The above-mentioned RCF mechanism discussed is
probably applicable to the service condition of thrust bearings; high strength steel with comparatively small inclusion or defect
that elongates perpendicular to the rolling contact surface under pure rolling contact with oil lubrication and without
macroscopic slip.
[Initial condition] [Crack initiation] [Crack propagation] [Flaking]
Rolling direction
tension
mode III
shear mode II
Artificial defect
mode III
Fig. 7 Process of RCF crack propagation
Conclusion
In order to clarify the RCF crack behavior and to discuss the mechanism of RCF crack propagation, we carried out RCF
test with an artificial defect, SR micro CT imaging. We found the following results:
(1) Two different types of fatigue cracks - perpendicular crack and shear crack - were induced in RCF.
(2) Both perpendicular and shear cracks initiated before N=1x104 cycles. Perpendicular cracks propagated in the depth
direction and perpendicular to the rolling direction of the artificial defect from N=1x104 to 1x106 cycles. Shear cracks
propagated in a horizontal direction simultaneously.
(3) The perpendicular crack accelerates the propagation of shear cracks.
(4) Interaction between perpendicular and shear cracks would appear to dominate RCF crack propagation originating from
defects such as inclusions.
References
1) K. Hashimoto, K. Hiraoka, K. Kida and E. C. Santos: Materials Science and Technology, 28 (2012), pp.39-43.
2) N. Matsui: ISIJ Int. 46-11 (2016), pp.1720-1727.
3) Y. Neishi, T. Makino, H. Matsumoto, M. Higashida and H. Ambai: Metallurgical and Materials Transactions A 44-5(2013), pp.
2131-2140.
4) M. Nagao, K. Hiraoka and Y. Unigame: Sanyo Tech. Report 12-1 (2005), pp. 38-45.
5) K. Hashimoto, K. Hiraoka, and K. Kida: TMS2011 140th Annual Meeting & Exhibition (2011, San Diego, USA).
6) T. Makino, Y. Neishi, D. Shiozawa, Y. Fukuda, K. Kajiwara and Y. Nakai: Int. Journal of Fatigue 68 (2014), pp.168-177.

Mechanical property of a low carbon steel containing 2 wt%Nb
Wentao Luo 1, Ling Zhang 1,2,*
1
International Joint Laboratory for Light Alloys (MOE), College of Materials Science and Engineering, Chongqing University,
Chongqing, 400044, P.R. China
2
Electron Microscopy Center of Chongqing University, Chongqing University, Chongqing 400044, P.R. China
3
Shenyang National Laboratory for Materials Science, Chongqing University, Chongqing 400044, P.R. China
*email: zhangling2014@cqu.edu.cn
Keywords: Steel, Microstructure, Mechanical properties, Nb-bearing steel
Abstract: Design of advanced alloys with simple compositions is a new strategy to improve the recyclability of the
alloys. In this study, a 2 wt% Nb bearing low carbon steel (2Nb steel) without addition of Ni, Cr and W was designed and
processed by hot forging, hot rolling and cold rolling followed by annealing. A fine grain size microstructure with NbC
precipitates formed. Microstructure and tensile properties were characterized at ambient and elevated temperatures. The good
strength was related to the pinning effect of large NbC precipitates present at the grain boundaries and small precipitates
formed in the grain interior that hinder the movement of grain boundaries and dislocations, respectively.
1. Introduction: In recent years, with the extensive development and application of a series of heat-resistant steels,
the design of heat-resistant alloys has gradually attracted the attention of researchers. Among some reported alloy designs,
such as Fe-20Ni-14Cr-2.5Al-(1-3) Nb (wt%) [1], Fe-18Cr-31Ni-4Nb (wt%) [2], Fe-20Cr-3Ni-3Si-2Nb-1Mn (wt%) [3],
Fe-21Cr-10Ni-2Nb-1Mn-(1-2) W (wt%) [4] add a large amount of alloying elements, including Ni, Cr, W, Nb, etc. However,
the more alloying elements are added, the more complex the material system is, and the more difficult it is to control the
microstructure and properties. For the sustainable development of global resources and environment, reducing alloy or using
simpler alloy to save material cost, increasing recyclability and improving sustainability without reducing the material
properties need considerations in material design [5].
Generally, niobium (Nb) is used as a microalloying element to enhance the mechanical properties of steel, but it is
added in large quantities in the composition design of heat-resistant steel. Precipitates such as Laves phase [2], G-phase
precipitates [3] and MC-carbides [6], are introduced in the grain interior or on the grain boundaries to improve the stability of
the microstructure at high temperatures. But Laves phase and G-phase generally lead to brittle failure of the material and are
detrimental to room temperature properties. For example, Padilha et al. [7] reportd that Fe2Nb phase is hard and fragile,
forming between austenite dendrites and result in loss of toughness and ductility in their investigated Fe-15Cr-15Ni-2Nb
(wt%) austenitic stainless steel. Thus, it is necessary to find better precipitates which can provide good properties at both room
temperature and high temperatures without sacrificing either. In the present study, a much plain material: Fe-0.2C-2Nb (wt%)
low carbon alloy steel was designed. The microstructure evolution of the alloy was systematically characterized by OM, SEM,
EBSD and TEM imaging techniques. The mechanical properties of the alloy at high temperature and room temperature were
tested to reveal the deformation mechanism and strengthening mechanism of the alloy.
2. Experimental: The designed chemical composition of the steel is 2 wt% Nb, 0.2 wt% C with balanced Fe,
shorted as 2Nb steel in the following part. After casting, the sample was hot forged, 80% hot rolled or 80% cold rolled. Heat
treatment was also performed at 200℃ to 400℃ to tune the microstructures and mechanical properties. Tensile tests were
performed at room temperature using dog-bone-shaped specimens, with gage dimension of 13  2.5  2 mm3, at an initial
strain rate of 6.4 × 10−4 s−1, and at high temperatures in the range of 600 ℃ - 1000 ℃ with cylindrical specimens (60  Ø 10
mm3, strain rate of 10−3 s−1). At least 3 specimens were used for each tensile test.
Microstructures of 2Nb steel were characterized by optical microscopy (OM), scanning electron microscopy
(SEM), electron backscatter diffraction (EBSD) and transmission electron microscopy (TEM). The specimen surface was
electro-polished in a solution of 5 vol.% HClO4 (perchloric acid) + 95 vol.% C2H5OH (ethanol) at -20 ℃ with a voltage of
20 V. SEM and EBSD measurements were carried out using JSM 7800 with Aztec program. For TEM observations, thin foils
were mechanically polished and then thinned by twin-jet in a solution of 5 vol.% HClO4 + 95 vol.% C2H5OH at -20 ℃ with
a voltage of 20 V. Conventional bright field (BF) images were taken by JEM 2100 operated at 200 kV.

3. Results
Fig. 1 Phase diagram of Fe-Nb containing 0.2 wt% C
Fig. 1 shows the phase diagram of Fe-Nb containing 0.2 wt% C using Thermo-Calc software, austenite transforms
into ferrite at around 920 ℃. NbC phase and Fe2Nb Laves phase may exist at low temperatures. Our microstructure and
XRD results found that the phases are mainly composed of ferrite matrix and NbC phase after casting and hot forging, Fe2Nb
phase was not found or with only a very small amount that can't be resolved by XRD. It can be seen from Fig.2 that much
equiaxed grains can be seen after hot forge (about 8.0 ± 1.0 μm) which is much finer than the as-cast sample.
Fig. 2 OP microstructures of 2Nb steel: (a) (b) as-cast; (c) (d) as-forged
Table 1 Mechanical properties of as-forged sample tested at various temperatures

Temperature YS (MPa) UTS (MPa) UE (%) TE (%)
RT 339 498 15 29
600 ℃ 297 430 13 25
700 ℃ 212 307 8 24
800 ℃ 129 187 8 23
900 ℃ 56 82 18 30
1000 ℃ 29 43 20 45

Fig. 3 TEM images and size distribution of NbC precipitates: (a) (b) as-forged sample; (c) (d) as-600 ℃ tensile tested sample
From Fig. 2(d) and Fig. 3, it is easily seen that larger particles (~ 300 nm) are pinned at the grain boundaries and triple
junctions while the smaller precipitates are widely dispersed in the grain interior and at the dislocations. According to the
statistics, the average size of the small precipitates in the grain interiors is ~ 34 nm. The NbC precipitates underwent a small
amount of coarsening during the tensile test at 600 ℃. The detailed properties can be found in Table 1.
Fig. 4 TEM image of 80 % hot rolled sample RD-ND surface (a) and 200 ℃, 15 min heat treated sample (b)
Fig. 4(a) is the TEM image of 80 % hot rolled sample observed on RD-ND surface. Deformed ferrite matrix has a
large amount of dislocations. Large NbC particles can be found along the grain boundaries or in the grain interiors, as
indicated by yellow arrows. Fig. 4(b) is the 200 ℃, 15 min heat treated sample. Some Fe2Nb precipitates can be found after
annealing at low temperatures. The low magnification images can be found by SEM images as shown in Fig. 5, where Fig.
5(a) is the as-hot rolled sample, and others are 300 ℃ annealed samples. Fig. 6 is the TEM image of 80 % cold rolled sample.
More elongated ferrite matrix can be seen as comparing with hot rolled condition.

Fig. 5 SEM microstructure of as-hot rolled (a) and 300 ℃ annealed samples: (b) 5 min, (c) 10 min (d) 15 min, (e) 20 min, (f) 25 min
Fig. 6 TEM image of 80 % cold rolled sample (RD-ND surface): (a)TEM image and corresponding microstructural sketch lines (b)
Acknowledgement
The authors wish to thank the financial support of the National State Key Research and Development Program of China
(2016YFB0700403), the Natural Science Foundation of China (NSFC, Grants No. 51671039), and the Fundamental Research
Funds for the Central Universities (Project No. 2020CDJDPT001).
References
1) Y. Yamamoto, M. P. Brady, Z. P. Lu, P. J. Maziasz, C. T. Liu, B. A. Pint, K. L. More, H. M. Meyer, E. A. Payzant, Science, 316
(2007) 433-436.
2) S.W. Chen, C. Zhang, Z.X. Xia, H. Ishikawa, Z.G. Yang, Materials Science and Engineering: A, 616 (2014) 183-188.
3) M. Yang, J. Zhu, T. Yang, J. Luan, Z. Jiao, X. Fan, B. Kuhn, X. Xiong, C. Wang, C.T. Liu, X. Liu, Materials Science and
Engineering: A, 745 (2019) 390-399.
4) Yinhui Zhang, Mei Li, Larry A. Godlewski, Jacob W. Zindel, Qiang Feng, Materials Characterization, 139 (2018) 19-29.
5) Y.H. Gao, S.Z. Liu, X.B. Hu, Q.Q. Ren, Y. Li, Vinayak P. Dravid, C.X. Wang, Materials Science and Engineering: A, 759 (2019)
298-302.
6) Seungmun Jung, Yong Hee Jo, Changwoo Jeon, Won-Mi Choi, Byeong-Joo Lee, Yong-Jun Oh, Gi-Yong Kim, Seongsik Jang,
Sunghak. Lee, Materials Science and Engineering: A, 682 (2017) 147-155.
7) A. F. Padilha, I. F. Machado, R. L. Plaut, Journal of Materials Processing Tech, 170 (2005) 89-96.

Obtaining the solubility product of TiC and TiN in austenite by
measuring the grain growth at elevated temperatures
Wei Wang1, Haijiang Hu2,*, Ping He2, Guang Xu2
1
Baosteel Research Intitute, 889 Fujin Rd, Shanghai 201900, China.
2
The State Key Laboratory of Refractories and Metallurgy, Wuhan University of Science and
Technology, Wuhan 430081, China.
*email: huhaijiang@wust.edu.cn
Keywords: Solubility product, Grain growth, Pinning effect, Precipitate
Aim and scope: Solubility products (SP) of TiC and TiN in austenite are briefly reviewed.
The SPs of carbides and nitrides are commonly described by logarithms in a form of
log([%𝑇𝑖][%𝑋]) = 𝐴 − 𝐵/𝑇 , where X is C or N, A and B are constant parameters,
𝑇 represents temperature. The austenite grain growth is essentially related to the dissolution of
precipitates, which can be determined by SP. The present work aimed to quantify the
connection between the SP and austenite grain growth. The model was proposed by analyzing
the austenite grain growth with considering the pinning effect of precipitates. The austenite
grain size increased from 8.7 μm at 950 ℃ to 183.5 μm at 1300 ℃. With the statistical data,
SP equations of a Ti containing steel were thereafter obtained based on the statistical data and
compared with those in literature.
Materials and method: A low-carbon micro-alloying steel with the composition of

Fe-0.07C-1.96Mn-0.50Cr-0.12Ti- 0.0037N (wt.%) was used in this study. Rectangle samples
with a size of 10mm × 10mm × 14mm were machined form the hot rolled plate. The samples
were then heated to 950 to 1300 ℃ with a temperature interval of 50 ℃ at the heating rate of
1 ℃/s. Finally, all samples were quenched to room temperature. The optical microstructures
(OM) were observed using Zeiss microscope, which was used for metallographical
measurement of austenite grain size. The prior austenite grain boundaries were revealed using
a solution of 10 ml dodecylbenzene sulfonate, 20 ml saturated aqueous picric acid mixed and
four drops of hydrochloric acid. The optimized temperature and time for etching were 65 ℃
and 280-300 s, respectively. The austenite grain size was measured by Nanaomeasure
software, ensuring that at least 150 grain intersections were counted for each sample.
Results
Measured austenite grain size
It can be seen from Fig. 1a that the average austenite grain size increases from 8.7 μm at
950 ℃ to 183.5 μm at 1300 ℃. The coarsening rates of austenite grains during the heating
process were given the Fig. 1b. There was a decrease in coarsening rate when the temperature
increased from 1150 ℃ to 1200 ℃. The SP of TiN is so small below 1250 ℃ that its effect on
the austenite growth can be neglected [1]. Thus, it is reasonable to speculate that the
coarsening before 1150 ℃ mainly depends on the dissolution of TiC particles.

Fig. 1 (a) Distribution of austenite grain size (diameter) and (b) coarsening rate as a function
of temperature.
Modeling SP with austenite grain
The grain growth of austenite can be stop by the second phase particles. The pining effect is
mainly determined by the volume fraction and particle size. The evolution of Ti-precipitates
(dissolution or coarsening) during austenitization has a significant influence on the kinetics of
austenite growth and the limiting grain size. Thus a model could be developed to describe the
correlation between austenite grain size and solubility of precipitates. The austenite grain
growth rate can be given as follows [2]:
𝑑𝐷 𝑄
𝑑𝑡
= 𝑀0 𝑒𝑥 𝑝 (− 𝑅𝑇 ) (𝑃𝑑 − 𝑃𝑧 ) (1)
where D is the grain diameter, 𝑀0 is the pre-exponential factor, 𝑄 is an activation energy, R

is the gas constant, and T is the absolute temperature. According to the Gibbs-Thomson
equation, the driving force 𝑃𝑑 for the grain growth can be expressed by [3]:
𝑃𝑑 = 2𝜎/𝑅 (2)
where 𝜎 is the interfacial energy and 𝑅 is the particle-limited radius of matrix grains. The
pinning force 𝑃𝑧 by particles against grain growth is given as follows [3]:
2/3
3𝜎𝑓𝑉
𝑃𝑧 = 4𝑟
(3)
where 𝑓𝑉 is the volume fraction of precipitates and r the mean particle radius. From Eq. (1)
the growth of austenite ceases when 𝑃𝑑 − 𝑃𝑧 = 0. Thus, by equaling driving (Eq.(2)) and
pinning (Eq.(3)) force, the following equation can be obtained.
8𝑟
𝑓𝑉 = (3𝑅 )3/2 (4)
In the present work, a very slow heating rate of 1 ℃/s was used, thus one can assume
that the equilibrium of dispersing precipitates was kept at each step. For a selected heating
temperature, the maximum distance between two particles, 𝐿max , can be expressed as
follows:
𝑡 1/2
𝐿max = (∫𝑡 𝐷𝑇𝑖 𝑑𝑡) (5)
0
where 𝐷𝑇𝑖 is the diffusivity of Ti, given as 𝐷𝑇𝑖 (m2 · s−1 ) = 2.8 × 10−4 exp (−286000/
𝑅𝑇) [1]. According to the assumption of Nishizawa [3], the inter-particle distance can be
expressed as a function of particle radius r and volume fraction 𝑓𝑉 , that is:

1/3
𝐿 = 𝑟/𝑓𝑉 (6)
Assuming 𝐿max = 𝐿 and combining Eqs. (4)-(6), the following equation can be obtained:
𝑡 1/2
1/3 8(∫𝑡 𝐷𝑇𝑖𝑑𝑡 )
𝑓𝑉 = 0
(7)
3𝑅
In addition, the total volume fraction of particles is essential related to the SPs of TiC
and TiN. Thus, the constant parameters A and B in the SP equations can be obtained by fitting
the measured austenite grain size R. The parameter t in Eq. (7) is heating time, which is
related to the heating rate and target austenitization temperature. The lower limit 𝑡0 of the
𝑡
integral formula ∫𝑡 𝐷𝑇𝑖 𝑑𝑡 can be termed as the beginning of dissolving precipitates in
0
austenite, which was prior evaluated as 900 ℃.

As mentioned above, we only consider the dissolution of TiC before 1150 ℃. The
calculated volume fractions of TiC at different heating temperatures are given in Fig. 2a. With
the increasing of austenitization temperature, the 𝑓𝑉 of TiC decreases from ~0.2 % to zero.
The full equilibrium dissolving temperature is approximated to 1150 ℃. The coarsening of
austenite above 1200 ℃ is assumed to be correlated to the dissolution and coarsening of TiN
particles. Fig. 2b shows the minor decreasing of TiN particles. Using the data in Fig. 2, the SP
equations of TiC and TiN can be fitted as follows:
log([%𝑇𝑖][%𝐶]) = 3.79 − 8335.1/𝑇 (8)
([ )
log %𝑇𝑖][%𝑁] = 4.4054 − 14937.3/𝑇 (9)
where [%𝑇𝑖], [%𝐶] and [%𝑁] are the solutes in weight percent, T is the heating
temperature.
Fig. 2 The calculated volume fractions of TiC (a) and TiN (b) as a fuction of heating
temperature.
Fig. 3 shows the comparison of the SP models in the present work with others from
literatures. It can be seen that the cited TiC and TiN SP models vary in a large range. The
present TiC model locates in a relatively dense region, which is neighbored to 2.75-7000/T
cited in most works. The TiN SP equation in the present work is close to 4.35-14890/T. It is
reported that alloying elements can affect the solubility of the second phase precipitates [3],
leading to variation of parameters A and B in the SP equation. Thus, the present SP model
could be used within similar composition. For the tested steel, the SP model was fitted by
austenite grains. This method is simplified compared to the way measuring precipitation

amount. It should be admitted that an experimental volume fraction of precipitates is better to
verify the present SP model. However, it is known that the quantity of the second phase
particles is too small to give an exact measuring data by metallography. The comparison
between the present SP model and previous works indicates that it is highly possible to obtain
the solubility product of TiC and TiN in austenite by measuring the austenite grain growth at
elevated temperature.
Fig. 3 Comparison of (a) TiC and (b) TiN SP model in the the present work with other works.
Conclusions: The austenite grain growth is essentially correlated to the dissolution of

precipitates, which can be determined by solubility product (SP). In the present work, the SPs
of TiC and TiN for the tested steel were reversely obtained by measuring the grain growth of
austenite. The SP models are be expressed as follows:
log([%𝑇𝑖][%𝐶]) = 3.79 − 8335.1/𝑇
log([%𝑇𝑖][%𝑁]) = 4.4054 − 14937.3/𝑇
References
[1] M. Maalekian, R. Radis, M. Militzer, A. Moreau, W.J. Poole. In situ measurement and
modelling of austenite grain growth in a Ti/Nb microalloyed steel. Acta Materialia, 60 (2012)
1015-1026.
[2] K. Banerjee, M. Militzer, M. Perez, X. Wang. Nonisothermal Austenite Grain Growth
Kinetics in a Microalloyed X80 Linepipe Steel. Metallurgical And Materials Transactions A,
41 (2010) 3161-3172.
[3] T. Nishizawa, I. Ohnuma, and K. Ishida. Examination of the Zener Relationship between
Grain Size and Particle Dispersion. Materials Transactions, JIM, 38 (1997) 950-956.

Possibility of Fully Recrystallized Ultrafine Grained Steels Managing Both High Strength
and Large Ductility
Nobuhiro Tsuji1,2
1
Department of Materials Science and Engineering, Kyoto University, Yoshida Honmachi, Sakyo-ku, Kyoto 606-8501, Japan
2
Elements Strategy Initiative for Structural Materials (ESISM), Kyoto University, Yoshida Honmachi, Sakyo-ku, Kyoto 606-8501,
Japan
*email: tsuji.nobuhiro.5a@kyoto-u.ac.jp
Keywords: ultrafine grained steels; strength and ductility; recrystallization; deformation modes; strain hardening.
Nowadays metallic materials are required to have

ultrahigh strength under social demands of increasing
fuel efficiency and light-weighting of transportation
devices like automobiles and huge constructions. For
example, the highest strength of steels used for
automobiles were 590 MPa in 2003, while steels with
strength of 1200 MPa and even 1500 MPa are used
now and furthermore higher strength is required [1]. At
the same time, structural metallic materials must have
enough ductility and toughness for satisfying
formability to make parts and crashworthiness in
accidents and disasters like big earthquakes. However,
strength and ductility/toughness of materials generally
show trade-off balances, as indicated in Fig.1 showing Fig.1 Trade-off strength-ductility balance of automobile steels [2].
strength-ductility balance of various kinds of
automobile steels [2].
Ultrafine grained metallic materials (or bulk
nanostructured metals (BNM)) are one of the
candidates of ultrahigh-strength metals. Severe plastic
deformation (SPD) processes that can fabricate
ultrafine grained (UFG) or nanostructured metallic
materials with average grain sizes much smaller than 1
µm through applying very high plastic strains have
given a huge breakthrough to studies on bulk
nanostructured metals. Resultant nanostructured metals
and alloys usually show strength 2-4 times higher than
that of the starting materials with conventionally coarse
grain sizes (larger than several tens micro-meter). On
the other hand, UFG or nanostructured materials
fabricated by SPD have limited tensile ductility due to
early plastic instability [3], which has been a big barrier
for practical applications of nanostructured metals. The Fig.2 Stress-strain curves of Fe-31Mn-3Al-3Si austenitic steel
fact that the nanostructured metals fabricated by SPD having fully recrystallized microstructures with various average
involve high densities of lattice defects grain sizes. [2].

(representatively dislocations) and are highly strain-hardened already is one of the main reasons for the early plastic instability
(i.e., limited ductility).
Annealing of deformed metals is known as a popular heat treatment to remove lattice defects and to recover their
ductility. It has been recently found that in some heavily-deformed alloys sub-micrometer grain sizes can be maintained even
after recrystallization and such metals having fully recrystallized nanostructures can perform quite good mechanical properties
managing both high strength and large ductility/toughness [4-8]. As an example, stress-strain curves of Fe-31Mn-3Al-3Si
austenitic steel having fully recrystallized microstructures with various average grains sizes are shown in Fig.2 [9]. The
ultrafine grained specimens with sub-micrometer grain sizes maintain good strain-hardening ability even after their yield
strength significantly increases by the grain refinement, resulting in large uniform and tensile elongation over 50%.
Fig.3 TEM images showing representative deformation microstructures in the ultrafine grained specimens at an early stage of
tensile deformation. (a) A grain with a size > 1 µm. (b) Grain size ~ 1 µm. (c) Grain size < 1 µm [10].
Their excellent mechanical properties are often given by a nucleation of new deformation modes, such as unusual slip
systems in HCP metals, nano deformation twins and deformation induced martensite all which were not expected to operate
in these metals and microstructures [5,7,8-10]. In case of the ultrafine grained Fe-31Mn-3Al-3Si austenitic steel, very thin
deformation twins with thickness of several nm ~ 30 nm nucleated from grain boundaries (Fig.3) [10], even though it has
been known that deformation twinning in FCC metals and alloys is suppressed by grain refinement. The activation of such
unexpected deformation modes leads to regeneration of strain-hardening ability. After these experimental results, a strategy to
overcome the strength-ductility trade-off is discussed on the basis of a new concept of plaston considering atomistic process in
nucleation of new deformation modes [11-13]. It is expected that the plaston concept could be a key to designing advanced
high-strength metallic materials managing both ultra-high strength and enough ductility/toughness.
Acknowledgement
This research work was financially supported by the Elements Strategy Initiative for Structural Materials (ESISM;
JPMXP0112101000), JST CREST (JPMJCR1994), and KAKENHI (Grant-in-Aid for Scientific Research from the Japan Society
for the Promotion of Science; 15H05767 and 20H00306), all from the Ministry of Education, Culture, Sports, Science and
Technology (MEXT), Japan. All the supports are gratefully appreciated.
References
[1] K.Saito: Materia Japan 53 (2014) 584-588.
[2] http://www.autosteel.com
[3] N.Tsuji, Y.Ito, Y.Saito, Y.Minamino: Scripta Materialia 47 (2002) 893-899.
[4] R.Saha, R.Ueji, N.Tsuji: Scripta Materialia 68 (2013) 813-816.
[5] Y.Z.Tian, L.J.Zhao, S.Chen, A.Shibata, Z.F.Zhang, N.Tsuji: Scientific Reports 5 (2015) 16707.

[6] L/Zhao, N.Park, Y.Tian, A.Shibata, N.Tsuji: Scientific Reports 6 (2016) 39127.
[7] R.Zheng, T.Bhattacharjee, A.Shibata, T.Sasaki, K.Hono, M.Joshi, N.Tsuji: Scripta Materialia 131 (2017) 1-5.
[8] R.Zheng, T.Bhattacharjee, S.Gao, W.Gong, A.Shibata, T.Sasaki, K.Hono, N.tsuji: Scientific Research 9 (2019) 11702.
[9] Y.Bai, H.Kitamura, S.Gao, Y.Tian, N.Park, M-h.Park, H.Adachi, A.Shibata, M.Sato, M.Murayama, N.Tsuji: Scientific Reports 11
(2021) 15870.
[10] C-Y.Hung, Y.Bai, N.Tsuji, M.Murayama: Journal of Materials Science & Technology 86 (2021) 192-203.
[11] N.Tsuji, S.Ogata, H.Inui, I.Tanaka, K.Kishida, S.Gao, W.Mao, Y.Bai, R.Zheng, J-P.Du: Scripta Materialia 181 (2020) 35-42.
[12] N.Tsuji, S.Ogata, H.Inui, I.Tanaka, K.Kishida, S.Gao, W.Mao, Y.Bai, R.Zheng, J-P.Du: Scripta Materialia 196 (2021) 113755.
[13] “The Plaston Concept -Plastic Deformation in Structural Materials” Editors: Isao Tanaka, Nobuhiro Tsuji, Haruyuki Inui, (2022)
Springer, ISBN: 978-981-16-7717-5, Open Access https://link.springer.com/book/10.1007/978-981-16-7715-1

Uncovering the relationships between processing parameters, interphase precipitation
and strengthening of ferritic high strength low alloy steels
Elena Pereloma1,2,3*, Navjeet Singh1,2, Andrii Kostryzhev1,2, David Wexler1, Gilberto Casillas3, Frank Niessen3 and
Chris Killmore2,4
1
School of Mechanical, Materials, Mechatronic and Biomedical Engineering, University of Wollongong, NSW 2522, Australia
2
ARC Research Hub for Australian Steel Manufacturing, University of Wollongong, NSW 2522, Australia
3
UOW Electron Microscopy Centre, University of Wollongong, NSW, 2519, Australia
4
BlueScope Steel Limited, Five Islands Rd, Port Kembla, NSW 2505, Australia
*email: elenap@uow.edu.au
Keywords: steel, interphase precipitation, scanning transmission electron microscopy, tensile properties, strengthening mechanisms
Currently, there is a significant interest in both academia and industry related to the development of ferritic
microalloyed steels strengthened by nanometer-sized Interphase Precipitation (IP). The acceleration of these efforts started in
early 2000s with a report by JFE of new Ti-Mo microalloyed steels reaching 734 MPa yield strength (YS) 1). One of the major
contributors to the yield strength was deemed ~3 nm size IPs. Interphase precipitation can occur during the γ→α
transformation in steels alloyed with carbide-forming elements: Ti, Mo, Nb, V, Cr, etc.2,3) Experimental and theoretical data
suggest that IP could provide a significant strengthening effect (Table 1) presumably via operation of a dislocation looping
mechanism. At the same time, IP-strengthened steels display other attractive characteristics, such as cost-effectiveness,
formability and weldability.
Table 1 Selected published data on strengthening contribution from interphase precipitation.
Carbide-forming
Yield strength, MPa Reference
elements, wt.%
4)
0.06C-0.1Ti-0.5Cr 220-320
5)
0.06C-0.1Ti-0.2Mo 230-400
1)
0.04C-0.09Ti-0.2Mo 300
0.1C-0.2Ti 240
0.1C-0.2Ti-0.5Mo 260 6)
0.1C-0.2V 130
0.1C-0.2V-0.5Mo 240
7)
0.1C-0.04Nb-0.11Ti 112
8)
0.44C-0.3V 180
9)
0.023C-0.34Nb 210
0.08C-0.035Nb-0.085Ti- 10)
320
0.11Mo
In addition to steel composition, the thermo-mechanical processing (TMP) of these steels includes several
important stages (reheating temperature, deformation amount and temperature, coiling temperature and time), which could
directly affect the size, morphology and volume fraction of IP. With respect to the effect of deformation, while the majority of
studies on IP were conducted on fully annealed materials, a limited number of results indicated a decrease in size and
intersheet spacing accompanied by an increase in volume fraction of IP with an increase in the amount of strain in the
non-recrystallised region 11-13). Decreasing coiling temperature also generally leads to the IP size refinement and an increase in
its amount. However, these effects are not straightforward as modification of TMP parameters leading to the consumption of

solute at earlier processing stages before the IP may have an adverse effect. In this project, we pursued several aims:
• To design the steel composition and TMP schedule to achieved >700 MPa yield strength;
• To gain insight into the strengthening mechanism of IP;
• To evaluate the effect of TMP parameters on IP and resultant tensile properties.
Steel containing ~(0.08±0.003)C, 1.5Mn, 0.3Si, 0.2Ni, 0.03Al, 0.003S, 0.015P, (0.0131±0.0002)N, and 0.73 (Cr +
V + Nb) (wt. %) was used for this study. The TMP was carried out using a Gleeble 3500 simulator with various processing
parameters.14,15). Tensile testing was performed using 3 mm wide, 1 mm thick and 7 mm gauge length flat specimens on a
Kammrath and Weiss GmbH mini-tensile stage at the constant crosshead speed of 7 μms-1. The microstructures were
characterised using optical, scanning and transmission electron microscopies. Selected samples were also examined using a
high resolution scanning transmission electron microscope ARM 200F and local electrode atom probe.
Representative images of microstructure (Fig. 1a) and of interphase precipitation (Fig. 1b) confirmed
predominantly polygonal ferrite microstructure with a very small amount of pearlite and that the majority of ferrite grains
contained the IP of (V, Cr)C. However, the TMP parameters affected the characteristics of IP and consequently, the tensile
properties. For example, for the same amount of deformation, but varying the deformation finish temperature from 900 to
850°C, the ferrite grain size has reduced by ~1.5 µm, the particles became finer but their density lower. The strength values
were not affected by this variation in the deformation temperature (~870 MPa YS and ~1030 MPa tensile strength), but
elongation was slightly higher after higher finish temperature (23% vs 21%). The intersheet spacing was not affected and was
~ 22 nm for both schedules. On the other hand, an increase in the amount of deformation imposed in the recrystallization
region by 0.3 resulted in a small amount of ferrite grain refinement, but enormous increases in IP density (intersheet spacing
reduction to 12 nm after coiling at 600°C) and significant improvement in the mechanical properties (increase in YS from
717±8 to 862±62 MPa was accompanied by small reduction in elongation from 21 to 19%). A slightly longer coiling time of
30 min, compared to 15 min at higher coiling temperature of 650°C, also delivered a high volume fraction of IPs with 12 nm
intersheet spacing and even further increase in YS to 960 MPa.
a b
Figure 1 (a) Representative optical micrograph of polygonal ferrite with pearlite (dark). (b) Bright field image of
interphase precipitation. Adopted from Ref. 15)
To elucidate the mechanism of interaction between IP and dislocations, high resolution investigation of precipitates
before and after tensile tests were conducted (Fig. 2). A clear formation of steps at the particle/matrix interface was visible after
deformation (Fig. 2b), which led to the conclusion of dislocations cutting the ~1-3 nm thick particles, instead of looping
around. Assuming operation of coherency strengthening and modulus mismatch strengthening mechanisms has taken place in
this steel, an estimated ~395 MPa contribution to the yield strength has arisen from these nano-sized particles. However, it
should be noted that when applying the Pythagorean flow stress addition law, the actual strength contribution will be less.
Atom probe studies have shown the presence, in addition to IP rows, of clusters of V between the particles in the rows and
between the rows in ferrite matrix. TEM also confirmed the presence of random precipitates in the ferrite matrix. In addition
to these very fine precipitates and clusters, a relatively low density of carbides and carbo-nitrides > 20 nm size was also
detected. These were assumed to form in austenite during TMP. Thus, the contributions to YS in these steels arises from

precipitates formed in austenite, IP particles, precipitates formed in ferrite, clusters, solid solution strengthening, dislocation
strengthening and grain boundary strengthening. Our estimations of all these various contributions showed that the main ones
are from grain boundary strengthening and from IP14). This is why tuning the TMP parameters to achieve both as fine as
possible ferrite grain size and maximisation of the volume fraction of nanosized IP is important.
Figure 2 STEM-HAADF images of VC (a) after TMP and (b) after tensile testing. Adopted from Ref. 16)
However, it needs to be considered that any change of one of the processing parameters may increase one of the
desirable microstructurural characteristics but have a detrimental effect on others. For example, increased deformation in the
non-recrystallisation region will lead to more nucleation sites for ferrite formation and its grain refinement, but it will also
trigger more abundant strain-induced precipitation. The latter will consume the microalloyed elements leaving a lesser amount
available for IP and random precipitation in ferrite, thus possibly reducing the volume fraction and density of IP, and their
associated strengthening effect. This may trigger a requirement to for additional modification of either the TMP and/or the
steel composition.
Acknowledgement
This work was funded by the Australian Research Council (ARC) Research Hub for Australian Steel Manufacturing under the
Industrial Transformation Research Hubs scheme (Project ID: IH130100017).
References
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13) C-Y. Chen, S.-F., Chen, C.-C. Chen and J-R. Yang: Mater. Sci. Eng. A634 (2015) 123-133.
14) N. Singh, G. Casillas, D. Wexler, C. Killmore and E. Pereloma: Acta Mater. 201 (2020) 386-402.
15) A. Kostryzhev, C. Killmore and E. Pereloma: Metals 11 (2021) 107 (1-14).
16) E. Pereloma, D. Cortie, N. Singh, G. Casillas and F. Niessen: Mater. Res. Lett. 8, 341-347 (2020).

Microstrucutre control in high toughness steel plates
Genichi Shigesato1*, Naoto Fujiyama2*, Shun Tanaka1*
1 Steel Research Laboratories, Nippon Steel Corporation, Futtsu, Chiba 293-8511, Japan
2 East Japan Research and Development Laboratories, Nippon Steel Corporation, Kimitsu, Chiba, 299-1141, Japan
*email: shigesato.59d.genichi@jp.nipponsteel.com
Keywords: steel, toughness, intragranular ferrite, bainite, incomplete transformation
1. Introduction
Steel plates are used for structural and construction applications, offshore structures, wind power plants, pressure vessels,
etc., for which safety and reliability are prime concern. Therefore, high toughness as well as high strength is required for the
material. In particular the properties of weld joints are important because the performance of welded structures is substantially
determined by them. Stress tends to concentrate at welded joints, and in addition, they are subject to thermal structural change
and residual stress due to welding. It is, therefore, not easy to obtain welded joints with high strength, toughness, fatigue prop-
erties, etc. The problem worsens when the heat input is increased to raise the efficiency of welding work. To solve these
problems, the development of steel materials and welding technology has to be done in a coordinated manner.
This paper focuses on the material side of development and outlines the investigations concerning the microstructure control
to obtain excellent toughness of the heat affected zones (HAZ) and weld metal. The toughness is governed by the properties of
the iron matrix, such as the grain size and the strength, and those of embrittlement phase acting as an initiation site of a crack. In
response to that, the grain refinement of ferrite grains and the reduction of embrittlement phase have been investigated to
improve the toughness of HAZ and weld metal. In the following section recent studies about the utilization and the mechanism
of intragranular ferrite transformation as a means of the grain refinement are shown. After that the carbon enrichment behavior
to austenite during bainite transformation will be presented, which is related to the formation mechanism of martensite-austenite
constituent (MA), which acts as an embrittlement phase.
2. Grain refinement by intragranular ferrite

The heat affected zone (HAZ) is heated over 1673 K during welding, causing significant grain coarsening of austenite (γ).
As a result of that, coarse ferrite grains, such as grain boundary ferrite allotriomorph (GBF) and Widmanstatten ferrite or
so-called ferrite side plate (FSP) are often observed at prior γ grain boundaries after cooling. Those coarse grains deteriorate
the toughness markedly. The situation is almost the same for the microstructure of weld metal, which is heated above the
melting point. Thus suppressing the coarse grain microstructures is key to obtaining welded joints with excellent toughness.
There are two methods for refining the microstructure in HAZ and weld metal. One is restraining the growth of γ grains by
using pinning particles. Nitrides, oxides and sulfides whose size is tens to hundreds nanometers and which are stable at high
temperatures are used for this purpose. The other is increasing the number of nucleation sites of ferrite transformation by using
particles whose size is several micrometers. Ferrite transformation occurs not only at γ grain boundaries but also at inclusions
distributed inside γ grains. Ferrite generated at inclusions is called intragraular ferrite (IGF).
It has been reported that some types of particles promote the formation of IGF. The mechanism of IGF formation have
been discussed mainly from 2 viewpoints, the lattice coherency between ferrite (α) and the particle 1-4) and the formation of
Mn-depleted zone 5,6).
Fujiyama et al. 7) showed that the both of them, good lattice coherency and Mn depletion promote the formation of IGF in
weld metal. They prepared 4 types of weld metals with different Mn contents and Al/O ratios and examined the composition
of particles, lattice coherency, the presence of Mn-depleted zone around the particles and IGF formation behavior. Following
results were reported.
i ) Most of the nucleation sites of IGF were particles covered with a thin TiO film.
ii) The observed TiO crystals had nearly the Baker –Nutting orientation relationship with IGF (Fig.1).

iii) The amount of IGF increased as the number of the TiO-coated particles increased (Fig.3, 4).
iv) The Mn depleted zones were formed in the vicinity of the TiO layer (Fg.2) when the Mn content in the weld metal was
high (1.6 %) while no Mn depletion was observed in the weld metals with low Mn content (0.5%).
v) IGF nucleation was accelerated in the high Mn weld metals than in the low Mn weld metals even though the number of
the TiO-coated inclusions was almost the same (Fig.4).
According to those results, it is indicated that the presence of TiO layer on the surface of inclusions promotes IGF
nucleation with two mechanisms, good lattice matching and Mn depleted zone formation. The potency of inclusions as IGF
nucleation sites becomes higher when the two effects are superimposed than each effect works alone.
The authors suggested that the Mn depleted zone is formed due to the absorption of Mn into the TiO layer. The TiO layer
contained some amount of Mn in the high Mn weld metals. Researchers have reported that the Mn depleted zone was formed
around Ti2O3 particles. Takamura et al 8) considered that oxides that contained many cation vacancies could absorb Mn from
the steel matrix because the absorbed Mn atoms rapidly diffused in the oxides via cation vacancies. According to Takamura,
TiO as well as Ti2O3 is cation-vacancy types of oxide, and thus, TiO is considered to be able to absorb Mn and form Mn
depleted zone.
Fig.2 Mn concentration profile in the

Fig.1 HAADF STEM images of the interface between TiO and IGF. vicinity of the TiO/IGF interface.
Fig. 3 The microstructure (15° boundaries measured Fig. 4 Relationship between the number of Ti containing
by EBSD) of weld metals. inclusions and the effective grain size, deff.

3. Carbon enrichment to austenite during bainaite transformation
HAZ and weld metal often contain martensite-austenite constituents (MA), which would cause deterioration of the
toughness. Carbon is partitioned into austenite during bainite transformation and a part of the high carbon austenite transforms
to martensite during the final cooling process. The islands of high carbon austenite/martensite between bainitic ferrite laths
could be the origin of brittle fracture. It is thus important to quantitatively understand the carbon enrichment behavior during
bainite transformation in order to improve the toughness of welded joints.
During isothermal bainite transformation the carbon concentration of the austenite increases and the austenite is stabilized
and as a result of that bainite transformation ceases, which is known as the incomplete transformation. There are 2 different
explanations of the incomplete transformation depending on whether the bainite transformation is regarded as a diffusionless
transformation 9,10) or a C diffusion-controlled transformation 11,12).
From the standpoint of the diffusionless transformation, bainite transformation is considered to stop when the
composition reaches T0’ composition at which the sum of the free energy of ferrite and the strain energy necessary for the
shear transformation (Gbcc+ΔGstrain) equals the free energy of austenite (Gfcc). Bhadeshia estimated the degree of ΔGstrain as
approximately 400 J/mol 9,10). In other words, the C concentration at which bainite transformation stasis occurs is characterized
by the degree of undercooling from T0.
In contrast, the other view considers that Widmanstätten ferrite and bainitic ferrite are essentially the same. Hillert
proposed the growth limit of acicular ferrite 11,12), the WBs limit, which is characterized by the undercooling from para-Ae3.
Wu et al. examined the C partitioning behavior in Fe–Si–C alloys at 400 ℃ and 450 ℃ using atom probe and the C
concentrations of the untransformed austenite near the austenite/ferrite interface significantly exceeded the T0’ (400 J/mol)
compositions. They concluded that WBs model can explain the results well13).
Those investigations about the bainite incomplete transformation have mainly been conducted below 500 ℃.
Considering the microstructure evolution of weld metal and HAZ in practical low-alloy steels, however, the bainite
transformation proceeds between 500–600 ℃. Tanaka et al. 14) measured the C concentration of the retained austenite in
Fe–0.1%C–0.5%Si–2.0%Mn during isothermal holding at 450–650 ℃ using EPMA. The following were presented.
i) The C concentration during the stasis was between the T0’ and WBs composition (Fig. 6).
ii) The results can be explained by changing ΔGstrain according to the temperature. The measured C concentrations
consistent with T0’ assuming ΔGstrain was 100 J/mol at 550 ℃, 150 J/mol at 500 ℃ and 300 J/mol at 450 ℃.
iii) Diffusional transformation to ferrite started after the stasis and the C concentration of the untransformed austenite
began to rise again.
Bhadeshia pointed out that ΔGstrain can be smaller than 400J/mol at a high temperature because of plastic relaxation. The
stored strain energy of 400 J/mol is proposed considering an isolated bainite plate which is elastically accommodated in the
Fig. 5 (a) Dilatation during isothermal holding at 550°C, SEM images after (b) 30 s, (c) 200 s, (d) 1000 s and (e) 10000 s.

Hillert11)
Spline interpolation
of Hillert’s data
Fig.6 Carbon concentration of untransformed austenite

Fig.7 Barrier energy for WBs theory.
during (solid) and after (open) the transformation stasis.
surrounding austenite, which is the upper limit of the stored energy. As the transformation temperature
lowers, ΔGstrain is considered to approach to 400J/mol.
On the other hand, it is possible to interpret the results by the WBs theory. The WBs line in fig.4 was calculated using the
values proposed by Hillert as the barrier energy to the growth of acicular ferrite. The WBs line can be fitted to the current results
by lowering the values by about 100 J/mol (Fig.7). Thus, it is difficult to judge from the current results which model is
appropriate. The physical meaning of the barrier energy should be examined quantitatively.
4. Summary
Recent investigations concerning the mechanism of IGF generation and the carbon partitioning behavior during during
bainite transformation, which were connected with the microstructure control to obtain excellent toughness of the heat affected
zones (HAZ) and weld metal, were reviewed.
Ti oxide that have NaCl type crystal structure, TiO, can promote IGF nucleation due to the combined effects of good lattice
matching and the formation of Mn depleted zone.
The carbon concentration of untransformed austenite during the transformation stasis in Fe–0.1%C–0.5%Si–2.0%Mn
alloy were measured using EPMA. The results can be explained by either theory, T0’and WBs supposing the transformation
barrier energy are appropriately adjusted.
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13) H. D. Wu, G. Miyamoto, Z. G. Yang, C. Zhang, H. Chen and T. Furuhara: Acta Mater., 133 (2017), 1.
14) S. Tanaka, H. Shirahata, G. Shigesato and M. Takahashi: Tetsu-to-Hagané 107 (2021), 835 (in Japanese)

Low-temperature tensile properties of aged ultra-low carbon steels
Norimitsu Koga1,*, Yuki Kanehira2, Pham Thi Thanh Huyen2, Kazuya Hori3, and Osamu Umezawa3,4
1
Faculty of Mechanical Engineering, Institute of Science and Engineering, Kanazawa University, Kakumamachi, Kanazawa,
Ishikawa, 920-1192, Japan
2
Graduate School of Engineering, Yokohama National University, 79-5 Tokiwadai, Hodogaya, Yokohama, 240-8501, Japan.
3
Faculty of engineering, Yokohama National University, 79-5 Tokiwadai, Hodogaya, Yokohama, 240-8501, Japan
4
Center of Advanced Innovation Technologies, Vysoká Škola Báňská - Technical University of Ostrava, 17. listopadu 15, 708 33
Ostrava-Poruba, Czech Republic.
*email: koga-norimitsu@se.kanazawa-u.ac.jp
Keywords: ultra-low carbon steel, low temperature, tensile property, aging, deformation twin
1. Introduction
Carbon is the most important alloying element for strengthening conventional steels and strongly affects their mechanical
properties, even in very small amounts such as tens of ppm. The several strengthening mechanism at room temperature by
aging of ultra-low carbon steel has been proposed such as precipitation strengthening by carbides [1], increase in the
Hall-Petch coefficient by segregation of carbon atoms to the grain boundary [2]. Furthermore, using a small ball rebound
hardness test, Koga et al. [3] demonstrated that a solid solution of ultra-low carbon (approximately 100 ppm) in the matrix
significantly enhanced the high-temperature hardness of steels with various carbon concentrations. The effect of ultra-low
carbon on the mechanical properties of steels above room temperature has been widely investigated; however, it is still unclear
whether ultra-low carbon influences the mechanical properties at low temperatures.
In this study, the microstructural changes and low-temperature tensile properties of ultra-low carbon steel with aging
treatment were examined and the relationship between the low-temperature tensile properties and the ultra-low carbon state
were discussed.
2. Experimental procedure
Ultra-low carbon steel with a carbon concentration of 75 mass ppm was used. The steel was cold rolled to a 90 % reduction
in thickness, annealed at 973 K for 1.8 ks, and then water-cooled. The annealed specimens exhibited equiaxial recrystallized
grains with an average grain size of approximately 50 μm. The annealed specimens were aged at 443 K for 0.06–600 ks and
subsequently water-cooled. The aged specimens were maintained at 77 K in liquid nitrogen to prevent further aging at room
temperature. Tensile test specimens were cut from plates where the tensile direction was parallel to the rolling direction (RD).
Tensile tests were conducted at an approximate initial strain rate of 5.2 × 10-4 s-1 at 293 K in air and at 77 K in liquid nitrogen.
The tensile tests were initiated after the specimens were maintained at the test temperature for 1.8 ks. The microstructure on
the surface of the normal direction (ND) specimen was observed using field-emission scanning electron microscopy
(FE-SEM). Electron back-scattered diffraction (EBSD) with FE-SEM was used to analyze the crystal orientation in the ferrite
matrix and twins. A twin-jet electro-polisher, using methanol-perchloric acid with a volume ratio of methanol, 1-butanol, and
perchloric acid of 12:7:1 at 233 K, was employed to (a) (b)
prepare the specimens for transmission electron
microscopy (TEM) observations.
3. Results and discussion

3.1. Microstructure of aged ultra-low carbon steel
Figures 2 (a)-(c) display TEM images of the specimens
aged at 443 K for 0, 6 and 600 ks, respectively. (c)
Precipitates were not observed at 0 ks (Fig. 2 (a)).
Precipitates of approximately 110 nm in length were
observed at 6 ks (Fig. 2 (b)). These precipitates grew with
increasing aging time and were approximately 800 nm in
length at 600 ks. These were considered to be cementite.
Figure 1 TEM images of the specimens aged at 443 K for

(a) 0, (b) 6 and (c) 600 ks. [4]

3.2. Tensile properties at 77 K in aged ultra-low carbon steel
Figures 2 shows the nominal stress-nominal strain 750
(SS) curves at 77 K for the specimens at various
700
Nominal stress, σn /MPa

aging times. The SS curves at 77 K and for all aging
times exhibited low elastic limits, and the plateau 650
regime appeared from an approximate nominal strain
600 600 ks
of 0.002, following which work hardening occurred. 60 ks
Herein, we refer to the three deformation stages as 550 6 ks
the “micro-yield”, “macro-yield”, and “work 0.6 ks
500
hardening” stages. The yield and tensile stresses 0.06 ks
increased until 6 ks and then decreased; however, the 0 ks
450
specimen aged for 600 ks exhibited higher strength 0 0.1 0.2 0.3
Nominal strain, σn /MPa
than the unaged specimen. The total elongation did
not significantly change, indicating that the aging Figure 2 Nominal stress – nominal strain curves at 77 K
treatment improved the strength-elongation balance for the specimens at various aging times. [4]
of ultra-low carbon steel at cryogenic temperatures.
3.3. Deformation behavior at 77 K in aged ultra-low carbon steel.

Figure 3 shows (a) a schematic illustration of the SS curve with interruption conditions and SEM images of identical regions
(b) before deformation and at the (c) elastic limit, and the (d) micro-yield stage, (e) macro-yield stage, and (f) work hardening
stage in the unaged specimen. The elastic limit is defined as the point where the stress and strain linear relationship gradient
during elastic deformation changes. Up to the elastic limit, the microstructure did not change (Figs. 3 (b) and (c)). At the
micro-yield stage (Fig. 3 (d)), bands appeared continuously across several grains, as indicated by the white arrows. The EBSD
analysis revealed that the band was a {112}<11-1> deformation twin. At the macro-yield stage (Fig. 3 (e)), the number of
deformation twins drastically increased and several twins were not continuous across grain boundaries, but independently
occurred inside single grains. At the work hardening stage (Fig. 3 (f)), the number of twins did not increase. It was
demonstrated that the high strain were generated by the deformation twinning. The generation of twins is closely related to
micro- and macro-yielding.
Macro-yield stage
Micro-yield stage
(a) (b) (c)

Stress
(c) (d) (e) (f) Strain 50 μm 50 μm
(d) (e) (f)
50 μm 50 μm 50 μm
Figure 3 (a) Schematic illustration of a stress-strain curve with interruption conditions, and SEM images of an identical region
(b) before deformation, at the (c) elastic limit, (d) micro-yield stage, (e) macro-yield stage, and (f) work hardening stage in the
unaged specimen. [4]

Figure 4 shows the length of the twin
Length of twin boundaries per unit area, L/ μm-1

boundaries per unit area at the micro-yield,
0.05
macro-yield, and work hardening stages in the
Unaged
unaged, 6 and 600 ks aged specimens. The 6 ks
0.04
observation area was 1 mm × 1 mm. The 600 ks
deformation twins occurred until the
0.03
micro-yield stage independent of the aging
conditions. At the macro-yield stage,
deformation twins increased in the unaged and 6 0.02
ks aged specimens, but it negligibly increased in

the 600 ks aged specimen. The length of the 0.01
twin boundaries per unit area at the work
hardening stage was equal to those at the 0
Micro-yield Macro-yield Work-hardening
macro-yield stage in all the specimens. In the
unaged and 6 ks aged specimens, Figure 4 Length of twin boundaries per unit area at the micro-yield,
macro-yielding occurred as a result of macro-yield, and work-hardening stages in the unaged, 6 ks and
deformation twinning, and then changed to slip 600 ks aged specimens. [4]
deformation at the work hardening stage. However, in the 600 ks aged specimen, macro-yielding occurred due to slip
deformation because the length of the twin boundaries per unit area were constant independent of the deformation stage.
4. Conclusion
Both the yield and tensile stresses at 77 K increased until the aging time of 6 ks, and then decreased until 600 ks. Under all
aging conditions, the nominal stress-nominal strain curves at 77 K exhibited low elastic limits, and the nominal stress plateau
regime appeared at a nominal strain of approximately 0.002, after which, work hardening occurred. In the unaged and 6 ks
aged specimens, several deformation twins occurred after the elastic limit and remarkably increased in the nominal stress
plateau regime, indicating macroscopic yielding. At the work hardening stage, the number of deformation twins increased
slightly. Therefore, macroscopic yielding occurred because of deformation twinning. In contrast, in the 600 ks aged specimen,
deformation twins negligibly increased at the macroscopic yield, indicating that macroscopic yielding occurred due to slip
deformation.
Acknowledgement
This work was performed under the support of the 28th ISIJ Research Promotion Grantt and the Grant-in-Aid for Scientific Research
(KAKENHI) Grant. (No. 20K1460.).
Reference
[1] N. Maruyama, M. Takahashi: Tetsu-to-Hagane, 93 (2007), 506.
[2] S. Araki, K. Fuji, D. Akama, T. Tsuchiyama, S. Takaki, T. Ohmura, J. Takahashi: ISIJ Int., 58 (2018), 1920.
[3] N. Koga, O. Umezawa, M. Yamamoto, T. Yamamoto, T. Yamashita, S. Morooka, T. Kawasaki, S. Harjo: Metall. Mater. Trans. A.,
52 (2021), 897.
[4] N. Koga, Y. Kanehira, P. T. H. Huyen, K. Hori, O. Umezawa: ISIJ Int., 61 (2021), 2308.

Local deformation behavior of ferrite + martensite dual-phase steels with different
martensite hardness
Myeong-heom Park1,*, Yuto Fujimura1 and Nobuhiro Tsuji1,2
1
Department of Materials Science and Engineering, Kyoto University, Yoshida Honmachi, Sakyo-ku, Kyoto 606-8501, Japan
2
Elements Strategy Initiative for Structural Materials (ESISM), Kyoto University, Yoshida Honmachi, Sakyo-ku, Kyoto 606-8501,
Japan
*email: park.myeongheom.8r@kyoto-u.ac.jp
Keywords: dual phase steels, mechanical properties, digital image correlation (DIC), strain distribution
Background
Low-carbon dual phase (DP) steels composed of soft ferrite and hard martensite are widely used in automotive industries
due to their good combination of strength and ductility. Over several decades, many studies of DP steels have been
achieving better mechanical properties by changing microstructural factors such as grain size, morphology, volume fraction
and strength (hardness) of each phase 1-4). It is believed that such a well-balanced strength-ductility of DP steels is attributed to
microscopically heterogeneous deformation accompanied with mechanical interaction between two phases having different
hardness. The difference in hardness (strength) between two phases may significantly affect local deformation behavior as
well as global mechanical response. For understanding underlying deformation nature of DP steels having different phase
hardness (strength), the local deformation behavior should be characterized. Digital image correlation (DIC) method 5, 6)
that can provide full-field local strain distributions may be one promising technique for quantitatively characterizing
deformation heterogeneity in DP steels 7, 8). In the present study, we prepared two kinds of DP structures having different
hardness of martensite through tempering heat treatment, and characterized global tensile properties and local deformation
behavior in terms of strain-partitioning evolution of each phase using microscopic DIC (μ-DIC) technique for understanding
local deformation nature of DP steels with the change of martensite hardness.
Experimental procedure
A low carbon steel with a chemical composition of Fe-2Mn-0.1C (wt. %) was used in the present study.
Homogenization at 1200℃ for 48 hrs + furnace cooling under a vacuum atmosphere and subsequent cold-rolling by 90%
reduction in thickness were carried out. Afterwards, the cold-rolled specimen was austenitized at 830℃ for 3 hrs and
subsequently furnace-cooled to obtain ferrite + pearlite (F+P) structure. DP structure was finally obtained by ferrite +
austenite two phases intercritical annealing at 750℃ for 1 hr and subsequent water-quenching (WQ) during which the
austenite transformed to martensite. This DP specimen obtained will be referred to as “as-quenched DP”. In parallel, the
as-quenched DP specimens were subjected to tempering heat treatment at 400 ℃ for 1 hr followed by WQ, and the obtained
specimen will be referred to as “tempered DP” hereafter. Microstructural observation was carried out by a field emission
type scanning electron microscope (FE-SEM) (JEOL, JSM-7800F) equipped with backscattered electron (BSE) detector at an
accelerated voltage of 15 kV. For SEM observation, the specimen was mechanically polished with 400-4000 grid-sized
emery papers and then electrolytically polished in a chemical solution of 90 vol% of CH3COOH and 10 vol. % of HClO4
with a voltage of 22 V for 30 s at room temperature. The ferrite grain size was measured by a linear interception method on
SEM microstructure images and the martensite volume fraction was estimated by the point counting method. Nano
hardness of each phase was measured by the use of a nano-indentation testing machine (TI 950 TriboIndenter, Hysitron) with
an indent load of 1000 μN and a dwell time of 0.5 s. Global mechanical properties of the DP specimens were characterized
by uniaxial tensile tests at room temperature with an initial strain rate of 8.3×10-4 s-1, Shimadzu AG-100kN Xplus tensile-test
machine. The tensile direction of the specimens was set to be parallel to the rolling direction of the sheets, and the tensile
specimens with a gage length of 10 mm and a cross section of 3 mm (width) × 1mm (thickness) were cut from the sheets.
Tensile strain of the tensile specimens was precisely measured by the digital image correlation (DIC) technique using a
dedicated DIC analysis software (Correlation Solutions, Vic-2D). For microscopic DIC (μ-DIC) analysis, surfaces of the
tensile specimen were polished prior to the tensile test, and identical area observations were carried out in SEM. For

achieving high-resolution μ-DIC strain analysis, fine random dot-patterns of colloidal silica (SiO2) having an average particle
radius of 0.04 μm were artificially introduced on the polished surface as a marker to track identical positions. The subset size
and strain-measurement step for the micro-DIC analysis were set to be 2.3 μm × 2.3 μm and 0.39 μm, respectively.
Results
Figure 1 shows SEM microstructures of (a) as-quenched DP and (b) tempered DP specimens. F and M indicated on
the images denote ferrite and martensite, respectively. Two kinds of DP specimens showed very similar microstructural
features in martensite distribution (i.e., network-shaped morphology surrounding ferrite grains), martensite volume fraction (~
25%) and ferrite grain sizes (~15 μm) in the low magnification SEM images. In high magnification SEM images, on the
other hand, a great number of fine precipitates with bright contrast were observed in the interior of martensite in the tempered
DP specimen, which were considered to be carbides formed by tempering treatment. In ferrite grains, no significant changes
were found even at high magnification observations.
Figure 1 SEM microstructures of the (a) as-quenched DP specimen and (b) tempered DP specimen.
Nano hardness of each phase was investigated by nano-indentation testing, and obtained hardness results are shown in
Table 1. It was found that a significant decrease in martensite hardness by tempering heat treatment was recognized,
whereas ferrite showed nearly the same hardness value, indicating that softening effect by tempering took place mainly in the
martensite due to a decrease of dislocation density and solid-solution strengthening effect of carbon.
Table 1 Nano hardness of ferrite and martensite in the as-quenched DP and tempered DP specimens.
Figure 2 demonstrates engineering stress-strain curves of the (a) as-quenched DP and (b) tempered DP specimens.
From the results of Fig. 1 and Table 1, it is expected that the difference in stress-strain behavior between two kinds of DP
specimens is mostly attributed to martensite hardness (strength). Discontinuous yielding was observed in the tempered DP
specimen, in which Lüders (strain localization) band propagation was confirmed in DIC strain distribution map during tensile
deformation. The tempered DP specimen having softer martensite exhibited decreased strength but enhanced ductility

(especially post-uniform elongation) compared with the as-quenched DP specimen with harder martensite. A great decrease
in strain hardening capability was recognized in the tempered DP specimen, which was probably related to the softening of
martensite by tempering treatment. For understanding the difference of stress-strain behavior and strain hardening capacity
between the as-quenched DP and tempered DP specimens, local strain distribution in microstructures was investigated by
μ-DIC analysis.
Figure 2 Engineering stress-strain curves of the (a) as-quenched DP specimen and (b) tempered DP specimen with an initial
strain rate of 8.3 × 10-4 s-1 at room temperature.
Figure 3 displays SEM microstructures and corresponding DIC strain distribution maps of the (a) as-quenched DP and
(b) tempered DP specimens tensile-deformed to ~ 2% plastic strain. Tensile direction is parallel to the horizontal direction of
images, and the colors superimposed on SEM images correspond to the value of normal strain (ε11) in the tensile-axis direction
according to the key strain color bar. The particles on SEM images are the colloidal silica (SiO2) acting as markers for
making the μ-DIC analysis precise. In the as-quenched DP specimen, some of ferrite grains experienced very strong strain
localization due to hardly deformed martensite phase. The tempered DP specimen, in contrast, exhibited relatively
homogeneous deformation in μ-DIC strain distribution maps as a result of more contribution of softened martensite to plastic
deformation. The significant difference in global ductility between two DP specimens can be understood by the local strain
distribution behavior, especially in terms of strain-partitioning between ferrite and martensite.
We confirmed the strain distribution difference between the as-quenched DP and tempered DP specimens using the μ-
-DIC technique in the current study. The evolution of internal stress and dislocation density in different constituent phases
obtained from in-situ XRD analysis will be presented in the presentation. Based on the experimentally obtained strain- and
stress-partitioning results, underlying deformation mechanism of the DP steels and an effective material design strategy that
can achieve simultaneous enhancement of strength and ductility will be also discussed.

Figure 3 SEM microstructures and corresponding DIC strain distribution maps of the (a) as-quenched DP and (b) tempered
DP specimens tensile-deformed to ~ 2%.
Conclusions
In summary, we have investigated global mechanical properties of the DP structures having different martensite hardness
and characterized local deformation behavior in terms of strain-partitioning between ferrite and martensite by means of the
μ-DIC analysis. The main conclusions obtained in the current study are as follows:
(1) Two kinds of DP specimens having different martensite hardness were successfully fabricated.
(2) In the stress-strain behavior, the DP specimen obtained by tempering treatment (tempered DP) having softer martensite
exhibited decreased strength but enhanced ductility especially in post-uniform elongation, compared with the
as-quenched DP specimen with harder martensite.
(3) In the as-quenched DP specimen, some ferrite grains experienced strong strain localization due to hardly deformed
martensite phase. The tempered DP specimen exhibited relatively homogeneous deformation in μ-DIC strain
distribution maps, as a result of more contribution of martensite to plastic deformation. Homogeneous deformation in
the microstructure shown in the tempered DP specimen could be one reason for the enhancement of global ductility (total
elongation), inhibiting strain localization.
Acknowledgement
This research work was financially supported by the Elements Strategy Initiative for Structural Materials (ESISM;
JPMXP0112101000), JST CREST (JPMJCR1994), and KAKENHI (Grant-in-Aid for Scientific Research from the Japan Society
for the Promotion of Science; 15H05767, 19H02459 and 20K14608), all from the Ministry of Education, Culture, Sports, Science
and Technology (MEXT), Japan. All the supports are gratefully appreciated.
References
1) M. Calcagnotto, Y. Adachi, D. Ponge, D. Raabe: Acta Mater. 59 (2011) 658-670.
2) A. A. Sayed and Sh. Kheirandish: Mater. Sci. Eng. A. 532 (2012) 21-25.
3) M. Soliman and H. Palkowski: Mater. Sci. Eng. A. 777 (2020) 139044.
4) M. Calcagnotto, D. Ponge and D. Raabe: Mater. Sci. Eng. A. 527 (2010) 7832-7840.
5) J. Zhang, A. Sweedy, F. Gitzhofer and G. Baroud: Opt. Lasers. Eng. 100 (2018) 259-266.
6) S. Hamada, T. Fujisawa, M. Koyama, N. Koga, N. Nakada and T. Tsuchiyama: Mater. Charact. 98 (2014) 140-146.
7) C.C. Tasan, J.P.M. Hoefnagels, M. Diehl, D. Yan, F. Roters and D. Raabe: Int. J. Plast. 63 (2014) 198-210.
8) K. Park, M. Nishiyama, N. Nakada, T. Tsuchiyama and S. Takaki: Mater. Sci. Eng. A. 604 (2014) 135-141.

Improvement of mechanical properties from the viewpoint of stress partitioning
Noriyuki Tsuchida1,*
1
Graduate School of Engineering, University of Hyogo, 2167 Shosha, Himeji, Hyogo 671-2280, Japan
*email: tsuchida@eng.u-hyogo.ac.jp
Keywords: steel, stress, strain, TRIP, neutron diffraction
1. Introduction
Steels are usually used as multi-phase or multi-microstructure steels which consist of different phases or microstructures.
Thus, it is very important to discuss their mechanical properties from the viewpoint of deformation behavior of each
constituent phase or microstructure 1,2). We have been studied the tensile deformation behavior of various multi-microstructure
steels from the phase strains and the lattice strains obtained by neutron diffraction experiments 3−5). From our previous studies,
it is found that the tensile deformation behavior of constituent phases and their difference, i.e., stress partitioning, play
important roles in the mechanical properties of various multi-phase steels. The stress partitioning also affects the
deformation-induced martensitic transformation (DIMT) behavior of austenite (γ) phase 6). In this study, I take notice of
transformation induced plasticity (TRIP) steels such as TRIP-aided multi-microstructure steels and metastable austenitic
stainless steels and try to discuss the improvement of mechanical properties due to the stress partitioning and TRIP effect.
neutron
Neutron
Slit
slit Load
dir
Collimator
collimator
-90- 90
degdeg +90
+90 degdeg
detector
detector  detector
detector
sample
Sample
Fig. 1 Schematic illustration of in situ neutron Fig. 2 Phase stresses of γ, α and α' in 0.2C (steel A)
diffraction experimental setup. and 0.4C (steel B) TRIP steels as functions of applied
true strain.
2. Analysis of deformation-induced martensite in TRIP steels

DIMT behavior and its effect on the strengthening mechanism in two TRIP-aided multi-microstructure steels (TRIP steels)
with different carbon contents (0.2 and 0.4 mass%) were monitored using in situ neutron diffraction experiments during
tensile tests 4). Neutron diffraction experiments were conducted at TAKUMI, a high-resolution high-intensity time-of-flight
neutron diffractometer for engineering sciences at Materials and Life Science Experimental Facility (MLF) of Japan Proton
Accelerator Research Complex (J-PARC) 4,7). The loading machine was installed at 45 degrees with respect to the incident
neutron beam and the neutron diffraction profiles in the axial and transverse directions were recorded by two detector banks
simultaneously (Fig. 1). The peak analyses of deformation-induced martensite (α') in the TRIP steels were performed by a
multi-peak fitting method 4,6). The different carbon content affected different volume fractions of parent phases before
deformation, where the higher carbon content increased the volume fraction of retained austenite (γR). The carbon

concentration in γR was measured to be similar in both steels, resulting the similar rates of relative amount of α' from γR with
respect to the applied true strain. The phase stress of α' was approximately 2.5 GPa and was found much larger than that of γR
or bainitic ferrite since the α' was generated at the beginning of plastic deformation (Fig. 2). The phase stresses obtained
during tensile deformation were multiplied by the volume fractions and were compared to the true stresses to evaluate the
stress contribution of each phase. The stress contribution of α' to the strength increased with the increase of applied true strain,
where that of bainitic ferrite was almost unchanged and that of γR decreased. We investigated the phase stress of α' in various
TRIP steels with various carbon contents 4−6). The phase stresses of α' in various TRIP steels were almost the same 8−10). This is
because the strength of α' is dependent on the carbon concentration in γR with about 1 mass%. On the other hand, it was found
that the effect of deformation temperature on phase stress of α' was very small from the experimental results of TRIP and
metastable austenitic stainless steels 5,8,9).
3. Enhancement of uniform elongation by controlling the deformation-induced transformation behavior

It is important to control the DIMT behavior up to the latter part of deformation to improve the uniform
elongation (U.El) through the TRIP effect. In our previous study 5), tensile tests with decreasing deformation
temperature were conducted to achieve continuous DIMT up to the latter part of deformation. As a result, U.El
was improved by approximately 1.5 times compared with that in the tensile test conducted at 296 K (Fig. 3).
The enhancement of U.El in the temperature change test was discussed by neutron diffraction experiments. In
the continuous DIMT behavior, a larger transformation rate at a larger true strain was obtained in the
temperature change test compared with that in the tensile test at 296 K (Fig. 4). The tensile deformation
behavior of ferrite (α), γ and α' phases were investigated from the viewpoint of fraction weighted phase stress.
The tensile test with decreasing deformation temperature caused the increase of fraction weighted phase stress
of α and that of α' affected by the DIMT behavior resulting in the increase in the work hardening, and also
controlled the ductility of α and α' resulting in the enhancement of U.El. Especially, the α phase contributed to
maintaining high strength instead of α' at a larger true strain. Therefore, not only the DIMT behavior but also
the deformation behavior of γ, α, and α' are important in order to improve U.El due to TRIP effect.
0.1
(a)
Temperature change test
deformation-induced martensite
0.08
800
296 K
Volume fraction of
0.06
296 K
Nominal stress (MPa)
600 0.04
Enhancement of 0.02
400 uniform elongation
(+18%)
0
Temperature change 0.5
Transformation rate
(b)
200 0.4 Temperature
296 K change test
0.3
0.2
0 0.1
0 0.1 0.2 0.3 0.4 0.5
Nominal strain 0
0 0.1 0.2 0.3 0.4
True strain
Fig. 3 Nominal stress–nominal strain curves Fig. 4 Volume fraction of deformation-induced

obtained by the temperature change tensile test and martensite (a) and transformation rate (b) as a
the tensile test at 296 K. function of true strain obtained by the temperature
change test B and the tensile test at 296 K.

4. Effect of strength for the deformation-induced martensite on TRIP effect
The strength of α' in the TRIP steels were almost the same because of the carbon concentration in γR 4−6). On the other hand,
the strength of α' transformed from γ phase in stainless steels can be controlled by N content. We prepared a
Fe–18%Cr–6%Ni–0.2%N–0.1%C (6Ni–0.2N–0.1C) steel and examined effect of deformation temperature on the tensile
properties 10). The tensile properties obtained by tensile tests at various deformation temperatures between 123 and 373 K were
compared with those of SUS304 steel. The 0.2% proof stress, tensile strength, and U.El of the 6Ni–0.2N–0.1C steel were
larger than those of SUS304 at all temperature studied (Fig. 5), and the mechanical stability of γ phase for the 6Ni–0.2N–0.1C
steel was higher than that for the SUS304 steel. Neutron diffraction experiments at room temperature showed that the
improvements in the mechanical properties in the 6Ni–0.2N–0.1C steel were associated with larger work hardening of the γ
phase and larger strength of the α'. The difference in the phase stress of α' between the 6Ni–0.2N–0.1C and SUS304 was
approximately 1 GPa (Fig. 6). The increase in strength of α' with N and C additions leads to better mechanical properties due
to the TRIP effect, despite of smaller amounts of DIMT of γ.
-150 -100 -50 0 50 100 (oC)

100 3500
0.2% proof stress and tensile strength (MPa)
1600 Tensile strength

■
□
?
?
●
○ a'
a' (6Ni-0.2N-0.1C)
(SUS304)
a'
3000
80
Estimated phase stress (MPa)

Uniform elongation (%)
2500
1200
60
Uniform elongation 2000
800 1500
40
?
0.2% proof stress
1000
400
20
500
Solid: 6Ni-0.2N-0.1C, Opened: SUS304

0
0 0 0 0.1 0.2 0.3 0.4 0.5 0.6
100 150 200 250 300 350 400
Temperature (K) True strain
Fig. 5 0.2% proof stress, tensile strength and uniform Fig. 6 Estimated phase stress of austenite (γ) and
elongation as functions of temperature in the deformation-induced martensite (α') phases vs. true strain
6Ni-0.2N-0.1C and SUS304 steels. in the 6Ni-0.2N-0.1C and SUS304 steels obtained by the
neutron diffraction experiments..
References
1) N. Tsuchida, S. Harjo, T. Ohnuki, Y. Tomota: Tetsu-to-Hagane 100 (2014) 1191.
2) R.G. Davies: Metall. Trans. A. 9 (1978) 451.
3) N. Tsuchida, T. Kawahata, E. Ishimaru, A. Takahashi, H. Suzuki and T. Shobu: ISIJ Int. 53 (2013) 1260.
4) S. Harjo, N. Tsuchida, J. Abe and W. Gong: Sci. Rep. 7 (2017) 15149.
5) N. Tsuchida and S. Harjo: Metals 11 (2021) 2053.
6) N. Tsuchida, T. Tanaka, Y. Toji: Tetsu-to-Hagane 105 (2019) 918.
7) S. Harjo, S. Kubota, W. Gong, T. Kawasaki, S. Gao: Acta Mater., 196 (2020) 584.
8) T. Yamashita, S. Morooka, S. Harjo, T. Kawasaki T, N. Koga, O. Umezawa: Scripta Mater. 117 (2020) 6.
9) N. Tsuchida, R. Ueji, T. Inoue: ISIJ Int. 61 (2021) 632.
10) N. Tsuchida, E. Ishimaru, M. Kawa: ISIJ Int. 61 (2021) 556.

Observation of deformation behavior of steels using pulsed neutron diffraction
Stefanus Harjo1), Wu Gong1), Takuro Kawasaki1), Wenqi Mao1), Satoshi Morooka1) 2)
1) J-PARC Center, JAEA

2) Materials Sciences Research Center, JAEA
Abstract:
The observation of deformation behavior, plays an important role in building basic knowledge and
providing feedback in material development. With the recent significant improvement in the properties
of advanced steel materials, the structure and deformation mechanism have become complicated.
Multi-phase structures have become commonplace, with microstructural changes and multiple
deformation modes occurring simultaneously during deformation. Such conditions have made
material characterization difficult.
Neutron diffraction is becoming one of the powerful probes to characterize various properties related
to the strength and microstructures of engineering materials, and its usefulness is also becoming well
known. Neutron has a high penetration depth and can be used to observe atomic arrangement using
diffraction. Careful analysis of the Bragg peaks in a neutron diffraction pattern can reveal important
structural details of a sample material such as internal stresses, phase conditions, dislocations, texture
etc. Such information is often crucial in engineering applications and the ability to carry out either ex
situ or in situ measurements makes neutron diffraction particularly useful in this respect. With the
application of neutron diffraction using the time-of-flight method, in situ neutron diffraction
measurement under various conditions became feasible, as well as to increase the accuracy by
measuring multi-diffraction peaks for analyses. Furthermore, due to the recent increase in the intensity
of the pulsed neutron source and the increase in the resolution of the neutron diffractometer, the
strength and microstructure of the material can be observed with finer changes, and more accurate
understanding of the materials mechanical or functional mechanisms can be achieved.
TAKUMI which was installed in J-PARC, is one of neutron diffractometers which are suited for studies
related to the observation of deformation behavior of steels. In the presentation, the current status of
TAKUMI, its capabilities, and some studies of deformation behavior of steels will be introduced.

Effect of grain size on the tensile properties of 304 stainless steel studied
by in situ neutron diffraction
Si Gao1), Yu Bai1) 2), Wenqi Mao1) 3), Wu Gong3) 5), Akinobu Shibata4) 5), Nobuhiro Tsuji1) 5)
1) Dept. Materials Science and Engineering, Kyoto University

2) School of Materials Science and Engineering, Dalian University of Technology
3) J-PARC Center, Japan Atomic Energy Agency
4) Research Center for Structural Materials, National Institute for Materials Science (NIMS)
5) Elements Strategy Initiative for Structural Materials (ESISM), Kyoto University
Abstract:
Conventional austenitic stainless steels (ASSs) exhibit excellent corrosion resistivity and
deformability but low yield strength due to their FCC structure with coarse grain sizes. In recent years
it has been found that the ultra-fine grained (UFG) ASSs, usually fabricated by heavy rolling and
annealing processes, exhibit good combinations of strength and tensile ductility which make them
prospective materials for future industrial applications. Deformation induced martensitic
transformation (DIMT) is believed to play an important role in the excellent mechanical properties of
the UFG ASSs, however, the effect of the ultra-fine grain size on DIMT has not yet been clarified and
the corresponding excellent mechanical properties of UFG ASSs are lacking of interpretation. In the
present study, commercial 304 ASS specimens having different grain sizes ranging from 0.3 µm to 22
µm were fabricated by cold rolling and annealing process, and tensile tests with in-situ neutron
diffraction were carried in order to investigate the grain size dependence of the kinetics of DIMT and
the stress partitioning between austenite and martensite during tensile deformation. Tensile test results
showed that the yield strength increased from 250 MPa to 1000 MPa and the total elongation decreased
from 80% to 50% when the grain size of the specimen decreased from 22 µm to 0.3 µm. Neutron
diffraction revealed that stress partitioning behavior between austenite and martensite did not exhibit
notable difference among the specimens, while the kinetics of the DIMT dramatically increased by
decreasing the grain size, which was believed to be the main reason for the excellent tensile properties
of the UFG specimens. The kinetics of the DIMT will be discussed in terms of the mechanical stability
of austenite. Other interesting deformation behaviors associated with the DIMT, such as the huge
Lüders deformation in the UFG specimen, will also be discussed.

The possibility of improved cryogenic toughness of medium-Mn steel by friction stir
welding
Jeongho Han1,*, Mun Sik Jeong1, Tak Min Park1, Dong-Il Kim2, Hidetoshi Fujii3, Hye Ji Im4, Pyuck-Pa Choi5,
Seung-Joon Lee2
Division of Materials Science and Engineering, Hanyang University, Seoul 04763, Republic of Korea
1
2
Department of Advanced Materials Engineering, Korea Polytechnic University, Siheung 15073, Republic of Korea
3
Joining and Welding Research Institute, Osaka University, Osaka 567-0047, Japan
4
Department of Materials Science and Engineering, Northwestern University, Evanston, IL 60208, USA
5
Department of Materials Science and Engineering, Korea Advanced Institute of Science and Technology, Daejeon 34141, Republic
of Korea
*email: jeonghohan@hanyang.ac.kr
Keywords: medium-Mn steel, welding, microstructure, impact toughness
Medium-Mn steels, which are composed of ~3-12 wt% Mn, <0.3 wt% C, and minor doping of steel alloying elements,
have been widely studied during last years, and they are suggested as next generation advanced high-strength steel and
cryogenic materials [1]. After hot rolling process, the steel normally reveals 100% α martensitic microstructure, however, it
shows two-phase microstructure with retained austenite (γR) and tempered martensite (αT) after intercritical annealing. Owing
to the large fraction of γR (< 40 vol%), the steel reveals an excellent combination of strength and ductility, and also shows the
high impact absorbed energy at ambient temperature. However, due to Mn segregation at pre-existed prior austenite grain
boundary (PAGB), the steel shows the severe intergranular crack when fractured at cryogenic condition (e.g., -196 °C),
leading to poor impact absorbed energy [2].
In the present study, to predict the possibility of application of medium-Mn steel for cryogenic materials, we investigated
the cryogenic impact toughness of medium-Mn steel after welding. Briefly, we propose a friction stir welding (FSW) is a
novel welding method of the medium-Mn steels for the cryogenic application [3]. The medium-Mn steel with two-phase
microstructure (retained austenite and martensite) was used as a base material, and the microstructures and impact toughness
after FSW and conventional tungsten inert gas (TIG) welding were systematically investigated and compared. The prime
scientific novelty of the present study is summarized below:
1. The FSW-processed steel revealed a greater impact absorbed energy than the TIG-welded steel owing to the presence
of retained austenite at weld zone.
2. The FSW-processed steel showed a higher toughness than base material, because the grain morphology tuning driven
by FSW could eliminate the weak microstructural feature of base material (i.e., prior austenite boundary) and lead to more
active transformation-induced plasticity.
Acknowledgement
This work was performed under the support of National Research Foundation of Korea (No. 2020R1F1A1070808) and Korea
Institute for Advancement of Technology (No. P0008425).
References
1) Y.-K. Lee and J. Han: Mater. Sci. Technol. 31 (2015) 843-856.
2) J. Han, A.K. da Silva, D. Ponge, D. Raabe, S.M. Lee, Y.-K. Lee, S.I. Lee, B. Hwang: Acta Mater. 122 (2017) 199-206.
3) M.S. Jeong, T.M. Park, D.-I. Kim, H. Fujii, H.J. Im, P.-P. Choi, S.-J. Lee, J. Han: J. Mater. Sci. Technol. 118 (2022) 243-254.

Carbon enrichment at coating/substrate interface and its effect on
bendability of Al-Si coated press hardening steel

L.L. Zeng1, D.P. Yang1, S. Zhou2 and H.L. Yi1,2,*
1
State Key Laboratory of Rolling and Automation, Northeastern University, Shenyang, PR China
2
Easyforming Materials Technology Co., Ltd., Suzhou, PR China
*Corresponding author: hlyi@ral.neu.edu.cn
Abstract: Al-Si coated press hardening steel (PHS) is widely applied on carbody due to its high strength,
which tensile strength usually exceeds 1500MPa. In addition to strength, the fracture strain of PHS in
bending deformation characterized by the bending angle in tests of VDA238 standard is critical for the
crash performance of carbody. The Al-Si coating transforms into Fe-Al intermetallics during
austenitization heating in the hot stamping process, and therefore prevents severe oxidation of the sheet
surface. However, the Al-Si coating was found to seriously deteriorate the fracture strain. In this research,
the fracture process of a press-hardened Al-Si coated PHS during bending test was investigated. The Al-
enriched alloying layers involving the intermetallic layers and the ferrite layer are not able to inhibit the
crack propagation, but the cracks are then blunted by the hard martensite substrate. Finally, fracture
happens by the shear band initiation and propagation from the surface of martensite. The carbon
enrichment about several micrometers in martensite at the coating/substrate interface after press-
hardening was found for the first time to deteriorate the bending fracture strain of Al-Si coated PHS.
The coating/substrate interface migration during austenitization heating leads to the carbon diffusion
into the austenite substrate because carbon has large solubility in austenite compared to the negligible
solubility in Al-enriched alloying layers. A novel method of reducing the coating thickness has been
then invented to suppress the carbon enrichment by suppressing the coating/substrate interface migration.
This invention will change the commercial practice of PHS by improving 20% of bending fracture strain
and sacrificing neither of the other performances such as spot-weldabiltiy, paintability and corrosion
resistance after e-coating. The thin coating has another advantage that the austenitization soaking period
is reduced by 20%~30% due to the much less heat absorption of Al liquidation and the formation of Fe-
Al intermetallics.
Keywords: Lightweight of automobile; Press hardening steel; Al-Si coating; Bendability;

Interfacial carbon enrichment

Hydrogen embrittlement in high-strength medium- and high-Mn steels:
From fundamental understanding to new H-resistant microstructure design
Dirk Ponge1,*, Binhan Sun1 and Dierk Raabe1
1 Max-Planck-Institut für Eisenforschung, Max-Planck-Straße 1, 40237 Düsseldorf, Germany
*email: d.ponge@mpie.de
Keywords: medium manganese steel, TRIP, hydrogen embrittlement resistance, austenite/ferrite interface boundary
Aim and scope

In steels with more than 4 wt.% of Mn microstructures can be formed which provide high strength, good ductility and tough-
ness. However, multiphase microstructures providing high strength and strain hardening rate enhancing mechanisms like
TRIP or TWIP might cause a reduced resistance against hydrogen embrittlement (HE). We show the weaknesses in such
microstructures and analyze HE mechanisms, especially for the occurrence of TRIP. In H charged material, fresh martensite
(formed from austenite with higher H solubility) inherits H from the parent austenite. This might lead to a high H
supersaturation in fresh martensite and fast H redistribution to dislocations and grain and phase boundaries due to faster H
diffusion in the bcc/bct lattice. We observe that the main damage mechanisms during slow strain rate tensile tests of H charged
samples are cracking along martensite/austenite interphase boundaries and cleavage fracture inside fresh martensite.
In order to overcome such problems, novel microstructures can be created: A temperature change during intercritical
annealing enables to introduce gradients of Mn concentration inside the reverted austenite. Austenite regions with lower Mn
content (metastable austenite) still provide a TRIP effect, enhancing the uniform elongation. If H microcracks form in this
fresh martensite, austenite regions with higher Mn concentration (stable austenite) are able to stop such microcracks by
blunting. Such damage tolerant microstructure requires a refined grain structure in order to keep the stress intensity at crack
tips at a low level. Details of this new multi-step intercritical annealing process are given and the performance of conven-
tionally (one step) intercritical annealed and multi-step intercritical annealed material will be compared.
Material
A model medium Mn steel 0.2C-10.2Mn-2.8Al-1Si (in wt.%) was cast, hot and cold rolled and intercritically annealed (IA).
Results and Discussion

IA at 700°C/10min leads to a reversion of austenite with a volume fraction of 26% (IA700, Fig.1a). An increase in IA
temperature (800°C/10min) leads to an austenite volume fraction of 59% (IA800, Fig.1c).
Fig. 1 (a) EBSD phase

map shows ferrite matrix
( matrix) with austenite
volume fraction of 26%
after intercritical
annealing (IA) at 700°C;
(b) schematic of IA;
(c) IA at 800°C leads to
higher austenite volume
fraction of 59% ( matrix)
Slow strain rate tensile testing was performed for IA700 and IA800 with samples not charged with H (black curves in Fig. 2a)
and samples after pre-charging with H (red curves in Fig. 2a). The electrochemical pre-charging was performed in 3 wt.%
NaCl and 0.3 wt.% NH4SCN at current density of 5A/m2 for 24 h. IA800 shows a lower value of the yield stress but higher
strain hardening rates compared to IA700. The reason for the higher strain hardening rate is the lower chemical austenite

stabilization in IA 800 (less partitioning of Mn and C to austenite at 800°C than at 700°C). This results in a more active TRIP
effect in IA 800 and a significant increase of uniform elongation.
Fig. 2 (a) Results from slow

strain rate tensile tests and
thermal desorption spectros-
copy (TDS);
(b) In IA700 a faster H diffu-
sion into the sample during
charging is expected (fast diffu-
sion along the percolating );
(c)Percolating  grains in
IA800 are expected to block
fast ingress of H along 
grains.
For H pre-charged samples, thermal desorption spectroscopy (TDS) revealed a lower total content of 6.2 wt. ppm H in IA800
than in IA700 (18.2 wt. ppm H) for identical charging conditions. This fits to the idea that in the case of IA800 ( matrix) the
fast ingress of H along  will be blocked by  grains (Fig. 2c). Important to stress here that, even with lower yield stress and
lower total H content in IA800, the charged material fails at a low strain (11%) than IA700 (24%) and the loss in ductility due
to HE in IA800 is very high. Unfortunately, this is due to the more active TRIP effect in IA800 and its lower austenite
mechanical stability. This is beneficial in the uncharged condition to postpone the necking. However, in the charged condition
this leads to early H cracking. The mechanism is shown and explained in Fig. 3. We report more details of the different
embrittling mechanisms in IA800 and IA700 in [1].
Fig. 3 (a) EBSD phase map with image quality
map shows partial transformation of austenite into
fresh martensite α'. This is due to a strain induced
martensitic transformation (or TRIP-effect).
A “fresh” α'/ α' grain boundary is highlighted by
two white arrows.
(b) Schematic of redistribution of H after partial
 -> α' transformation:  has a higher H solubility.
During the displacive  -> α' transformation
all H atoms will be inherited from  to α'.
The higher oversaturation and faster diffusion
in α' lead to a fast redistribution of H to
dislocations and boundaries.
(c, d) At larger local strain, cracks along H en-
riched α'/α' and /α' boundaries are observed,
very often initiated at triple junctions.
(e) Schematic of cracking mechanism in (c, d).
This HE mechanism in IA800 can be classified as a phase transformation-driven H-enhanced decohesion (HEDE). In contrast,
in IA700 we observed a less detrimental effect of hydrogen (a ductile fracture mode with increased void nucleation rate by H)
[1]. But this comes with the drawback to hinder the TRIP effect by the higher mechanical stability of the austenite (higher Mn
and C content) in IA700. Is there a way to still take advantage of the ductility enhancing TRIP effect without significantly
decreasing HE resistance? The answer is “yes” and a way is shown in the following (more details in [2] and [3]):

The idea is to create two “types” of austenite: The “first austenite” is lean in Mn (Mn-lean) and optimized for enhancing
ductility by a TRIP effect. In case of a H uptake the “second austenite” (Mn-rich), richer in Mn and stable against strain induced
martensite transformation, can stop cracks formed in fresh martensite ` by blunting sharp crack tips by plastic deformation in
a non-transforming austenite.
Fig. 4 shows a conventional microstructure (HOM) with only one austenite, optimized for TRIP. Mn is distributed homogene-
ously in  and early failure by phase transformation-driven H-enhanced decohesion can take place as described above.
However, the microstructure with a heterogeneous Mn distribution in austenite (HET, Fig. 5) provides both: Mn-lean areas in
austenite (Mn-lean) improve ductility by the TRIP effect but in the presence of H microcracks can form in the fresh α'
martensite. However, the Mn-rich areas in austenite (Mn-rich) are able to stop such microcracks by blunting the crack tips. This
occurs by dislocation activity and requires a higher mechanical stability to avoid the formation of fresh α' martensite in Mn-rich.
Fig. 4 One step IA leads to a homogeneous distribution of Mn Fig. 5 New multistep IA treatment creates inhomogeneous Mn
in  when α' forms, H redistribution favors sharp cracks distribution. Mn-lean austenite allows for TRIP effect.
along boundaries and cleavage cracks inside α'. Possible cracks are blunted by the stable Mn-rich austenite.
Fig. 6 shows the modified treatment (Fig. 6 b,c,d) to create the HET microstructure and schematically the microstructure
changes along all processing steps (Fig. 6 e,f,g,h,i).
Fig. 6 Multistep treatment

for HET microstructure:
(a) IA temperature effect
on Mn and C content in 
(b) Mn-rich forms in 1st IA
step at low temperature of
700°C with high Mn
content (~15 wt. %).
(c) cold rolling (50%
reduction) to partially
transform Mn-rich into α'
(accelerates reversion of
new  during next IA step
and fragments Mn-rich to
refine final microstructure)
(d) short IA step at higher
temperature to form
Mn-lean.
(e,f,g,h,i) schematics of mi-
crostructure changes
during treatment steps,
grey scale indicates Mn
content.

Fig. 7 shows the heterogeneous Mn distribution in austenite (HET sample) versus the homogeneous Mn distribution in
austenite (HOM sample) after a conventional single step IA (750°C/5min).
Fig. 7 (a) Phase map shows  and  after treatment shown in Fig. 6. Fig. 8 In comparison the EDX Mn map for the single
(b) corresponding EDX Mn map reveals heterogeneous Mn step IA annealing (cold rolled to same thickness as
distribution in  (Mn-rich highlighted by red circles). HET and 750°C/5min).
In uncharged condition the stress-strain curves of HET and HOM samples are similar [3]. The transformed austenite fraction
versus local strain curves are also similar for HET and HOM samples [3], indicating a similar TRIP effect and mechanical
performance in H free condition.
In contrast, tensile tests of H charged HET and HOM samples reveal a significantly higher total elongation of HET samples in
comparison to HOM samples (Fig. 9) and samples of other advanced high strength steels of similar strength (Fig. 10).
Fig. 9 Results from slow strain rate tensile tests for HOM and Fig. 10 Comparison of total elongation versus H
HET samples; TDS shows similar total H content after H concentration (HET, HOM and other advanced high
charging (3 wt.% NaCl, 0.3 wt.% NH4SCN, 5A/m2, 24 h). strength steels with similar strength level).
Acknowledgement
Binhan Sun was supported by Alexander von Humboldt Foundation.
References
1) B. Sun, W. Krieger, M. Rohwerder, D. Ponge and D. Raabe: Acta Materialia 183 (2020) 313–328.
2) B. Sun, W. Lu, B. Gault, R. Ding, S. K. Makineni, D. Wan, C.-H. Wu, H. Chen, D. Ponge and D. Raabe: Nat. Mater. 20 (2021)
1629–1634. https://doi.org/10.1038/s41563-021-01050-y
3) Supplementary inf. to 2). https://static-content.springer.com/esm/art%3A10.1038%2Fs41563-021-01050-y/MediaObjects/41563_2021_1050_MOESM1_ESM.pdf

Effects of Microstructure and Deformation on the Hydrogen Embrittlement of a Pearlitic
Steel
Sang-Hyun Yu1, Hyun-Bin Jeong1, Jae-Seung Lee2, and Young-Kook Lee1,3*
1
Department of Materials Science and Engineering, Yonsei University, Seoul 03722, Republic of Korea
2
Technical Research Laboratories, POSCO, Pohang 37859, Republic of Korea
3
Graduate Institute of Ferrous Technology, Pohang University of Science and Technology, Pohang 37673, Republic of Korea
*email: yklee@yonsei.ac.kr
Keywords: Hydrogen embrittlement, Pearlitic steel, Lamella, Cold drawing, Axial crack
1. Introduction
The tensile strength of pearlitic steel is greatly improved by the refinement of lamellar spacing or cold drawing.
However, in general an increase in ultimate tensile strength (UTS) causes the reduction of the resistance to hydrogen
embrittlement (HE) 1-3). Nevertheless, pearlitic steel has a superior resistance to HE to tempered martensitic steel at the same
level of tensile strength due to its unique microstructure without prior austenite grain boundaries 4). Although many studies
have been performed on the HE of pearlitic steel, it is still needed to investigate the resistance to HE as functions of lamellar
spacing (λ) and prestrain. Therefore, in the present study the resistance to HE was evaluated using pearlitic steel specimens
with various lamellar spacings and cold drawing ratios (CDRs) by means of thermal desorption analysis (TDA), fractography
and silver decoration 5).
2. Experimental method
Pearlitic steel with a chemical composition of Fe-0.72C-0.20Si-0.70Mn-0.03Al (wt %) was used for this study. To
examine the effect of cold drawing on the resistance of HE, the wires of pearlitic steel were cold-drawn from 17 mm in
diameter to 14.2 mm, 12.6 mm and 10.8 mm after austenitizing at 1323 K and lead patenting at 923 K. The ASTM E-8M-03
subsized, round-shaped tensile specimens were machined using the cold-drawn wires. To investigate the effect of lamellar
spacing, undeformed pearlitic steel wires were machined to make tensile specimens. Tensile specimens were austenitized at
1273 K for 30 min, quenched to 823 K, 873 K and 923 K, and then held at a given temperature for 30 min, followed by air
cooling to room temperature. The specimens were electrochemically charged with H using a 3% NaOH aqueous solution
containing 0.3% NH4SCN. The H charging was conducted with a current density of 50 A/m2 at 300 K for 24 h. For thermal
desorption analysis (TDA), all H-charged specimens were heated at a constant rate of 100 K/h from 300 K to 693 K. slow
strain rate tensile tests (SSRTs) were performed at a crosshead speed of 0.1 mm/min. Fracture surfaces of tensile specimens
were observed using a FE-SEM after the SSRTs. The diffusion behavior of H was examined through the silver decoration
technique by immersed the samples into a 4.3 mM Ag[K(CN)2] aqueous solution for 1 h.

The H-charged, undeformed specimens exhibited only a peak (peak 1), which can be separated into two sub-peaks
(peak 1-1 and peak 1-2), in their H desorption rate curves regardless of the λ. Peaks 1-1 and 1-2 were generated by H
detrapping from the pearlitic ferrite (Fp)/cementite (θ) interface and dislocations in FP, respectively. The activation energy (Ea)
values of H desorption for peaks 1-1 and 1-2 are 23.2 kJ/mol and 26.1 kJ/mol, respectively. The H content was almost similar
regardless of λ (Fig. 1a). However, the resistance to HE was higher in the specimen with the narrower λ and the higher tensile
strength, in spite of the similar H content (Fig. 1b).

Fig. 1. Variations of (a) H content and (b) the losses of elongation (El) loss and reduction of area (RA) with isothermal transformation
temperature in pearlitic steel.
To analyze the reasons for the unusual results, we observed fracture surfaces and microstructures. In the H-charged,
undeformed specimen with a narrow λ, tearing topography surface (TTS) appeared inside the tensile specimen after SSRT
(Fig. 2a). The TTS is an initiation site for HE in the pearlitic steel 6), and its location is related to H diffusion 7). Accordingly, H
permeation occurred more actively in the specimen with a narrow λ during tensile deformation (Fig. 2b).
Fig. 2. (a) Macroscopic fracture surface of H-charged, undeformed specimen with a fine lamellar spacing after SSRT 8) and (b) SEM image
showing the microstructure of the specimen isothermally transformed at 823 K.
Meanwhile, the H-charged, cold-drawn specimens showed not only peak 1 at ~375 K, but also a second peak
(peak 2) at ~600 K (Fig. 3a) in their H desorption rate curves. When tensile strain increased, peak 1 decreased whereas peak 2
increased. The main H trap site of peak 2 is the strained FP/θ interface with interfacial dislocations. Unexpectedly, when the
CDR was above 30%, both tensile strength and the resistance of HE were simultaneously improved despite the higher
diffusible H content (Fig. 3b).
Fig. 3. Variations of (a) H content and (b) the losses of El and RA with cold drawing ratio in pearlitic steel.
To find the cause of the improvement of the resistance to HE, the fracture surface of the H-uncharged specimen

was carefully observed. The elongations of H-uncharged and charged specimens decreased until the CDR of 30%, and then
was maintained with increasing CDR further, despite a continuous increase in UTS. The reason is that the tensile failure was
delayed due to micro-axial cracking (Fig. 4a) in the specimens with the CDR above 30%. When the CDR exceeded 30%, the
fracture mode changed from the brittle fracture characterized by TTS and cleavage surfaces to the ductile fracture
characterized by dimples and micro-axial cracks. The formation mechanism of micro-axial cracks is as follows: When CDR
was 30% or higher, some micro-cracks were already present inside the well-aligned pearlite colonies (Fig. 4b). Micro-cracks
were further formed and merged during the SSRT of H-uncharged, unnotched specimens (Fig. 4c). The merged cracks
propagated across the pearlite colonies to neighboring unaligned colonies (Fig. 4d). They developed micro-axial cracks while
growing along the direction of cold drawing and tensile deformation (Fig. 4e). In the H-charged specimens, H atoms near
micro-cracks diffused into micro-cracks, and the micro-axial crack generation was accelerated. As a result, ductile fracture
occurred in the region near the micro-cracks.
Fig. 1. (a) The surface of a micro-axial crack almost parallel to the direction of cold drawing in a H-uncharged, 60% cold-drawn specimen.
Schematic illustrations showing (b) pre-existing micro-cracks in as cold-drawn specimen, (c) additional formation of micro-cracks, (d) crack
coalescence, and (e) micro-axial cracking through a misaligned colony during tensile deformation 9).
4. Conclusions
1) As the λ decreased, the resistance to HE was improved despite the increase in tensile strength. This is because the formation
of TTS was delayed in the specimens with fine λ and short θ platelets.
2) Both the tensile strength and the diffusible H content of unnotched specimens was raised with increasing CDR.
Nevertheless, the resistance to HE was improved when the CDR was higher than 30% due to micro-axial cracking.
Acknowledgement
This work was performed under the support of the POSCO Technical Research Laboratories, Pohang, Republic of Korea (No.
2016Z008).
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Environment-induced degradation of iron based multicomponent alloys
Hong Luo*, Zhimin Pan, Xuefei Wang, Xiaogang Li
National Materials Corrosion and Protection Data Center, Institute for Advanced Materials and Technology, University of Science
and Technology Beijing, Beijing 100083, China
*email: luohong@ustb.edu.cn
Keywords: Fe contained alloys, Corrosion, Hydrogen embrittlement, Fracture
Traditional alloys use a metal element as the main element to make it a basic component, and then add different
alloying elements on this basis to obtain certain specific properties. Now it has been widely used by humans such as iron
alloys, aluminum alloys, Magnesium alloy, titanium alloy, etc. With the development of science and technology and the
improvement of human needs, especially the desire for space and deep-sea exploration, human beings have higher and higher
requirements for the physical and mechanical properties of materials. Traditional alloys and traditional preparation methods
have been difficult to meet this demand. Alloys face serious challenges. However, the design ideas of traditional alloy systems
are based on one or two components as basic components, and a small amount of other elements are added on this basis to
improve their properties. This design idea leads to the crystal structure, physical and mechanical properties of the alloy. All are
subject to the main element, which has an adverse effect on the overall performance of the alloy [1, 2]. It is based on this
thinking that multi-component alloys are developed. Multi-principal alloys are alloys that are formed by mixing equal or
relatively large proportions of five or more elements. These alloys are currently the focus of significant attention in materials
science and engineering because they have potentially desirable properties. Furthermore, research indicates that some alloys
have considerably better strength-to-weight ratios, with a higher degree of fracture resistance, tensile strength, and corrosion
and oxidation resistance than conventional alloys. Among them, the iron-based multi-principal alloys currently developed
account for a very high proportion of the entire multi-component alloy field. Like many alloys, multi-component alloys often
face corrosion, hydrogen embrittlement and cracking during environmental service, and their environmental sensitivities such
as corrosion and hydrogen embrittlement are closely related to the composition and structure of the passive film on the surface.
In the present work, we use traditional electrochemical methods, XPS and ICP-MS to study the environmental corrosion
behavior and mechanism of FeCoCrNiMn and carbon-doped FeCoCrNiMn multi-component alloys. The relationship
between the elements of Fe, Cr, Ni and the stable of the passive film are demonstrated. The mechanism of corrosion failure of
the multi-component alloy in acidic and neutral is well established. In addition, the influence of hydrogen element on the
surface microstructure and morphology of various iron-based multi-component alloys was in-situ observed by ECCI. The
hydrogen induced cracking of iron-based multi-component alloys were studied by SEM, TEM, ECCI and other analytical
testing and characterization methods. The influence of inclusions, precipitates and deformation structure on crack initiation
and crack propagation are invesitaged and the fracture behavior and mechanism of iron-based multi-component alloys in
hydrogen environment are also revealed [3-5].
Acknowledgement
This work was performed under the support of National Natural Science Foundation of China (No. 52071014).
References
1) Fu Y, Li J, Luo H, et al. Journal of Materials Science & Technology, 2021, 80: 217-233.
2) Luo H, Zhao B, Pan Z, et al. Materials Science and Engineering: A, 2021, 819: 141490.
3) Luo H, Lu W, Fang X, et al. Materials Today, 2018, 21(10): 1003-1009.
4) Luo H, Li Z, Mingers A M, et al. Corrosion Science, 2018, 134: 131-139.
5) Luo H, Zou S, Chen Y H, et al. Corrosion Science, 2020, 163: 108287.

Issue of hydrogen embrittlement evaluation
Shusaku Takagi1*
1
Steel Research Laboratory, JFE Steel Corporation, 1-1, Minamiwatarida-cho, Kawasaki-ku, Kawasaki, Kanagawa 210-0855,
JAPAN
*email: s-takagi@jfe-steel.co.jp
Keywords: delayed fracture, high strength steel, hydrogen content, local approach, high pressure hydrogen gas
The hydrogen society will come in the near future. Nowadays, the construction of hydrogen infrastructure and the
improvement of efficient energy consumption in various transportation and facilities are accelerated. In the situation, the
application of high strength steels must be expanded because the weight reduction of mobility and the downsizing of
equipment which are effective for the improvement of energy efficiency and the cost reduction of hydrogen infrastructure can
be realized with application of high strength steels. On the other hand, mechanical properties of high strength steels deteriorate
due to hydrogen atoms intruding into steels11-2). With the construction of a hydrogen society and the increase in the application
of high strength steels, the situation in which hydrogen atoms contact high strength steels increase. Therefore the issue of
hydrogen embrittelment in high strength steels becomes important more and more. For expansion of the application of high
strength steels, the risk of hydrogen embrittlement (hereinafter HE) have to be evaluated appropriately. In this topic, various
HE evaluation methods are shown and issue of HE evaluation are introduced.
There are many HE susceptibility evaluation index, for example, critical hydrogen content at fracture limit (Hc),
fracture stress, total elongation, reduction of area and fatigue crack growth rate. These properties are obtained by Constant
Load Test(CLT), Slow Strain Rate Technique(SSRT), Constant Strain Test (for example, 4-point bending test, U or V-bending
test) ,fatigue crack growth rate test.
By CLT with circumferential notch specimens under hydrogen pre-charging environment, various studies were
carried out on tempered martensitic steels with tensile strength of about 1500MPa for bolt3-6). The critical diffusible hydrogen
content (Hc) which is the maximum diffusible hydrogen content in the unfracture specimens can be determined. The value of
Hc is one of the index of hydrogen embrittlement resistance of steels and it becomes lower with increase of stress
concentration factor at notch root which is influenced notch root radios and specimen diameter and specimen diameter5-6).
Initial cracks are generated at the position where stress along tensile direction and hydrostatic stress are maximum7). It is
suggested HE critical condition can be determined by local hydrogen content and local stress around the fracture point.
Diffusible hydrogen atoms diffuse to high hydrostatic stress region and accumulate. In detail, stress distribution and hydrogen
distribution in the fracture process zone are important and if the material is more brittle, the process zone is limited close to the
maximum stress and the maximum hydrogen content position8-9). In CLT, when cracks are generated all at once, those cracks
absolutely propagate due to the severe stress and hydrogen content conditions at the crack tip7). Therefore, the crack initiation
condition is equal to the fracture critical condition.
SSRT has been using in various field10-12). SSRT is conducted under strain rate from about 10-4/s to 10-6/s because
HE phenomena is clearly shown under the strain rate lower than about 10-4/s12-13). Testing time of SSRT is about several hours.
It is shorter than that of CLT which is about several days to several month. So, by SSRT a lot of data can be obtained more
easily than by CLT. On the other hand, by SSRT unfracture data cannot be obtained14). HE is evaluated with decrease of
elongation, strength or reduction of area. Degree of HE increase with increasing hydrogen content in specimens or severe
hydrogen charging condition11).
Constant strain tests can be easily conducted with a small apparatus. High strength steel sheets for automobile are
used after press forming. Since microstructural damage introduced by press forming affects the HE failure limit, specimens
for the evaluation of HE sensitivity should better simulate the forming mode. A U-bending specimen has been used which
was tightened by bolt for applying stress in order to evaluate the HE susceptibility of roll-formed pipe applied to the impact
beam15-18). Nowadays, the application of ultra-high strength steel sheets is expanding and it is necessary to evaluate the HE
susceptibility in various forming modes. V-bending test19), 4-point bending test20), drawn cup method15, 21-23) and so on, are used
corresponding to the situation. Sometimes as-sheared specimen is also used for simulation of shear or punched edge after

blanking. Microstructure damage and residual stress introduced shearing or punching are so severe that HE fracture limit of
sheared or punched specimen deteriorates compared to machined specimen24)..
In the field of hydrogen infrastructure, HE susceptibility in high pressure hydrogen gas over 10MPa to 120MPa is
evaluated. SSRT with smooth specimen, fatigue crack growth test and fatigue test are mainly conducted11, 25-27). In the
environment, materials continue to be exposed to high pressure hydrogen gas and hydrogen atoms continuously intrude into
the materials on the new surface generated during deformation. The fatigue crack growth rate of tempered martensitic Cr-Mo
steels with tensile strength less than 900MPa was accelerated by about 30 times in high pressure hydrogen gas with pressure
of 90-115MPa is accelerated about 30times compared with that in air25). It is reported that oxide films on materials and
impurities as O228) and CO29) contained in hydrogen gas affect hydrogen uptake.
Although HE evaluation researches are actively conducted, there are still many issues.
① Clarification of HE fracture limit difference among evaluation methods which are CLT, SSRT and Constant strain test
such as 4-point bending test.
In the previous study, the HE fracture limits obtained by various evaluation method for the same material were compared20,
30)
. There were some difference in those results, but the reason are not clarified. If cause of difference in HE fracture limit
obtained by the various evaluation methods is clarified, it is very useful because HE evaluation can be obtained more
efficiently and some hints for elucidation of the mechanism of HE can be obtained.
② Quantification of diffusible hydrogen directly contributing to HE fracture.
By CLT, Hc can be obtained. However, what fraction of the total diffusible hydrogen content contribute to HE fracture?
The Pre-strained specimen sometimes has higher Hc than the original material even though the fracture critical stress of the
pre-strained specimen is equal to or lower than that of the original material in the same environment31). Hydrogen uptake
increase with strain but a part of the hydrogen doesn’t influenced to HE. If hydrogen contributing to HE can be measured,
more appropriate evaluation and material development for high HE resistance are possible.
③ Development of hydrogen charging method with easy control of hydrogen content.
It is difficult to predict how much hydrogen is charged in specimens. Therefore the appropriate hydrogen charging
conditions are determined by a trial and error process. In addition, under high pressure hydrogen gas environment it is difficult
to conduct experiment due to the need for special equipment and strict regulations for safety. If an alternative hydrogen
charging method for high pressure hydrogen gas is developed, the evaluation and prediction of property in high-pressure
hydrogen gas environment become easily and cost reduction or material development for hydrogen gas infrastructure are
accelerated26)..
④ Standardization of “diffusible” hydrogen measurement methods and procedures
The quantification of diffusible hydrogen is very important for HE evaluation. There are many kinds of equipment for
hydrogen analysis32). In the case that diffusible hydrogen is measured by the same equipment and researcher, diffusible
hydrogen on the order of 0.01ppm can be compared in a series of studies. However, the analysis results obtained by different
equipment or researchers can vary widely. Diffusible hydrogen can so easy to diffuse in materials that process of measurement
also affects the analysis results. If hydrogen analysis method and procedure of diffusible hydrogen content is standardized,
many research results can be compared and HE research progress further.
There are many issues and interests in the HE research field for the clarification of HE phenomena besides those
issue for HE evaluation. Many researches and deep discussion are necessary in this research field.
References
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2) S.Matsuyama：Delayed Fracture (The Nikkan Kogyo Shimbun, LTD. Tokyo, (1989). (in Japanese)
3) S.Yamasaki and T.Takahashi：Tetsu-to-Hagané, 83(1997), pp.454-459. (in Japanese)
4) S. Yamasaki, M.Kubota and T.Tarui : Nippon Steel Technical Report, 80(July 1999), pp.50-55.
5) S. Takagi, T. Inoue, T. Hara, M. Hayakawa, K. Tsuzaki and T.Takahashi: Tetsu-to-Hagané, 86 (2000), pp.689-696. (in Japanese)
6) S. Takagi, T. Inoue, K. Tsuzaki and F. Minami: Proceedings of International Symposium on Today and Tomorrow in Science and
Technology of Welding and Joining (7WS), Kobe, Japan, (2001), pp.1159-1164.
7) S. Yamasaki and T. Takahashi: Tetsu-to-Hagané, 83(1997), 460-465. (in Japanese).
8) S. Takagi, T. Inoue, K. Tsuzaki and F. Minami: J. Jpn. Inst. Met., 65(2001), pp.1073-1081. (in Japanese)

9) S. Takagi, S. Terasaki, K. Tsuzaki, T. Inoue and F. Minami: ISIJ Int., 45(2005), pp.263-271.
10) W. Urushihara, F. Yuse, T. Nakayama, Y. Namimura and N. Ibaraki : Research and Development KOBE STEEL
ENGINEERING, REPORTS, 52(No.3 2002), pp.57-61. (in Japanese)
11) H. Matsunaga, M. Yoshikawa, R. Kondo, J. Yamabe ans S. Matsuoka : Int. J. Hydrogen Energy, 40(2015), pp.5739-5748.
12) T. Hojo, R. Kikuchi, H. Waki, F. Nishimura, Y. Ukai and E. Akiyama : ISIJ Int., 58(2018), pp.751-759.
13) Y. Momotani, A. Shibata, D. Terada and N. Tsuji : Int. J. Hydrogen Energy, 42(2017), pp.3371-3379.
14) M. Wang, E. Akiyama and K. Tsuzaki: Mater. Sci. Eng. A, 398A(2005), pp.37-46.
15) S. Takagi, Y. Toji, M. Yoshino and K. Hasegawa : ISIJ Int., 52(2012), pp.316-322.
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17) Y. Toji, S. Takagi, M. Yoshino, K. Hasegawa and Y. Tanaka : Tetsu-to-Hagané, 95 (2009), 887-894. (in Japanese)
18) Y. Toji, S. Takagi, M. Yoshino, K. Hasegawa and Y. Tanaka : Mater. Sci. Forum, 638–642 (2010), pp.3537-3542.
19) H. Miyake, J. Tobata, S. Sumikawa, T. Shinmiya, S. Ootsuka, Y. Yamasaki, Y. Toji and Y. Tamai : Proc. JSAE, 50(2019)
20194369, pp.951-956. (in Japanese)
20) S. Takagi, Y. Hagihara, T. Hojo, W. Urushihara and K. Kawasaki : ISIJ Int., 56(2016), pp.685-692.
21) S. Takagi, Y. Toji, K. Hasegawa, Y. Tanaka, N. Rössler, B. Hammer and T. Heller : Inter. J. Automotive Eng., 2 (2010), 7-13..
22) S. Takagi, Y. Toji, K. Hasegawa, Y. Tanaka, N. Rössler, B. Hammer and T. Heller : Mater. Sci. Technol. Conf. Exhib., (2010), No.
3, pp.1769-1777.
23) N. Rössler, B. Hammer, T. Heller, I. Thomas, Y. Toji, S. Takagi, K. Hasegawa and K. Seto : Proc. Int. Conf. Steels in Cars and
Trucks(SCT2011), TEMA, Germany, (2011), 503-.511.
24) M. Yoshino, Y. Toji, S. Takagi and K. Hasegawa : ISIJ Int., 54(2014), pp.1416-1425.
25) S. Matsuoka, H. Matsunaga, J. Yamabe, S. Hamada and T. Iijima : Transactions of the JSME 83 854 (2017). (in Japanese)
26) S. Takagi, H. Okano and A. Nagao : Proc. the ASME 2016 Pressure Vessels and Piping Conference (PVP2016), Vancouver,
British Columbia, Canada (2016) PVP2016-63336.
27) A. Nagao, H. Okano, K. Matsubara, N. Ishikawa and T. Takano : Proc. the ASME 2018 Pressure Vessels and Piping Conference
(PVP2018), Prague, Czech Republic (2018) PVP2018-84726.
28) B.P.Somerday, P.Sofronis, K.A. Nibur, C. San Marchi and R. Kirchheim : Acta Materialia, 61(2013), 6153-6170.
29) R. Komoda, M. Kubota, S. Yoshida, A. Staykov, P. Ginet, F. Barbier and J. Furtado : Proc. International Society of Offshore and
Polar Engineers (ISOPE 2018), ISOPE-I-18-504.
30) T. Chida, Y. Hagihara, E. Akiyama, K. Iwanaga, S. Takagi, M. Hayakawa, H. Ohishi, D. Hirakami and T. Tarui : ISIJ Int.,
56(2016), pp.1268-1275.
31) S. Takagi, Y. Toji, M. Yoshino, K. Hasegawa, N. Wada, K. Takai and Y. Hagihara : STEELY HYDROGEN CONFERENCE
PROCEEDINGS 2014, pp. 13-20.
32) H.Suzuki and K. Takai : ISIJ Int., 52(2012), pp.174-180.

Hydrogen-related crack propagation behavior in martensitic steel
Akinobu Shibata1,*, Ivan Gutierrez-Urrutia1, Akiko Nakamura1, Goro Miyamoto1,2, Yazid Madi3, Jacques Besson3,
Toru Hara1 and Kaneaki Tsuzaki1
1
2
Institute for Materials Research, Tohoku University, Aoba-ku, Sendai, 980-8577, Japan
3
Centre des Matériaux, MINES ParisTech, CNRS UMR 7633, BP 87, 91003, Evry, France
*email: SHIBATA.Akinobu@nims.go.jp
Keywords: martensitic steel, hydrogen embrittlement, intergranular fracture, 3D analysis
1. Introduction
From economic and environmental viewpoints, the demand for high-strength steels is increasing. As the susceptibility to
hydrogen embrittlement of high-strength steels, particularly martensitic steels, is considerably high, hydrogen embrittlement is
one of the serial issues hindering wide application of high-strength martensitic steels. To develop advanced high-strength
steels with high resistance to hydrogen embrittlement, understanding the underlying mechanism of hydrogen embrittlement is
very important. However, the detailed fracture sequence of hydrogen embrittlement has not yet been clarified. The typical
modes of hydrogen-related fracture are classified into quasi-cleavage and intergranular. The hydrogen-related intergranular
fractures are often linked with significantly more severe brittle behaviors. Crack morphology is an important characteristic
which is closely related to the macroscopic mechanical properties. Although conventional 2D surface observation by using
SEM is appropriate for statistical analysis, it has inevitable limitations for analyzing crack morphology in detail. On the other
hand, 3D observation with different scales is a promising method for deeply understanding crack morphology. We employed
a multi-scale 3D analysis, i.e., X-ray computed tomography and FIB-SEM serial sectioning, to understand the morphology of
hydrogen-related intergranular crack in martensitic steel.
2. Experimental Procedure
The material used in the present study was an Fe-8Ni-0.1C alloy with a high nickel content to obtain high hardenability. This
is a model steel which exhibits intergranular fracture even in the uncharged state 1). Compact tension specimens with a
thickness of 12.5 mm (B) and a width of 25 mm (W) were cut from the heat-treated steel plates via spark wire cutting. The
pre-cracked CT specimens with side grooves were cathodically pre-charged with hydrogen in an aqueous solution of 3%
NaCl +3 g L-1 NH4SCN for three days at ambient temperature. Unloading compliance tests were performed to obtain the J –
a resistance curves based on ASTM E1820-17 standard. Unload / reload sequences were performed for a displacement
interval of 0.025 mm, and the rate of crack mouth opening displacement for the test was 2.5 × 10-5 mm s-1.
Conventional 2D observations on the fracture surface and crack propagation were performed using SEM and SEM / EBSD.
The macroscopic 3D crack propagation morphologies were analyzed by computed tomography using X-ray microscopy. A
specimen with the dimensions of ~ 2 mm (W) × 16 mm (L) × 1 mm (T) was cut from the mid-thickness region of the tested
compact tension specimen by spark wire cutting. For microscopic analysis, a pillar with the dimensions of ~ 25 m × 25 m
× 25 m containing cracks was fabricated from the tested compact tension specimen using an FIB. Then, the 3D crack
propagation behavior was analyzed by FIB-SEM serial sectioning.

The load – crack mouth opening displacement curve of the unloading compliance tests and the analyzed J – a curves are
shown in Figure 1. We found that the crack-growth resistance decreased with increasing hydrogen content. However, the
slope of J – a curves is still positive after the initiation of crack propagation. This indicates that the hydrogen-related
intergranular cracks propagated in a stable manner even when the hydrogen content was large (up to 4 wt. ppm). Through 2D
observation, we have observed that intergranular crack propagated along prior austenite grain boundaries in both the
uncharged and hydrogen-charged specimens. Some of the crack-tips were blunted in the uncharged specimen. By contrast,
the tip of the hydrogen-related intergranular crack was not blunted, and a high strain was localized around the crack tip 2).

Figure 1 (a) Load – crack mouth opening displacement curves and (b) crack-growth resistance curves (J – a resistance
curves) of the specimens with different HD 1).
The macroscopic crack morphology in the uncharged specimen reconstructed by X-ray computed tomography is presented
in Figure 2. The fracture propagated discontinuously with a
certain area of un-cracked ligaments as indicated by yellow
arrows 3). We have confirmed that the crack propagation tended
to be more continuous with increasing hydrogen content.
Accordingly, we can propose that the macroscopic continuous
crack propagation resulted in the decrease of crack-growth
resistance with increasing hydrogen content.
One typical example of the morphology of hydrogen-related
intergranular crack (HD = 0.42 wt ppm) obtained by FIB-SEM
serial sectioning is presented in Figure 3 (blue: intergranular
crack component, red: transgranular (quasi-cleavage) crack
component). On a microscopic scale, the crack frequently Figure 2 3D crack propagation morphology
deviated from prior austenite grain boundary. The prior austenite reconstructed by X-ray computed tomography in the
grain boundary is the position of the grain boundary in the uncharged specimen.
austenite state before transformation. Because several martensite
variants form by transformation, it exhibits an inhomogeneous
structure. The crystallographic analysis revealed that the
low-angle grain boundary plane segment acted as an obstacle to
crack propagation. Based on the results, we concluded that local
crack-arrestability of low-angle grain boundary plane segment
could be the possible reason for the stable crack propagation even
when the hydrogen content was large.
Acknowledgement
This study was financially supported by JST PRESTO (Grant
Number JPMJPR2096), JSPS KAKENHI (Grant Numbers
JP19H02459 and JP20K21083). In addition, this study is based on
results obtained from a project commissioned by the New Energy
and Industrial Technology Development Organization (NEDO) Figure 3 3D morphology of the hydrogen-related
[JPNP14014]. intergranular crack (HD = 0.42 mass ppm)
reconstructed by FIB-SEM serial sectioning.

References
1) A. Shibata, Y. Madi, K. Okada, N. Tsuji and J. Besson: Int. J. Hydro. Energy 44 (2019) 29034.
2) A. Shibata, I. Gutierrez-Urrutia, K. Okada, G. Miyamoto, Y. Madi, J. Besson and K. Tsuzaki: Mater. Sci. Eng. A 831 (2022)
142288.
3) A. Shibata, I. Gutierrez-Urrutia, A. Nakamura, G. Miyamoto, Y. Madi, J. Besson, T. Hara and, K. Tsuzaki: Acta Mater. in press.

Evaluation of Hydrogen Embrittlement Properties of Ultrahigh-Strength TRIP-Aided
Steels
Tomohiko Hojo1,*
1
Institute for Materials Research, Tohoku University, Sendai, Miyagi 980-8577, Japan
*email: tomohiko.hojo.a1@tohoku.ac.jp
Keywords: Hydrogen embrittlement, TRIP-aided steels, retained austenite
The ultrahigh-strength steel sheets are expected to apply for the mobile frame parts due to the wight reduction of
frames, the improvement of collision safety and the protection of fuel cell batteries against collision damages. The tensile
strength of 1500 MPa, the total elongation of more than 20% and the excellent cold formability are required for the
ultrahigh-strength steel sheets. To achieve these mechanical properties and formability, it is expected that the ultrahigh-strength
transformation-induced plasticity (TRIP)-aided steels associated with TRIP of retained austenite are applied for the
automotive frame parts. On the other hand, the occurrence of hydrogen embrittlement which is caused by the absorption of
small amount of hydrogen becomes serious problem in the ultrahigh-strength steel sheets with tensile strength of 1500 MPa.
In this presentation, the hydrogen embrittlement properties of the ultrahigh-strength TRIP-aided steels which are
systematically investigated will be reported.
(1) Effect of matrix structure

In the low alloy TRIP-aided steels, TRIP-aide steels with polygonal ferrite matrix (TDP), annealed martensite
matrix (TAM), bainitic ferrite matrix (TBF) and martensite matrix (TM) are expected to apply the high- and ultrahigh-strength
steels for automotive structural parts. The TDP steels exhibited excellent ductility, whereas the TAM steels possessed both
excellent ductility and formability. In addition, the TBF and TM steels exhibited ultrahigh strength and excellent formability of
hole expansion. The hydrogen embrittlement properties of the TRIP-aided steels were investigated using tensile testing
technique to clarify the effects of matrix structure. The TDP and TAM steels possessed excellent hydrogen embrittlement
resistance in comparison with the TBF and conventional martensitic steels. This might be caused by the low hydrogen
susceptibility due to the low tensile strength compared with that of the TBF steel and the occurrence of dimples with large
diameter.
(2) Effect of austempering temperature

It is expected that the hydrogen embrittlement resistance is changed since the retained austenite characteristics (i.e.
volume fraction and carbon concentration) are changed by the austempering temperature in the TBF steels. The hydrogen
embrittlement properties of the TBF steels were evaluated by means of tensile test and four-point bending constant load test to
clarify the effects of retained austenite characteristics. In the TBF steels without hydrogen, the tensile strength decreased with
decreasing austempering temperature, whereas the total elongation was improved at the austempering temperature of 400 ℃.
On the other hand, when the TBF steels were charged with hydrogen, the total elongation decreased with decreasing
austempering temperature. In addition, the maximum applied stress evaluated by four-point bending constant load test
decreased with decreasing austempering temperature. The similar trend of hydrogen embrittlement properties between tensile
test and four-point bending constant load test was obtained in the TBF steels.
(3) Effect of hydrogen on Charpy impact properties

Generally, it is known that the hydrogen embrittlement of high-strength steel drastically occurs under the constant
load or slow deformation rate (slow strain rate). However, it is concerned that hydrogen embrittlement occurs under high
deformation rate such as a collision when hydrogen is homogeneously distributed in the steels. Thus, the effect of hydrogen
on impact properties of the TBF steels was investigated. The Charpy impact absorbed value was improved at the
austempering temperatures between 350 and 425 ℃. This might be attributed to the high volume fraction of retained
austenite at those austempering temperatures. When Charpy impact tests were carried out with hydrogen, the similar trend of
the values was obtained although the Charpy impact absorbed values with hydrogen were slightly lower than those without

hydrogen. Thus, it was implied that the hydrogen embrittlement hardly occurred due to the hydrogen absorption in the TBF
steels.
(4) Effect of strain rate

The hydrogen embrittlement susceptibility increased with decreasing strain rate because of the interaction between
hydrogen diffusion and deformation rate of the steels. The effects of strain rate and hydrogen on tensile properties of the TBF
steels were investigated. The strain rate hardly affected the total elongation of the TBF steels without hydrogen. On the other
hand, when the TBF steel was charged with hydrogen, the total elongation decreased with decreasing strain rate. The fracture
surface of the hydrogen charged TBF steels was changed from fully dimple to coexistence of dimple and quasi cleavage as
decreasing strain rate. In addition, the flat facet which corresponds to the cracks initiated at transformed martensite or
matrix/transformed martensite interfaces was observed on the fracture surface of the hydrogen-charged TBF steels tensile
tested at slow strain rate. The occurrence of the flat facet on the fracture surface was attributed to the increase in the hydrogen
concentration in the transformed martensite and at the matrix/transformed martensite interfaces due to the difference of
hydrogen solubility between austenite and martensite.
(5) Effect of pre strain

Generally, the high-strength steels are applied for the automobile structural parts after cold press forming. Thus, it is
necessary to investigate the hydrogen embrittlement properties of the pre-strained high-strength steels. The hydrogen
embrittlement properties of the pre-strained TBF steels were investigated by the tensile testing and four-point bending constant
load testing techniques. When hydrogen embrittlement properties were evaluated by the tensile test, the total elongation was
improved at the pre strain of 0-10%. In addition, the maximum applied stress evaluated by four-point bending constant load
test hardly decreased because of the pre strains of 2.5 and 5% in the TBF steels. The suppression of deterioration of hydrogen
embrittlement resistance of the TBF steels due to the pre-straining was attributed to the removal of unstable retained austenite
which suppress the transformation and the occurrence of cracking during tensile and four-point bending constant load tests
and relatively low hydrogen absorption due to the slight increase in the dislocation which acts as hydrogen trapping sites.
References
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224 (2020), pp.253-260

Design of ferritic heat resistant steels
with improved long term structural stability
Satoru Kobayashi
Tokyo Institute of Technology
Abstract:
Laves phase, such as Fe2Mo and Fe2W, is often reported to precipitate during creep deformation
within tempered martensitic matrix in conventional high Cr ferritic steels. Different Laves phase
morphologies have been observed in the steels: fine particles along the lath/block boundaries and
coarse globular ones. The effects of Laves phase formation on the creep resistance of ferritic steels are
under debate and have not yet been fully understood.
We have recently found the formation of periodically arrayed rows of very fine Fe2Hf Laves phase
particles in the 9 % Cr ferritic matrix through interphase precipitation along the eutectoid type reaction
of delta-ferrite - gamma-austenite + Fe2Hf and a subsequent gamma-alpha phase transformation.
In the present paper, we will show our recent results on the microstructure formation along the new
route, alloying effect, creep propeties, and alloy design perspective.

Effect of Co addition on creep strength
and magnetic properties of high chromium ferritic steel
Shigeto Yamasaki, Masatoshi Mitsuhara, Hideharu Nakashima

Kyushu university
Abstract:
The relationship between changes in the magnetic properties and the creep strength with the addition
of 3 or 6 mass% Co was investigated for ferritic steel containing 15 mass% Cr. Co addition up to 6
mass% hardly contributed to solid solution strengthening or precipitation strengthening. However, in
the range of 650 to 750°C, the steel with the larger amount of Co exhibited higher creep strength,
which is explained by a reduction in the diffusion rate associated with a change in magnetic properties
by Co addition. An increase of the magnetization of the steel with increasing Co content in the range
from room temperature to ~800°C was confirmed. Comparing the difference in magnetization and the
ratio of the creep strain rate for steels with different amounts of Co, a clear correlation was found. That
is, at the temperature at which the difference in magnetization reached a maximum, the peak of the
creep strain rate ratio was also observed. This result is explained as follows. In a low temperature
region where the magnetization is large or in a high temperature region above the Curie point of both
steels, the steels exhibit no significant difference in the creep strength. However, at a temperature
where one steel loses its ferromagnetism but the other steel retains it, a significant difference in the
creep strength is observed.

Nano-SIMS observation on the boron segregation evolution during tempering
of a hear resistant ferritic steel
Nobuaki Sekido1*, Takumi Osanai1, Miyuki Takeuchi2, Mitsuharu Yonemura3,
Kouich Maruyama1, and Kyosuke Yoshimi1
1
Graduate School of Engineering, Tohoku University, Sendai, Miyagi 980-8579, Japan
2
Graduate School of Engineering, The University of Tokyo, Tokyo, 113-8656, Japan
3
Advanced Technology Research Laboratories, Nippon Steel Corporation, Amagasaki, Hyogo, 660-0891, Japan
*email: sekido@material.tohoku.ac.jp
Keywords: Boron, grain boundary segregation, nano-SIMS
Introduction
The development of the creep strength-enhanced ferritic (CSEF) steels has led to increased steam temperature and
pressure, and thereby enhanced power generation efficiency in coal-fired power plants 1). Recently, there has been a
growing demand for the development of new high-Cr heat-resistant ferritic steels that can be used at temperatures up to
650°C. Some promising candidates include 9Cr-3W-3Co-V-Nb-B-N steels (MARBN steels) 2), 9Cr-3W-3Co-V-Nb-Ta
-Nd-B steels (SAVE12AD)3), and 0.035C-9Cr-2.4W-1.8Co-V-Nb steels 4).
It is reported that trace B additions (~ 100 wt. ppm) to 9-12%Cr ferritic steels are beneficial for improving the
long-term creep strength 2,5-7). Although the detailed mechanism of this creep strength enhancement by B addition
remains unclear yet, it is believed that boron atoms segregated on austenite grain boundaries (PAGBs) during
austenitizing are partitioned into M23C6 carbides (M23(C,B)6) during tempering and creep deformation, which then
suppresses the coarsening of M23(C,B)6 carbides 7-10). Since the B concentration of M23(C,B)6 carbides precipitated near
PAGBs is higher than that formed in the grain interiors of a 9Cr-3W-B steel 7), the B content in M23C6 can be affected by
the presence of B segregation when they nucleates on the PAGBs. The purpose of this study is to investigate the
evolution of B segregation during tempering by using nano-SIMS.
Experimental procedures
A steel with the composition of Fe-0.081C-0.27Si-0.51Mn-8.96Cr-2.80Co-2.82W-0.20V-0.051Nb-0.013B-0.007N
(wt.%) 11) was used in this study. It should be noted that the present steel falls within the range of composition, where
boron nitride (BN) will not form 12). The steel was austenitized at 1100°C for 4 h, followed by water-quenching (AQ
specimen). The AQ specimens were tempered at 600 and 790°C from 10 min to 8 h, followed by water-quenching. All
the specimens were sealed in quartz tubes under vacuum (< 10-1 Pa) during the austenitizing and tempering treatments.
Microstructures of the steel were characterized by optical microscopy (OM), scanning electron microscopy (SEM),
and transmission electron microscopy (TEM). The acceleration voltage of TEM was 200 kV, and the TEM specimens
were prepared by the focused ion beam (FIB) lift-out method. The spatial distribution of B was visualized by
nano-SIMS (NanoSIMS 50L 13)). The 11B16O2- and 11B12C- ions were used for visualizing the B distribution. Since the
ionization efficiency of 11B16O2- is affected by both B and O, the distribution of O atoms on the surface must be uniform
for precise measurement of B distribution. Therefore, the specimen was pre-sputtered for removing contamination and
surface oxide layers, and left until micro-leak gaseous O2 molecules were adsorbed on the surface 14). An open-source
software, “Open MIMS,” was used for processing the nano-SIMS images 15). Further detailed information on the
nano-SIMS measurement was described elsewhere 16).

Figure 1 shows SEM micrographs and nano-SIMS 11B16O2- maps for the AQ specimen (a,c) and the specimen
tempered at 790°C for 10 min (b,d). Note that the SEM and nano-SIMS images presented in Fig. 1 were not taken from

Fig. 1: SEM micrographs and nano-SIMS 11B16O2- maps of (a) the AQ specimen and (b) the tempered
specimen (790°C for 10 min).
the same areas. The specimens show a typical lath martensite microstructure that consists of laths, blocks, and packets
within the prior-austenite grains (PAGs). High intensity of the 11B16O2- ions was depicted on the PAGBs of the (c) AQ
and (d) tempered specimens, suggesting that B segregation has developed on PAGBs during austenitizing and it retains
after the tempering at 790°C for 10 min. The enrichment of B was not observed on the block and packet boundaries in
the AQ specimen because they were newly formed boundaries by the martensite transformation. No precipitates are
observed in the AQ specimen, while some are observed in the tempered specimen. The precipitates formed during
tempering show the high intensity of the 11B16O2- ions as shown in Fig. 1(d). Along with TEM analysis, these
precipitates are found to be B-containing M23C6 carbides; i.e., M23(C,B)6.
Although the present tempering temperature of 790°C was within a typical temperature range of tempering for 9%Cr
steels, M23(C,B)6 precipitation has initiated within a short tempering duration of 10 min. To facilitate the investigation of
the boron segregation evolution and its relation to the carbide precipitation, the tempering temperature was lowered to
600°C in this study.
Figure 2 summarizes EBSD-IPF maps, and the corresponding 11B16O2- and 11B12C maps for the specimen tempered at
600°C for (a,d,g) 10 min, (b,e,h) 2 h, and (c,f,i) 8 h. High intensities of 11B16O2- ions are depicted on PAGBs for all the
specimens shown in Fig. 2, suggesting that the B segregation retains after tempering at 600°C for, at least, 8 h. It should
be noted that the B segregation can be distinguished from M23(C,B)6 by comparing the 11B16O2- and 11B12C- ion maps, i.e.,
B segregation results in high 11B16O2- intensity and low 11B12C- intensity, but M23(C,B)6 yields high intensity for both
11 16
B O2- and 11B12C- 16). Although some M23(C,B)6 carbides have formed at the grain interiors in the specimens tempered
at 600°C for 10 min and 2 h, few were confirmed on the PAGBs. Besides, the block boundaries near the PAGBs exhibit
high 11B16O2- signals, suggesting that B atoms segregated at PAGBs have oozed through the block boundaries during
tempering.
The present study indicated that, when tempered at 600°C, the amount of M23(C,B)6 carbides formed on the PAGBs
was fewer than those on block and packet boundaries. In addition, the M23(C,B)6 carbides formed on block and packet
boundaries were coarser than those formed on PAGBs. This tendency was supported by OM and SEM observations as
shown in Fig. 3. Here, the specimen tempered at 790°C for 10 min show a typical tempered martensite microstructure
(Fig. 3(a)), however, the specimen tempered at 600°C for 8 h shows a precipitation-free zone (PFZ) like microstructure,
where the PAGBs were enclosed by bands with a brighter contrast, as shown in Fig.3(b). The brighter contrast on
PAGBs is originated from the difference in the number of carbide precipitates. That is, the volume fraction of
precipitates near PAGBs is much lower than that at the grain interior, as depicted by the SEM micrograph shown in Fig.
3(c), so the etching rate difference by the Villela reagent between the area near PAGBs and the grain interior causes
some contrast in OM micrographs.
It has been demonstrated that the size of M23C6 precipitates in tempered Gr. 91 steels (without B additions) becomes
larger in the order of the ones formed at PAGBs, packet boundaries, block boundaries, and lath boundaries 17). This
indicates that nucleation and/or growth of M23C6 precipitates are kinetically faster on the PAGBs of the Gr. 91 steels.
However, this tendency appears to be the opposite in the present steel; i.e., M23C6 precipitation was not observed on the
PAGBs when tempered at 600°C for 8 h. This suggests that the B segregation suppresses precipitation and growth of

Fig. 2: EBSD-IPF maps, and the corresponding 11B16O2- and 11B12C maps for the specimen tempered at
600°C for (a) (d) (g) 10 min, (b) (e) (h) 2 h, and (c) (f) (i) 8 h.
Fig. 3: OM micrographs of the specimens tempered at (a) 790°C for 10 min and (b) 600°C for 8 h, and (c)
a magnified SEM image of (b).
M23C6 carbides in the vicinity of PAGBs. This consideration is supported by the previous studies, where B addition
results in the reduced coarsening rate of M23C6, but this is only evident in the vicinity of PAGBs 2,10).
The mechanisms for the suppression of carbide precipitation and growth by B segregation are not clear, but it is
speculated that B segregation results in the reduction of other elemental segregation or diffusivity on grain boundaries. It
has been demonstrated that the segregation of solute atoms with weaker segregation energy is reduced by the presence
of the other solute atoms with stronger segregation energy because the segregation sites are preferentially occupied by
the latter (site competition) 18-20). Since the segregation energy of B at austenite grain boundaries is higher than that of C

20,21)
, it is possible that the B segregation reduces the segregation and diffusivity of C and other carbide forming elements
at grain boundaries, by which the nucleation and growth of carbide are kinetically retarded at the PAGBs.
Conclusions
The evolution of B segregation during tempering was investigated using nano-SIMS in a B-doped 9Cr steel. In the
specimen quenched from the austenitizing temperature, B segregation was confirmed on the prior-austenite grain
boundaries (PAGBs) but not on block and packet boundaries. Carbide precipitation was not confirmed at the early stage
of tempering at 600°C. Although precipitation of M23C6 was confirmed to occur at the grain interior of the tempered
specimens, the precipitation and/or growth of M23C6 carbide were suppressed near PAGBs. It is suggested that the B
segregation on PAGBs is effective to suppress the carbide precipitation and growth during tempering at 600°C.
Acknowledgments
This work was supported by ISIJ Research Promotion Grant, Iketani Science and Technology Foundation Research
Grant, JSPS KAKENHI (JP18K18930), and the University of Tokyo Advanced Characterization Nanotechnology
Platform, as a program of “Nanotechnology Platform” of the MEXT Japan (JPMXP09A19UT0286).
References
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Improvement in Creep Strength of Precipitation Strengthened Ferritic Steels
Yoshiaki TODA1,*, Nina KOBATA1 and Yoko YAMABE-MITARAI2
1
2
Graduate School of Frontier Science, The University of Tokyo, Kashiwa, Chiba 277-8561, Japan
*email: TODA.Yoshiaki@nims.go.jp
Keywords: creep strength, ferrite matrix, ferritic heat-resistant steels, Laves phase, M23C6 carbide, steam oxidation resistance
Aim and scope

To save fuel resources and reduce CO2 emissions, there is a growing need to increase the energy efficiency of not
only conventional thermal power plants but also renewable energy plants of geothermal, biomass, solar heat and so on. One
strategy is to develop high-strength and high-oxidation-resistant materials with reasonable prices that permit operation under
higher temperature and pressure conditions. The development of austenitic heat-resistant steels and nickel-based superalloys
has been investigated because of their superior creep strength and oxidation resistance 1, 2). However, we believe that the de-
velopment of ferritic steels with high creep strength and high oxidation resistance would also be advantageous for realizing
energy-efficient plants. Ferritic steels are ideal for large and thick structural components for use at high temperatures due to
their useful properties of high thermal conductivity, low thermal expansion coefficient, low susceptibility to thermal fatigue,
little need for rare metals, and lower cost than austenitic steels or nickel-based superalloys 3).
Conventional high chromium ferritic heat-resistant steels are strengthened by their tempered martensitic micro-
structure and the homogeneous distribution of carbides and/or nitrides 4). However, a martensitic microstructure is obtained by
rapid cooling, and is unstable at elevated temperatures. During creep exposure, the fine lath structure is recovered and precipi-
tates are coarsened. The easy movement of the highly dense dislocations introduced during the martensitic transformation
causes plastic deformation and ultimately creep rupture 4). This is one reason for the inferior creep strength of conventional
ferritic steels. In conventional ferritic steels, the chromium content (chromium being one of the most effective elements for
improving oxidation resistance) is restricted to 12 mass% or below in order to obtain a fully austenite phase at a normalized
temperature and to avoid the formation of a δ-ferrite phase. This is one reason for the inferior oxidation resistance of conven-
tional ferritic steels. Therefore, we believe that employing a tempered martensitic microstructure prevented us from greatly
improving either the creep strength or the oxidation resistance of ferritic steels.
Kimura et al. have proposed 15Cr steels with a ferrite matrix to replace conventional 9-12Cr ferritic heat-resistant
steels with a tempered martensitic microstructure 5). It has also been discovered that a higher long-term creep strength than that
of conventional steels can be obtained by employing a new material concept, namely, 15Cr ferritic steels with a ferrite matrix
strengthened by some precipitates such as intermetallic compounds 6-9). In the present study, we investigated the possibility of
improving both the long-term creep strength and the steam oxidation resistance of 15Cr ferritic steels. We believe that the
findings reported in this study will prove useful for the development of new ferritic heat-resistant steels for use in high-energy
efficiency plants operated at higher temperatures than that in conventional plants.
Materials and methods

Table 1 shows the chemical compositions of conventional 9Cr (ASME SA-213/SA-213M Grade T91 and T92) fer-
ritic heat-resistant steels 10) and the precipitation strengthened 15Cr steel used in this study. The content of the following ele-
ments was modified to make the developed 15Cr steels. We increased the chromium content to 15 mass% to obtain a ferrite
matrix 5), because we believe that the ferrite phase is more suitable for improving the long-term creep strength than a tempered
martensitic microstructure 8). In addition, the increase in chromium content is expected to improve the steam oxidation re-
sistance. The tungsten content was increased to 6 mass% to promote the precipitation of the Laves phase (Fe2W), which is a
kind of intermetallic compound, as a precipitation strengthening factor 6). The high-temperature and long-term stability of Fe2W
is expected to be good, because the melting point of tungsten is high and its diffusion rate is low. A 3 mass% cobalt addition
reduces the coarsening rate of Fe2W and makes the morphology very fine 6). The carbon content and nitrogen content were both
reduced to improve the long-term stability of the microstructure 8).

Table 1 The chemical compositions of 9Cr (T/P91 and T/P92) ferritic heat-resistant steels 10) and the 15Cr steels (mass%).
Samples Fe C Si Mn Ni Cr Mo V Nb W Co N B
0.08~ 0.20~ 0.30~ 8.00~ 0.85~ 0.18~ 0.06~ 0.030~
T/P91 Bal. ~0.40 ― ― ―
0.12 0.50 0.60 9.50 1.05 0.25 0.10 0.070
0.07~ 0.30~ 8.00~ 0.30~ 0.15~ 0.04~ 1.50~ 0.030~ 0.001~
T/P92 Bal. ~0.50 ~0.40 ―
0.13 0.60 9.50 0.60 0.25 0.09 2.00 0.070 0.006
15Cr Bal. 0.046 0.22 0.49 <0.01 15.00 1.00 0.19 0.043 6.07 2.97 0.033 0.0030
The steel was melted in a vacuum induction furnace. An ingot weighing 10 kg was hot-forged into square bars with
20-mm long sides and solution-treated for 0.5 h at 1473 K, followed by water quenching. The creep test specimens were
round-bar test pieces with a gauge diameter of 6 mm and a gauge length of 30 mm. The creep tests were conducted at 923,
973, and 1023 K at stresses ranging from 30 to 240 MPa for up to about 65 000 h in air. The microstructure of the
creep-ruptured specimens was observed with a cold cathode field-emission type scanning electron microscope.
The specimens used for the steam oxidation tests were cut from the water-quenched bars into coupons of about 10
mm  20 mm  2 mm by electrical discharge machining, and then finished with 600 grit abrasive paper. The specimens
were washed with methanol in an ultrasonic bath and then placed in ceramic crucibles, which were carefully set in the furnace
chambers for a steam oxidation test. The air in chambers were replaced with argon gas with a dew point of about 210 K and
including 0.3 ppm oxygen. Then, the chambers were heated to the test temperatures in about 3 or 4 h. When the chamber
temperature exceeded 473 K, steam was introduced to replace the argon gas. The flow rate of the steam was controlled at
about 240 ml/h by controlling the water supplied to the steam generator. The oxygen concentration of the water in the tanks
was maintained at below 30 ppb by argon bubbling, and its electrical conductivity was controlled at below 10.0 μS/m by
passing it through ion exchange resins. The steam oxidation duration was defined as the time period between reaching the test
temperatures and shutting down the power to the furnace chambers. The weight gains of the specimens were measured with a
microbalance for various oxidation durations up to 3 000 h.
Results
Figure 1 shows creep stress versus time to rupture curves for 15Cr steels (solid curves) and conventional 9Cr ferrit-
ic heat-resistant steel Grade T92 11) (dashed curves) at 923 K (circles), 973 K (triangles), and 1023 K (squares). The Grade T92
steel possesses the highest creep strength of practical ferritic heat-resistant steels. The creep strength of the 15Cr steels is about
twice that of T92 steel at every temperature. The creep rupture lives of the steels are approximately one hundred times longer
than those of T92 steel at 923 and 973 K, and from ten to one hundred times longer than those of T92 steel at 1023 K. By ex-
trapolating the curves in Fig. 1, the creep rupture strength of the 15Cr steels after 100 000 h can thus be estimated to be 130
MPa at 923 K and 45 MPa at 973 K. This strength level is double that of conventional ferritic heat-resistant steels, and com-
parable to that of conventional austenitic steel 12).
Figure 2 (a) shows the scanning electron micrograph in the vicinity of a triple junction of grain boundaries for the
15Cr steel creep-ruptured at 973 K-80 MPa after 23 592 h. The blocks with white and light gray contrast as shown by the
white arrows in the Fig. 2 (a) were identified as Laves phase and M23C6 carbide, respectively. Most precipitates formed on
grain boundaries, and few precipitates were observed within grains. Then, it is supposed that a precipitation strengthening
effect on grain boundaries contributed to the high creep strength of the 15Cr steel under this condition as shown in Fig. 1. Fig-
ure 2 (b) is an enlarged figure of the grain boundary shown in Fig. 2 (a). Some small voids were observed in the interfaces
between ferrite matrix and M23C6 carbide as shown by the white arrows in Fig. 2 (b), and few voids were formed around the
Laves phase. The details of these voids’ formation mechanism are unclear. The large incoherency of the lattice structure be-
tween the ferrite phase and M23C6 carbide is supposed to be the reason for the voids’ formation. These voids could be an origin
of creep rupture, and we believe that it is necessary to reduce the coarsened M23C6 carbide. We are measuring the creep
strength of 15Cr steels with a lower carbon content than 0.05 mass%.

Fig. 1 The creep stress versus time to rupture curves for 15Cr steels (solid curves) and conventional 9Cr ferritic
heat-resistant steels Grade T92 11) (dashed curves) at 923 K (circles), 973 K (triangles), and 1023 K (squares).
Fig. 2 The scanning electron micrographs of the 15Cr steel creep-ruptured at 973 K-80 MPa after 23 592 h. (a)
shows the microstructure in the vicinity of a triple junction of grain boundaries, and (b) is the enlarged figure of
the grain boundary in (a).
Figure 3 shows the mass gain of the 15Cr steel (solid curves) and conventional 9Cr ferritic heat-resistant steel
Grade T91 (dashed curves) at 923 K (circles), 973 K (triangles), and 1023 K (squares) for different steam oxidation durations.
At 923 K, the mass gain of the 15Cr steel after 3 000 h is about 60% that of the T91 steel. At temperatures higher than 973 K,
the weight of the T91 steels continues to increase like power math functions. By contrast, the mass gains of the 15Cr steels are
relatively small at 973 and 1023 K. The differences between the mass gains of 15Cr steels and T91 steels are very significant
at elevated temperatures. In addition, higher oxidation resistance than that of conventional ferritic steels was obtained by a
ferrite matrix with a higher chromium content than that of the conventional one.
Conclusions
We have proposed precipitation strengthened 15Cr ferritic steels that have a solution-treated ferrite matrix and that
are strengthened by the precipitation of intermetallic compounds of the Fe2W Laves phase to replace conventional 9Cr ferritic
heat-resistant steels with a tempered martensite phase. The creep strength of the 15Cr steels is twice that of conventional steels.
Also, the steam oxidation resistance of the 15Cr steels is higher than that of conventional steels. We then successfully im-

proved both the creep strength and steam oxidation resistance by using our new material design concept for heat-resistant steel.
We have been trying to improve the high-temperature performances of the 15Cr steel by optimizing the steel compositions
and controlling the microstructure. We believe that the 15Cr steel is an excellent candidate material for the high-temperature
structural components of advanced high-efficiency plants.
Fig. 3 Mass gain of 15Cr steels (solid curves) and conventional ferritic heat-resistant steel Grade T91 (dashed
curves) at 923 K (circles), 973 K (triangles), and 1023 K (squares) for various steam oxidation durations.
Acknowledgement
A part of this study was supported by Grants-in-Aid for Research (KAKENHI) of the Japan Society for the Promotion of Science
(Grant Number 17K06581). We would like to thank Dr. M. Auchi at National Institute for Materials Science (Present address: Kyu-
shu University) for his measuring the steam oxidation resistance.
References
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(ASME SA-335/SA-335M Grade P92) (2002).
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Microstructure and Creep Strength of Grade 91 Steel under Long-term Service
Condition
Masatsugu Yaguchi1,*, Kenji Kako1 and Susumu Yamada1
1
Materials Science Division, Central Research Institute of Electric Power Industry, Yokosuka, Kanagawa 240-0196, Japan
*email: yaguchi@criepi.denken.or.jp
Keywords: creep, welded joint, precipitation, Grade 91 steel, heat-to-heat variation
ASME Grade 91 steel has been used as structural materials at ultra-super-critical (USC) plants and has
considerably contributed to the improved efficiency of plants. However, the decrease in the creep strength of the steel with
increasing time (long-term creep strength) and the decrease in strength at welded joints have become an issue for maintenance
of USC plants. To solve the problem, the long-term creep strength has been evaluated by committees in Japan, and creep life
curves as well as allowable tensile stress and the weld strength reduction factor were changed on the bases of the evaluation
results. However, the number of data obtained in long-term creep tests was not sufficient and it was pointed out that the
long-term creep strength should be continuously examined. Therefore, we have conducted studies on microstructure and
creep strength of ASME Grade 91 steel in a region exceeding 100,000 hours, utilizing materials used at USC plants for a long
time because in practice it is difficult to conduct creep tests exceeding 100,000 hours.
Six straight and three elbow pipes that had been used as hot reheat pipes (HRP) were used as the materials. For
elbow pipes, the creep strength on the intrados side, where the stress is higher than that on the extrados side, was basically
examined. The hoop stresses applied to the straight and elbow pipes were calculated using the equation for the mean diameter
with the dimensions of the pipes and the steam pressure. Table 1 shows a summary of the temperature, hoop stress, and
operation time for each material. Table 2 shows chemical compositions of the materials used, where a product form of those is
plate (KA-SCMV28).
Table 1. Service conditions and operation time of materials.
Table 2. Chemical compositions of materials.

Figure 1 shows the results of a creep test on specimens cut from the materials, along with the curve used to estimate
the creep life of Grade 91 steel welded joints (virgin material) proposed by Japanese committee in 2015 1), where solid line
stands for average property and broken line stands for 99% lower limit. The results differ greatly among the materials: some
materials show similar creep lives to the average creep life, whereas other materials show a shorter life than the 99% lower
limit. Note that a shorter life than the 99% lower limit of virgin materials is not a problem as the test materials are not virgin
ones and have been used for long-term in plants. Approximately half of the ruptures occurred in heat-affected zones (HAZs),
which is expressed by red solid symbols in Fig.1, and the remaining ruptures occurred in weld metal regions, which is
expressed by black open symbols in Fig. 1.
500 500
1)
Assessment in 2015 Plant Assessment in 2015 1) Plant
Average property ○ A Average property ○ A
300 - - - 99% lower limit 300
□ B - - - 99% lower limit □ B
＋ C1 ＋ C1
Stress (MPa)
Stress (MPa)
◇ G1 ◇ G1
⊿ L ⊿ L
△ N △ N
100 ▽ Q 100 ▽ Q
S S
⊿
⊿
80 80
60 60
40 Rupture location
40 Rupture location
Black : Weld metal Black : Weld metal
Red : HAZ Red : HAZ
20 1 20 1
10 102 103 104 105 106 10 102 103 104 105 106
Time to rupture (h) Time to rupture (h)
(a) 600oC (b) 650oC
Figure. 1 Creep test results on welded joint of long-term used materials.
Then, remaining creep lives of the materials for operating condition were calculated on a fitting curve using
Larson-Miller parameter. Total creep life of the material, which means a creep life at initial state, was presumed to be a
summation of the service time at the plants and the remaining creep life. The estimation was conducted for welded joints used
at five plants for long-term, and all results lay within 98% confidential band (between 99% lower limit and 99% upper limit)
by the creep life evaluation curve 1) as shown in Fig.2, while a significant heat-to-heat variation of creep strength was found
even in the region exceeding 100,000 hours. Creep tests on base metals related to each welded joint were also conducted, and
the estimation results of the total creep life of the base metals were compared to those of the welded joints. Figure 3 shows a
relationship between the creep property of welded joint and the base metal. The abscissa is the value obtained by dividing the
estimated initial creep life of the base metal by the value obtained from the curve used to estimate the creep life of the base
metal (plate) in the 2015 assessment 2) (normalized creep life of the base metal). The ordinate is the value obtained by dividing
the estimated initial creep life of welded joint under the operating conditions of an actual plant (temperature, hoop stress) by
the value obtained from the curve in the 2015 assessment 1) (normalized creep life of welded joint). Although the number of
data is limited, there is a positive correlation between the normalized creep life of the base metal and that of the welded joint
under the conditions examined in this study. Namely, the initial creep property of the welded joint depends on that of the base
metal; in other words, as the initial creep strength of the base metal increases, the initial creep strength of the welded joint also
increases. The above findings indicate the possibility of estimating the creep property of welded joint if the creep property of
the base metal of pipes can be evaluated by a certain method.

500
Assessment in 2015 1)
Average property
300 - - - 99% lower limit
Stress (MPa)
100
80
60
40 Present
Data (10) estimation Temperature
△ 550℃
○ □ 600℃
▽ 650℃
20 1 2 3
10 10 104 105 10 106
Time to rupture (h)
Figure. 2 Estimation results in comparison with creep data and master curves on welded joint of Grade 91 steel 1).
10.0
Normalized creep life property
of welded joint
1.0
0.1
0.1 1.0 10.0
Normalized creep life property
of base metal
Figure. 3 Relationship between creep property of welded joint and that of base metal.
Microstructural analyses were conducted using spherical aberration-corrected TEM. Because Grade 91 steel has a
multilevel structure consisting of prior austenite grain boundaries, packet/block boundaries and laths, the precipitations densities
significantly vary with the observation site. Figure 4 shows images of high-strength and low-strength base metals. As Cr-type
precipitations (mostly M23C6) and Mo-type precipitations (mostly the Laves phase) are irregularly distributed, the condition of
the precipitations appears to be completely different depending on the observation site. To reduce an influence of differences in
the observation site on the analysis results, an observation area is specified for each precipitation, ≤380 μm2 for the Cr-type and
the Mo-type and ≤65 μm2 for the V-type. Then, we have obtained results that there is no correlation between Cr-type and the
normalized creep property in base metal, and no correlation between Mo-type and the normalized creep property in base metal,
but a positive correlation is observed between the densities of V-type precipitations and the normalized creep property in base
metal, which suggests that creep strength of the material is improved due to pinning of dislocations by V-type precipitations.
Figure 5 shows the relationship between the normalized creep property of Grade 91 steel base metal and the densities of V-type
precipitations obtained from the analyses of the observation area specified above. The results indicate the possibility of
estimating the creep property of the material by determining the densities of V-type precipitations.

(a) High-strength base metal (b) Low-strength base metal
Fig. 4 Elemental mapping of Grade 91 steel used for a long time.
1.5
Normalized creep property of base metal
0.5
0
0.0 5.0 10.0 15.0
Density of precipitations (mm-2)
Fig. 5 Relationship between normalized creep property and number density of V-type precipitations in Grade 91 steel base
metal.
Here are summaries of the present study. The total creep lives of Grade 91 steel welded joint, which was presumed
to be the sum of the service time at the plants and the remaining creep life, lay within the 98% confidential band of the creep life
evaluation curve of the material adopted in Japan, while a significant heat-to-heat variation of creep strength was found even in
the region exceeding 100,000 hours. The comparison of the total creep life property of the welded joint with that of base metal
suggested that the heat-to-heat variation of the welded joint depends on the creep life property of the corresponding base metal.
From microstructural analysis on the material, it was found that there was a strong correlation between the density of V-type
precipitation and the creep life property of the base metal.
References
1) Yaguchi, M., Nakamura, K. and Nakahashi, S., “Re-evaluation of Long-term Creep Strength of Welded Joint of ASME Grade 91 Type
Steel”, Proc. PVP2016, Vancouver, Canada, PVP2016-63316, (2016).
2) Kimura, K. and Yaguchi, M., “Re-evaluation of Long-term Creep Strength of Base Metal of ASME Grade 91 Type Steel”, Proc.
PVP2016, Vancouver, Canada, PVP2016-63355, (2016).

Effect of grain boundary characters on growth of M23C6 carbides
in 9Cr ferritic heat-resistant steel
Masatoshi Mitsuhara, Hideharu Nakashima

Kyushu university
Abstract:
The recovery behavior of lath martensite microstructure during creep in 9Cr ferritic heat-resistant
steels is controlled by the M23C6 carbides on grain boundaries. So, the growth behavior of M23C6
carbides should be essentially taken into account to completely understand the creep deformation
mechanism of the steels. In this presentation, we focused on the effect of grain boundary character,
stress, and pre-tempering on the growth behaviors of M23C6 carbides in the lath martensite
microstructure. There are four types of boundaries in the lath martensite, those are the prior-austenite
grain boundary (PAGB), the packet boundary, the block boundary, and the lath boundary. We clarified
that the growth rates of M23C6 carbides during both aging and creep strongly depended on the
boundary character. The growth rate of carbides on the PAGB was most rapid, and that on the lath
boundary was slowest. The stress applying obviously accelerated the growth rate of carbides on the
PAGB and the packet, though that on the block and lath boundaries were apparently insensitive. It
means that the growth of carbides was controlled by not only atomic diffusion but also the
microstructural factors. In the presentation, we will show the detail analysis of crystal orientation
relationship (COR) between M23C6 carbides and matrix and discuss the effect of deviation of COR
by the creep on the growth rate of carbides..

Effect of microstructure change on the creep deformation behavior of
18Cr–9Ni–3Cu–Nb–N steel
Tomotaka Hatakeyama1*, Kota Sawada2, Toru Hara3, Kaoru Sekido2, Kazuhiro Kimura2
1
International Center for Young Scientists, National Institute for Materials Science, Tsukuba, Ibaraki 305-0047, Japan
2
3
Research Network and Facility Services Division, National Institute for Materials Science, Tsukuba, Ibaraki 305-0047, Japan
*email: hatakeyama.tomotaka@nims.go.jp
Keywords: steel, creep, precipitation, creep rate, grain boundary
1. Aims and Scope

To save the CO2 emission, efficiency of thermal power plants must be improved by increasing the operating
temperature and pressure. Therefore, further improvement of the creep strength of heat-resistant materials used for the
structural components of the plants are required. In addition, accurate prediction of long-term creep strength of the
heat-resistant materials is important to ensure the reliability of the plants.
18Cr–9Ni–3Cu–Nb–N steel (KA-SUS304J1HTB, ASME Code Case 2328) is widely used in boiler tubes for
power plants due to its excellent creep resistance. Fig. 1 shows the creep rate vs time curves of the steel at 873 K.1) Complex
creep behavior with multiple local minima in creep rate is observed. This indicates that complex microstructure changes
occurred during creep deformation. In other word, the microstructure changes toward the second local minimum involves the
positive microstructure change for the creep strength, which would contribute to the microstructure design of the steels.
Fig. 2 shows the relationship between stress and time to rupture of the steel, and creep fracture mode at each creep
2)
condition. As indicated by dashed lines on the plot for 973 K, creep strength degradation can be seen as “breakdown” in the
longer-term side, which seems to be correlated to the transition of the creep fracture mode to the cracking at the interface
between matrix and σ phase. In other word, it was considered that σ phase formation is detrimental for the creep strength.
However, the negative microstructural change related to the σ phase formation has not well understood due to the rapid
coarsening kinetics of the σ phase. The microstructural change that degrades the creep strength must be identified because the
“breakdown” invalidates the lifetime prediction by the extrapolation of the short-term data.
In short, this study aimed to identify both positive and negative microstructural factors for the creep strength by
focusing on the complex creep rate change and the “breakdown” by σ phase formation. Microstructure change during creep
deformation was carefully characterized.
Fig. 1 Creep rate vs time curves of 18Cr–9Ni–3Cu–Nb–N Fig. 2 Relationship between stress and time to rupture of
steel at 873 K.1) 18Cr–9Ni–3Cu–Nb–N steel at 873–1073 K.2)

Table 1 Chemical composition of 18Cr–9Ni–3Cu–Nb–N steel (mass%).2-3)
C Si Mn P S Ni Cr Nb N Cu
Requirement 3) 0.07–0.13 ≤0.30 ≤1.00 ≤0.040 ≤0.010 7.50–10.50 17.00–19.00 0.30–0.60 0.05–0.12 2.50–3.50
This study 2) 0.08 0.24 0.78 0.030 0.001 8.79 18.68 0.48 0.102 2.92

The sample material was a 18Cr–9Ni–3Cu–Nb–N steel tube.2) The chemical composition and requirement are
shown in Table 1. 2-3) Creep tests were performed at 873 K under 280 MPa (terminated after crept for 0, 30, 150, 2000, and
5020 h; ruptured after 14237.1 h), and 973 K under 60 MPa (ruptured after 50214.3 h). Microstructure of the crept specimens
were characterized by scanning electron microscopy (SEM), electron backscattered diffraction (SEM-EBSD), transmission
electron microscopy (TEM), energy dispersive X-ray spectroscopy attached in SEM or scanning transmission electron
microscopy (SEM-EDS, STEM-EDS). In addition, serial sectioning by orthogonally arranged focused ion beam (FIB)-SEM4)
was performed for the grip portion of the ruptured specimen crept at 973 K for three-dimensional (3D) analysis.

3-1. Complex change in creep rate
To identify the microstructural factors that cause
the complex change in creep rate at 873 K, shown in Fig. 1,
microstructure characterization of the gauge portion of the
creep interrupted/ruptured specimens was performed. Fig. 3
shows the suggested dominant microstructural factors for
the creep rate change in each creep stage described on the
creep rate vs time curve of the steel at 873 K under 280
MPa.1)
At the first local minimum creep rate (30 h),
coherently precipitated NbX phase was confirmed, and
dislocations are accumulated around the NbX. This Fig. 3 Dominant microstructural factors for the creep behavior
indicates that precipitation strengthening by NbX phase in each creep stage on the creep rate vs time curve for the steel
reduced the creep rate at the beginning stage of the creep at 873 K under 280 MPa.1)
deformation.
Fig. 4 shows the change in the average kernel average misorientation (KAM) value, measured by EBSD–OIM, as
a function of time. From the first local minimum (30 h) to the following local maximum in creep rate (150 h), significant
decrease in the KAM value was observed. This indicates that dislocation density is decreased between 30 and 150 h, which is
caused by dynamic recovery.
Fig. 4 Change in the average KAM value Fig. 5 Coverage ratio of the precipitate on grain boundary
as a function of time.1) as a function of time.1)

After 150 h, the creep rate decelerated again. Fig. 5 shows the coverage ratio of the precipitate on grain boundary,
evaluated from the SEM images, as a function of time. While no precipitates observed in the virgin sample, the coverage ratio
markedly increased around 150 h. Here, M23C6 phase is the main precipitate on the grain boundary. In addition, STEM-EDS
observation clarified that precipitation of Cu phase in grain interior starts between 150 and 2000 h. Therefore, it was
considered that the second decrease in the creep rate is caused by the retarded precipitation of M23C6 and Cu phase, result in
the grain boundary precipitation strengthening (GBPS) by M23C6 phase and precipitation strengthening by Cu phase. In other
word, they are the effective microstructural factors to reduce the creep rate.
After exhibited the second local minimum at around 5000 h, the creep rate significantly accelerated, resulted in the
creep rupture after 14237.1 h. As indicated in Fig. 2, the creep fracture mode at this condition is creep void formation. The
ruptured specimen had creep void around the grain boundary, and the higher KAM value around the void was confirmed.
Therefore, it was considered that local deformation near grain boundary, followed by the void formation were the causes of
the second acceleration and creep rupture.
3-2. Creep strength degradation in the longer-term side

To identify the microstructural factors of the creep strength degradation in the longer-term side, shown in Fig. 2, 3D
microstructural observation was performed for the grip portion of the crept specimen ruptured after 50214.3 h at 973 K.
963 slices of SEM image, 15×15 μm with a resolution of 1000×1000 pixels, were collected by repeating the
observation by an in-lens type secondary electron (SE) detector and the milling by FIB with a step size of 15 nm, i.e., the
voxel size of the reconstructed image is 15×15×15 nm3. The
relationship between the precipitates and their contrast were
confirmed by SEM-EDS on the first slice. The phases are
classified into matrix, M23C6+Nb-rich, Cu, and σ phase from
their contrast of SE images with the aid of machine learning
tool of Trainable Weka Segmentation (TWS)5), which is
distributed as an open source for Fiji.6)
3D precipitation behavior obtained by the
reconstruction of the classified images are shown in Fig. 6.7)
Cu phase is illustrated in red, and M23C6+Nb-rich phases in
green. Both matrix and σ phase are transparent in the image,
while they are distinguishable as no Cu phase are existed in
σ phase. The front plane of Fig. 6(a) is the first slice of the
serial sectioning, and the subsequent slices are stacked
behind along the z-axis. Fig. 6(b) and (c) are the tilted view
of (a) (please see the x-y-z axis and the line segment O-X to
confirm their correspondence). Fig. 6(b) clearly shows that
M23C6+Nb-rich phases are formed along the grain boundary,
and σ phase is nucleated on the triple junction. Fig. 6(c)
shows that Cu phase are coarsened at the interface between
matrix and σ phase, while no Cu phase in σ phase. This
indicates that Cu phase precipitated around the grain
boundary are swept out by the coarsened σ phase and
aggregated at the matrix/σ interface. In addition,
M23C6+Nb-rich depleted grain boundary is confirmed
around the σ phase, and density of M23C6+Nb-rich phase
embedded in σ phase is markedly less than that in the matrix.
This suggests that M23C6 phase is consumed for the σ phase Fig. 6 Reconstructed 3D precipitation behavior of the steel
formation. obtained from the grip portion of the crept specimen ruptured
From these results, it was revealed that σ phase after 50214.3 h at 973 K.7)

formation on the triple junction accompanies the coarsening of Cu phase and depletion of M23C6 phase near the grain
boundary. Therefore, it was considered that locally reduced contribution of the precipitation strengthening by Cu phase and
GBPS by M23C6 phase around the σ phase are the causes of the degraded creep strength in the longer-term side.
4. Conclusions
This study focused on the effect of microstructure change on the creep behavior. Identification of the
microstructural factors that cause double local minima in creep rate suggested that GBPS by M23C6 phase and precipitation
strengthening by Cu phase are effective to reduce the creep rate. However, 3D observation of the long-term aged specimen
clarified that the contributions of GBPS by M23C6 and precipitation strengthening by Cu phase are locally reduced around the
σ phase, result in the premature failure in the longer-term side.
Acknowledgement
The authors thank Ms. Yuka Hara (NIMS) and Ms. Akiko Nakamura (NIMS) for their support with the microstructural
observations. This work was performed under the support of JSPS KAKENHI (No. JP20K22474).
References
1) T. Hatakeyama, K. Sawada, K. Sekido, T. Hara and K. Kimura: Mater. Sci. Eng. A, 831 (2021) 142225.
2) NIMS Creep Data Sheet, Metallographic Atlas of Long-Term Crept Materials, No. M-11 (2016).
3) KA-SUS304J1 HTB, The material specification in the Technical Regulation of Equipment for Thermal Power Plant, 2007.
4) T. Hara, K. Tsuchiya, K. Tsuzaki, X. Man, T. Asahata, and A. Umeto: J. Alloys Compd., 577S (2013) S717–S721.
5) I. Arganda-Carreras, V. Kaynig, C. Rueden, K. W. Eliceiri, J. Schindelin, A. Cardona, H. S. Seung: Bioinformatics, 33 (2017)
2424–2426.
6) J. Schindelin, I. Arganda-Carreras, E. Frise et al.: Nature methods, 9 (2012) 676–682.
7) T. Hatakeyama, K. Sawada, T. Hara K. Sekido, and K. Kimura: Scr. Mater., 200 (2021) 113904.

Microstructure and Mechanical Properties of Long-term Used Super 304H Steel Boiler
Tubes
Shengde Zhang1,*, Hayato Tokunaga1, Masayuki Kanai1, Kenji Kako1, Masatsugu Yaguchi1, Koji Tamura1 and
Yusuke Minami1
1
Materials Science Division, Energy Transformation Research Laboratory, Central Research Institute of Electric Power Industry,
2-6-1 Nagasaka, Yokosuka, Kanagawa 240-0196, Japan
*e-mail: zhangsd@criepi.denken.or.jp
Keywords: Super 304H, Mechanical property, Microstructure, Aged material, Boiler tube
Introduction
Super 304H steel (18Cr-9Ni-3Cu-Nb-N, ASME Code Case 2328) has been widely used as superheater (SH) and
reheater (RH) boiler tubes in ultra-supercritical (USC) power plants due to its excellent creep strength, oxidation/hot corrosion
resistance and weldability 1). This steel was developed to have superior creep strength to that of SUS 304H steel by the
addition of copper, niobium and nitrogen. The superior creep strength of Super 304H steel is obtained by the formation of
finely distributed coherent copper phase, Nb (C, N), M23C6 and NbCrN particles, which results in higher allowable stress than
other austenitic stainless steels used in boiler tubes, such as SUS 347HTB and SUS321HTB. The steel has been applied to
actual plants for more than 20 years, and several steam leakage accidents have occurred in the superheaters with the operating
time more than 100,000 hours in Japan. Recent studies have indicated that times to creep rupture in the longer term are shorter
than those predicted by straight extrapolation of the short-term data points to the lower stresses or to the lower temperatures,
and the long-term creep strength of Super 304H may be lower than originally assumed 2, 3). This may result from the
difference in local deformation at the interface between matrix and σ phase that precipitates in creep exposure, which can lead
to crack initiation easily reported by Kubushiro 4) and Kimura 5) et al. It is important to understand the long-term
microstructural evolution and stability, and one way to investigate the microstructural evolution is to study service exposed
materials used in actual plants.
In this study, microstructures and mechanical properties of several long-term used Super 304H steel boiler tubes
were presented. The aged superheater tubes that have been in service for about 140,000 hours at the approximate metal
temperature ranged from 550°C to 640°C, have been investigated. The microstructures were observed by optical, scanning
and transmission electron microscopies including chemical analysis techniques. In addition, the hardness, impact value and
tensile properties of aged materials were measured, and these properties were discussed in relation with the microstructures.
Materials and Experimental Procedure

Materials used were three kinds of aged materials used in the superheaters of USC plants (D2, N and X). A new
tube with 45.0 mm in outer diameter and 7.9 mm in thickness was used for comparison. Table 1 shows the detailed
information of aged materials. Note, the main steam temperature and pressure are the operating condition of the plant, and
operating time includes the temperature reduction period in the plant. Since the metal temperature of tube in the plant is
unknown, the design values are given for reference. Applied stress is the hoop stress calculated from the design pressure and
nominal dimensions of tube based on the mean diameter formula. In case of X plant, both flame and rear sides were
investigated. Table 2 lists measured chemical compositions of the materials with the specification of Super 304H. Although
Mo is not specified in the standard, the steel contains a small amount of Mo.
Microstructural characterization was performed using OM (Optical Microscopy), FE-SEM (Field Emission
Scanning Electron Microscopy) and Cs-corrected TEM (Spherical aberration corrected Transmission Electron Microscopy,
Titan Themis 300) equipped with EDX (Energy Dispersive X-ray analysis). Combining with STEM and EDX analysis,
precipitates were identified by the elements mapping, and image analysis software-Winroof was used for quantitative
evaluation of precipitates.
Hardness was measured with a test force of 2.94 N and a holding time of 10 s using microhardness machine. The
machine has an automatic moving stage and hardness was measured at 0.25 mm intervals in the direction of thickness.

Figures 1(a) and 1(b) show the geometry and dimensions of charpy and tensile specimens. Width of the charpy specimen was
adjusted to 5~7.5 mm depending on the thickness limitation of tube. The axes of charpy and tensile specimens were aligned to
axial direction of the tube. Impact tests were conducted three times for the new material, D2 and N plants, and two times on
the flame and rear sides of X plant. Tensile tests were performed at room temperature (R.T), 600°C and 650°C in air
according to JIS G 0567 6).

Figure 2 shows the scanning electron (SE) and STEM images of X plant on cross section perpendicular to the axial
direction of the tube. Some large particles with bright contrast in Fig. 2(a) were observed randomly, and those particles were
identified as niobium carbonitride (Nb (C, N)) by dispersive x-ray spectrometer (EDS). These large size niobium carbonitrides
are present from the initial structure due to unconsolidated Nb. On the other hand, coarse phases with dark contrast were
found at grain boundaries, and those phases were identified as σ phase by EDS. In addition, many fine needle-shaped phases
(Yellow circled phases) that also appear dark were observed in the grains. These fine phases were also identified as σ phase.
The precipitation of σ phases at grain boundaries and ingrains was more clearly seen in the STEM image shown in Fig. 2(b).
Fine M23C6 carbides (indicated by blue allow) with grey contrast identified by EDX were also observed at grain boundaries.
There were some white circular holes around σ phases, which is presumed to be dropout of Cu phases.
In order to identify fine precipitates easily, the STEM image with combination of elements map is shown in Fig. 3.
Many fine Cu phases (red particles) were observed in the grains. Fine particles of niobium carbonitride (Nb-rich pink
particles) and complex nitride of niobium and chromium (NbCrN), Z-phase, were also observed. Above fine particles are
precipitated during long-term exposure in the plant.
Table 1 Lists of long-term used Super 304H steel tubes

Main steam 1) Nominal dimensions Applied Design conditions at tube
Plant Operating time 2) Component
Temperature/Pressure Outer diameter thickness stress 3) Temperature/Pressure
D2 600℃/24.5MPa 148,000h Final Superheater 45.0mm 6.5mm 80.0MPa 636℃/27.0MPa
N 593℃/24.1MPa 140,000h 2nd superheater 57.0mm 7.0mm 97.9MPa 548℃/27.4MPa
X 600℃/25.0MPa 138,000h 4th superheater 45.0mm 6.8mm 77.2MPa 640℃/27.5MPa
1) Main steam temperature and pressure are the operating condition of the plant.
2) Operating time includes the temperature reduction period in the plant.
3) Applied stress is the hoop stress calculated from the design pressure and nominal dimensions of tube based on the mean
diameter formula.
Table 2 Chemical compositions of new and aged materials (wt%)

Material C Si Mn P S Cr Ni Cu Mo Nb N Sol-Al
17.00~ 7.50~ 2.50~ 0.30~ 0.05~
Specification 0.07~0.13 <0.30 <1.00 <0.04 <0.01 - -
19.00 10.50 3.50 0.60 0.12
New 0.08 0.23 0.80 0.03 0.001 18.54 8.57 2.96 - 0.50 0.11 0.018
D2 0.08 0.17 0.97 0.03 0.001 18.42 9.01 2.76 0.25 0.47 0.11 <0.005
N 0.08 0.19 0.81 0.03 0.001 18.57 8.65 2.96 0.25 0.49 0.11 0.011
X 0.08 0.23 0.79 0.03 <0.001 18.83 9.22 2.95 0.26 0.53 0.11 0.016
Heat treatment of new material: Solution annealed at 1150 °C for 2 min followed by water quenching
M10P1.5
O 6
8
10
55 15 10 30 10 15
7.5
5~7.5
(a) Charpy specimen (b) Tensile specimen

Figure 1 Shape and dimensions of specimens tested

Cr Nb Cu CrFe
σ phase
σ phase
Nb(C, N) σ phase Nb(C, N)
σ phase σ phase
σ phase
M 23C6
Z phase
σ phase
σ phase
10µm 2µm 500nm
(a) SE image (b) STEM image Figure 3 STEM image with

Figure 2 Microstructure observation of X plant combination of elements map
Flame
Note: Average value is
shown for D2, because side
flame side is unknown.
Rear
side
N D2 X N D2 X
Figure 4 Area fraction of σ phase at the middle Figure 5 Mean and the maximum diameters of Cu
part in thickness direction of aged materials phase of aged materials
Figure 4 compares area fraction of σ phase at the middle part in thickness direction of aged materials. The total area
and the area at grain boundary are shown to distinguish the amount of σ phase at the grain boundary and ingrain. The area
fraction of σ phase increased in the order of N, D2 and flame side of X, and the value on the rear side was smaller than that on
the flame side. This is due to the difference in metal temperature of each material. That is, the N plant has the lowest operating
temperature, the X plant has the highest operating temperature as shown in Table 1, and the metal temperature on the rear side
is lower than that on the flame side.
Figure 5 shows mean and the maximum diameters of Cu phase of aged materials. Note that the value of X plant is
measured on the flame side. Both mean and the maximum diameters increased in the order of N, D2 and X as well as the area
fraction of σ phase. However, the maximum value does not necessarily depend only on temperature since Cu phase
preferentially precipitates around σ phase as shown in Fig. 2(b).
Figure 6 presents hardness distributions in thickness direction of new and aged tubes. The hardness on the outer
surface side of new tube were higher than the rest part, possibly due to cold calibration during the tube manufacturing process.
The hardness on the outer surface side of aged tubes were comparable to those of the new tube, indicating that the effect of the
cold calibration remains. In addition, the hardness on the inner surface side of D2 and X were also higher, which may be due
to work hardening from the shot peening process. On the other hand, the hardness at the middle part in thickness direction of
all the aged tubes were higher than those of the new tube, approximately 200 HV, and no difference was confirmed depending
on the metal temperature of aged tube.
Figure 7 shows average values of impact energy of new and aged materials. The impact energy decreased
significantly due to long-term exposure, to about 60% of new material for the N plant and about 20% for the D2 and X plants.
The impact energy on the flame side was smaller than that on the rear side. This means that the impact energy decreases with
increasing the metal temperature of aged material. The change in impact energy corresponds to the microstructural evolution
of σ phase shown in Fig. 4. That is, material with larger amount of σ phase in Fig. 4 had the smaller impact energy in Fig. 7.

Rear
Flame side
side
New N D2 X
Figure 6 Hardness distributions of all materials Figure 7 Impact energy of all materials
Requirement value
at R.T
New N D2 X
Figure 8 Stress-strain curves of all materials at 600°C Figure 9 0.2% proof stresses of all materials
Figure 8 shows stress-strain curves of new and aged materials at 600°C as a representative case. Ultimate tensile
strength of the N plant was larger than that of new material while those of the D2 and X plants were smaller. Rupture
elongations of all the aged materials, on the other hand, were smaller than that of new material. Similar to the impact energy,
the rupture elongations of the D2 and X plants were smaller than that of the N plant, which is also due to the difference in the
amount of σ phase.
Figure 9 compares 0.2% proof stress (σ0.2) of new and aged materials at R.T, 600°C and 650°C. The 0.2% proof
stresses of the aged materials at each temperature were larger than those of new material. This is resulted from precipitation
strengthening by fine M23C6, Cu phase, Nb (C, N) and Z phase precipitated during long-term exposure.
Conclusions
Microstructures and mechanical properties of several long-term used Super 304H steel tubes were investigated.
Several typical phases were observed in aged materials such as M23C6, Cu phase, Nb (C, N), Z phase and σ phase. σ phases
were precipitated not only at grain boundaries but also within grains in the aged materials with high operating temperature.
The hardness at the middle part of tube thickness of aged materials were larger than those of new material as well
as the 0.2% proof stress. The elongation and impact energy, on the other hand, were significantly lower than those of the new
material, and the reduction increased with increasing the metal temperature of the aged material. The change in impact energy
and elongation corresponds to the microstructural evolution of σ phase.
References
1) H. Semba, Y. Sawaragi and K. Ogawa, Materia Japan, 48-2 (2007) pp. 99-101.
2) NIMS Creep Data Sheet, No. 56A, (2018).
3) K. Sawada, K. Sekido, M. Murata, K. Kamihira and K. Kimura, Materials Characterization, 141 (2018) pp. 279-285.
4) K. Kubushiro, Y. Shioda and K. Nomura, Journal of the Society of Materials Science, Japan, 66-2 (2017) pp. 179-184.
5) T. Kimura, Y. Shioda and K. Kubushiro, Journal of the Society of Materials Science, Japan, 68-2 (2019) pp. 142-147.
6) JIS G 0567: 2012, (2012).

The insights from crystallography into the effect of boundaries on the toughness in a
heavy gauge high strength low alloy steel
Chengjia Shang
Collaborative Innovation Center of Steel Technology

University of Science and Technology Beijing, BEIJING , CHINA,
email: cjshang@ustb.edu.cn
Keywords: HSLA, bainite/martensite, variants, boundaries, heavy gauge
High performance low alloying structural steel has many applications in humanity activities. Increasing the strength
of steel is a trend for reduce structural weight, save cost and declining environment load. However, with the increasing the
strength, toughness always degenerating, especially for the heavy gauge plate. For the safety of the high-rise building, long
span bridge, large container ship and long-distance pipeline etc., excellent lower temperature toughness is one of the key
challenges of the metallurgist.
Low carbon bainitic and/or martensitic phases are the dominant microstructure to achieve high strength and high
toughness. Conventionally, prior austenite grain, packet, block and variant boundaries are the crystallographic microstructure
of bainite and/or martensite. Definitely, chemical elements (C and Ni), recrystallization (prior austenite grain size), and cooling
rate dramatically influence the phase transformation of bainite and/or martensite. Although, the prior austenite grain size and
the cooling rate can be controlled properly for the thin plate, it is obviously very difficult to control the homogeneity
microstructure of throughout cross section in a heavy gauge plate.
The quantitative characterization of bainite and/or martensite microstructure is based on parents and daughters (K-S
or N-W) relationship. By the computational materials engineering approach, homemade software and model have been
developed to digitalization the variants and boundaries in bainite and/or martensite 1,2).
To simulating the heavy gauge plate, Jominy end quenching test has been carried out to reveal the effects of
composition, prior-austenite grain size and cooling rate on the variant selection and boundary characteristics. In this
presentation, the crystallographic characteristic of boundaries of low carbon bainitic and/or martensitic microstructure will be
investigated. There will be three parts in the presentation:
(1) Effect of carbon and Ni content on the variant selections 3,4)
(2) Effect of prior austenite grain size refinement on the variant selection 5)
(3) Effect of kinetic and thermodynamic on the variant selection 6)
References
1)Wu B B, Wang Z Q, Wang X L, et al. Toughening of martensite matrix in high strength low alloy steel: Regulation of variant pairs.
Materials Science and Engineering: A, 2019, 759: 430-436.
2)Li X C, Zhao J X, Cong J H, et al. Machine learning guided automatic recognition of crystal boundaries in bainitic/martensitic
alloy and relationship between boundary types and ductile-to-brittle transition behavior[J]. Journal of Materials Science &
Technology, 2021, 84: 49-58.
3)Yu Y S, Wang Z Q, Wu B B, Zhao J X, et al. Tailoring variant pairing to enhance impact toughness in high-strength low-alloy
steels via trace carbon addition, Acta Metallurgica Sinica (English Letters), 2021, 34: 755-764.
4)Huang S, Yu Y S, Wang Z Q, et al. Crystallographic insights into the role of nickel on hardenability of wear-resistant steels,
Materials Letters, 2022, 306: 130961.
5)Wu B B, Wang X L, Wang Z Q, et al. New insights from crystallography into the effect of refining prior austenite grain size on
transformation phenomenon and consequent mechanical properties of ultra-high strength low alloy steel. Materials Science and
Engineering: A, 2019, 745: 126-136.
6)Wu B B, Wang Z Q, Yu Y S, et al. Thermodynamic basis of twin-related variant pair in high strength low alloy steel. Scripta
Materialia, 2019, 170: 43-47.

Development of atomic resolution electron microscope for magnetic materials and steels
Naoya Shibata1,2,3*
Institute of Engineering Innovation, The University of Tokyo, Tokyo 113-8656 Japan

1
2
Nanostructures Research Laboratory, Japan Fine Ceramic Center, Nagoya 456-8587, Japan
3
Quantum-Phase Electronics Center (QPEC), The University of Tokyo, Tokyo 113-8656, Japan.
*email: shibata@sigma.t.u-tokyo.ac.jp
Keywords: Scanning transmission electron microscopy, differential phase contrast, electromagnetic field, steels, magnetic materials
Aberration-corrected scanning transmission electron

microscopy (STEM) is a powerful technique for directly
observing atomic-scale structures and chemistry of individual
defects such as grain boundaries and dislocations, inside
materials and devices. In the state-of-the-art STEM, a probe size
of less than 0.5Å in diameter has been experimentally realized1).
However, in ordinary STEM, atomic-resolution observation of
magnetic materials (such as steels) is essentially difficult, since
high magnetic fields (~2T) are inevitably exerted on samples
inside the magnetic objective lens. In recent years, we have
succeeded in developing a new magnetic objective lens system
that realizes a magnetic field free environment at the sample
position. This lens system is basically composed of two round
lenses and the sample is inserted in between the lenses. We excite
the magnetic round lenses so that the perpendicular magnetic
0.5nm
fields at the sample position can be cancelled out. Using this new
objective lens system combined with the state-of-the-art higher
order aberration corrector, direct atom-resolved imaging of Figure1: ADF STEM image of Fe-3%Si alloy.
magnetic materials such as silicon steels is realized in STEM2).
Figure 1 shows an annular dark field STEM image of Fe-3%Si
alloy, one of the most important engineering soft magnetic
materials. It has been extremely challenging to observe atomic
structures of magnetic materials in electron microscopy, but now
observation becomes routinely possible. This novel electron
microscope (Magnetic-field-free Atomic Resolution STEM:
MARS) (see Figure 2) is expected to be useful for research and
development of advanced magnetic materials and steels.
On the other hand, by using elaborate detectors such
as segmented or pixelated detectors in STEM, we can not only
image atoms, but can also image electromagnetic field
distribution inside samples through differential phase contrast
(DPC) imaging techniques3). Applying DPC imaging in atomic
resolution STEM, we can now directly visualize the electric field
distribution within single atoms4), i.e. the electric field between
the positively charged atomic nucleus and the negatively charged
electron cloud. Therefore, it now becomes tempting to directly
observe magnetic fields at atomic resolution by MARS, which
should strongly correlate with the fundamental properties of
magnetic materials.
However, to visualize magnetic fields at atomic scale, Figure 2: MARS at U. Tokyo

we must solve remaining
major difficulties even after
magnetic-field-free
atomic-resolution STEM
imaging becomes possible.
One major difficulty is that
both the specimen’s electric
and magnetic fields
inevitably contribute to the
phase shift of the incident
electron probe. To visualize
magnetic fields, we must
differentiate between electric
and magnetic phase shift __
Figure 3: (left) Unit cell averaged and tiled ADF image of α-Fe2O3 observed along the [11
components in the
20] direction. (right) The corresponding projected magnetic field vector color map. The
atomic-resolution DPC
images. The other major antiparallel magnetic field component on the adjacent Fe-Fe double atomic layers is clearly
difficulty is that the phase observed, visualizing antiferromagnetic order in this crystal5).
shift induced by the
atomic-scale magnetic field is predicted to be extremely small. Thus, very high signal-to-noise ratio imaging conditions
should be fulfilled. We have demonstrated that real-space visualization of intrinsic magnetic fields of an antiferromagnetic
material is possible by combining kernel filtering and unit-cell averaging techniques to solve the difficulties of differentiating
between electric and magnetic phase shift components and extremely small magnetic phase shifts5). Figure 3 shows the
magnetic field image (unit cell averaged and tiled image) of a hematite (α-Fe2O3) crystal. The details of this
magnetic-field-free STEM and the material application results will be presented in the talk.
Acknowledgement
The author thanks all the collaborators of this research, especially Y. Kohno (JEOL Ltd.), T. Seki, T. Matsumoto, Y. Ikuhara (U.
Tokyo), S.D. Findlay (Monash U.) for their contribution to the works shown in this presentation. The author acknowledges support
from the JST SENTAN Grant Number JPMJSN14A and the JSPS KAKENHI Grant numbers 20H05659, 19H05788, 17H06094.
References
1) S. Morishita et al., Microscopy, 67, 46 (2018).
2) N. Shibata et al., Nature Comm. 10, 2380 (2019).
3) N. Shibata et al., Nature Phys., 8, 611-615 (2012).
4) N. Shibata et al., Nature Comm. 8, 15631 (2017).
5) Y. Kohno et al., Nature 602, 234-239 (2022).

Atomistic investigation of clustering and precipitation in Nb-microalloyed steel
Jae Hoon Jang1,* and Sung-Dae Kim1
1
Korea Institute of Materials Science, Changwon, 51508, Republic of Korea
*email: jhjang@kims.re.kr
Keywords: steel, niobium, cluster, first principles calculation, TEM
1. INTRODUCTION
High strength low alloy (HSLA) steels have a good combination of strength and formability, so they have many applications
in the building, energy transportation, and automotive industries. In HSLA steels, microalloying elements such as Ti, V and
Nb are used to control microstructure and mechanical properties. In particular, Ti and Nb are used to control the austenite
grain size or to induce precipitation strengthening. The improvement effects of Ti and Nb carbides in ferrite on strength have
been extensively studied 1-3). According to one recent study, TiC precipitates appeared after the Ti-clustering process, and it
was confirmed that the strengthening effect of Ti clustering was more effective than that of TiC type precipitates 4). Although
many theoretical studies have been conducted on the formation of MC (M=Ti, Nb) type carbide and on interfacial properties 5),
studies on clustering in the early stages of the precipitation process have rarely been reported. In this study, first principles
calculations were used to analyze the generation of Ti and Nb clusters in the ferrite matrix. In addition, the process of
changing into MC type precipitates from cluster was analyzed, and this was experimentally confirmed by observing Nb
microalloyed steel using high resolution transmission electron microscopy.
2. EXPERIMENTAL
First-principles modeling was employed to estimate the formation energy and the lattice misfit at the ferrite/cluster interface.
The spin-polarized Vienna ab-initio simulation package (VASP) was used in projector augmented wave (PAW) formalism.
To calculate the lattice parameter and formation energy of the bcc M (M=Ti, Nb) with carbon, the atomic structure of a 2x2x2
supercell of conventional bcc unit cell was used. It was assumed that the carbon atom was located at the octahedral interstitial
site of the bcc lattice, and the arrangement of additional carbon was assumed to be at the site with the greatest distance from
the nearest atom among 16 octahedral interstitial sites. The internal atomic positions and lattice parameters were fully relaxed
using the total energy and force minimization scheme with the gradient quasi-Newton method. We assumed that convergence
was achieved when the forces acting on the atoms did not exceed 0.01 eV/ Å.
3. RESULTS AND DISCUSSION

The initially generated Nb cluster contains less carbon than does NbC. According to the formation energy, determined from
first principles and thermodynamic equilibrium calculations, pure bcc Nb is not stable in the ferrite matrix. In the case of
ferrite matrix and pure bcc Nb, the lattice misfit is about 17%, and the strain energy due to this misfit is about 0.76 eV. On the
other hand, the calculation results for formation energy of pure bcc Nb are positive, and clusters without carbon cannot be
spontaneously created. As the carbon content increases, the formation energy dramatically decreases to a negative value, and
clusters can be formed containing certain amounts of carbon. However, at the same time, tetragonality is induced due to the
carbon contained in the cluster, as shown in Fig. 1, which leads to larger misfit in the [001] direction. In the [110] direction, the
lattice contracts and the coherency is improved. Due to the high coherency in the [110] direction, the cluster grows into a disk
shape. In the cluster stage, the content of carbon is limited to maintain a coherent interface in the [001] direction. As the carbon
content increases and the size of the cluster increases, the interface changes from a coherent type to a semi-coherent type, and
transforms into a MC type precipitate. This process in Nb containing ferritic steel was directly observed using high resolution
in-situ TEM in Nb containing ferritic steel.

4.4
Lattice parameter / A
4.0
Nb c-direction
Nb a-direction
3.6 Ti c-direction
Ti a-direction
3.2
a
2.8
0.0 0.5 1.0
Site fraction of C
Fig. 1. Calculated lattice parameter changes as a function of carbon contents.
References
1) J. H. Jang, C.-H. Lee, Y.-U. Heo, D.-W. Suh: Acta. Mater. 60 (2012) 208-217
2) C. Y. Chen, C. C. Chen, J. R. Yang: Mater. Char. 88 (2014) 69-79
3) S. Jukherjee, I. Timokhina, C. Zhu, S. P. Ringer, P. D. Hodgson: J. Alloys Compd, 690 (2017) 621-632
4) J. Wang, M. Weyland, I. Bikmukhametove, M. K. Miller, P. D. Hodgson, I. Timokhina: Scr. Mater. 160 (2019) 53-57
5) S. Lu, J. Agren, L. Vitos: Acta Mater. 156 (2018) 20-30

In-situ neutron diffraction study on lattice parameter changes of austenite and martensite
during transformation in Fe-18Ni alloy
Wu Gong 1,*, Stefanus Harjo 1, Yo Tomota 2, Takuro Kawasaki 1, Satoshi Morooka 3, Akinobu Shibata 4, and
Nobuhiro Tsuji 5
1
J-PARC Center, Japan Atomic Energy Agency, 2-4 Shirane Shirakata, Tokai, Naka, Ibaraki, 319-1195, Japan
2
National Institute of Advanced Industrial Science and Technology, 1-1-1 Umezono, Tsukuba, Ibaraki, 305-0047, Japan
3
Materials Science Research Center, Japan Atomic Energy Agency, Tokai, Ibaraki 319-1195, Japan
4
Research Center for Structural Materials, National Institute for Materials Science (NIMS), 1-2-1 Sengen, Tsukuba 305-0047, Japan
5
Department of Materials Science and Engineering, Kyoto University, Yoshida-honmachi, Sakyo-ku, Kyoto, 606-8501, Japan
*email: wu.gong@j-parc.jp
Keywords: martensitic transformation, neutron diffraction, phase stress, lattice parameter, Fe-18Ni alloy
Austenite to martensite transformation in steels is a volume expansion phase transformation. Under the prediction given by the
Eshelby’s inclusion theory, a hydrostatic compressive stress will be generated in martensite during the martensitic transformation,
because the martensite grain cannot expand to its ideal volume under the constraint of surrounding austenite. As a results, a tensile
hydrostatic stress will be generated in the untransformed austenite due to the stress balance condition. The phase stresses generated
by martensitic transformation have been studied experimentally for a long time, however, the puzzling results have still been
reported. In 1980, Tanaka and Shimizu claimed the generation of hydrostatic compressive stress in austenite with MT during sub-
zero cooling estimated from the change in austenite lattice parameter measured by in-situ X-ray diffraction below room
temperature (RT) for Fe-Mn-C alloys, in which the austenite lattice parameter was smaller than that extrapolated from thermal
expansion coefficient 1). On the other hand, Hayakawa and Oka observed a decreasing of the austenite lattice parameter for a
rapidly cooled sample while little change in a slowly cooled sample and then concluded that the macroscopic residual stress near
the specimen surface generated by temperature gradient during quenching after solution treatment was relaxed with MT 2). That
is, macroscopic residual stress should be considered to evaluate phase stresses, correctly. To avoid the surface effect, synchrotron
X-ray diffraction with high penetration ability has been employed for studying this issue in recent years. Several studies have
reported that the austenite phase stress change from tensile hydrostatic to compressive with increasing of martensite volume
fraction 3,4). To clarify this puzzling topic, we carried out neutron diffraction experiments having higher penetration ability than
above methods to investigate the lattice parameter changes in real time during martensitic transformation. A high-purity Fe-18Ni
binary alloy was selected to avoid the chemical contribution from the interstitial element. Several measuring processes were
carefully designed and performed by in-situ neutron diffraction.
Chemical composition of the alloy used in this study was Fe-17.76Ni-0.037Al-0.0016C-0.0012N (wt%). In-situ neutron
diffraction experiments were conducted at the beam-line 19 ‘TAKUMI’ in MLF, J-PARC with a thermomechanical processing
simulator installed on it as shown in Fig. 1(a). Cylindrical specimens of the alloy with height of 11 mm and diameter of 6.6 mm
were used. As shown schematically
in Fig. 1(b), an optical dilatometry
was used to simultaneously measure
the change in diameter of the
specimen with in-situ neutron
diffraction to compare volume
change of a whole sample with
crystalline diffraction data.
Diffraction profiles were analyzed
via Rietveld refinement to obtain the
volume fractions and lattice
Fig. 1 Schematic illustration showing (a) the thermomechanical processing simulator
parameters of austenite and
installed on TAKUMI (b) the diffraction geometry of in-situ neutron diffraction
martensite. Single peak fitting was
experiment.
also carried out to obtain the

diffraction reflection dependent behavior. Microstructures of the specimens were analyzed by EBSD.
Fig. 2 shows the temperature history and kinetics of MT during the continuous cooling process. The specimen was austenitized
at 900 °C for 180 s, and cooled down to 400 °C at a cooling rate of -1 °C/s, and finally cooled down to 20 °C (RT) at a cooling
rate of -0.1 °C/s (Fig. 2a). Fig. 1(b) present the changes in diffraction profile with decreasing the temperature. The diffraction
profile at 323 °C shows single austenite phase. The martensite peaks appeared at 293 °C and their intensity increased gradually
with cooling, and austenite peaks disappeared completely in the diffraction profile of 20 °C. The volume fraction of martensite
(f α¢ ) obtained by a quantitative analysis on all profiles is shown in Fig. 1(a). The martensite start temperature (Ms) of the Fe-18Ni
alloy is determined to be 315 °C and the martensite finish temperature (Mf) is approximately 120°C.
Fig. 2 (a) Temperature history and change in volume fraction of martensite. (b) Changes in neutron diffraction profile during
continuous cooling.
Fig. 3 shows the changes in lattice parameters of austenite and

martensite during continuous cooling. Interestingly, the lattice
parameter of austenite became lower than the extrapolated line from
the thermal contraction in a single austenite region (Ms ~ 400°C),
while the lattice parameters of martensite during martensitic
transformation were higher than the extrapolated line from the
thermal expansion in a single martensite region (20°C ~ Mf). Both
phases exhibited large deviation when they became the minority
phase, which seems to be consistent with the stress balance
requirement at a glance. If the lattice parameter variation was only
caused by the phase stresses, the present results would result in
hydrostatic compressive stress in austenite and tensile stress in
martensite, which is opposite to the prediction by the Eshelby’s
inclusion theory.
In order to further examine the change in lattice parameter during
tempering, a cyclic treatment consists of continuous heating and
cooling was carried out on a partially martensitic transformed
specimen. Fig. 4(a) shows the variation of temperature history and the
corresponding f α¢ as a function of elapsing time. After austenitization
at 900°C for 180s, the specimen was quickly cooled to 700°C
followed by a continuous cooling to 290°C at -0.1°C/s. The f α¢ Fig. 3 Changes in lattice parameters of (a) austenite
gradually increased to approximately 68% during the continuous and (b) martensite during continuous cooling.
cooling. Then, the specimen with dual-phase microstructure was subjected to two heating-cooling cycles in the temperature region

of 290°C~520°C at a rate of 0.1°C/s (-0.5°C/s for the final cooling step). f α¢ was unchanged during the cyclic process. For
comparison, the process was divided into 4 steps as follows, step 1: the 700°C→290°C cooling; step 2: the first 290°C→520°C
heating; step 3: the first 520°C→290°C cooling, and step 4: the second 290°C⇄520°C cycle.
The lattice parameter changes of austenite and martensite are shown in Fig. 4(b) and (c), respectively. In step 1, the lattice
parameter of austenite became lower than the thermal contraction line below Ms similar to that in Fig. 3a. In step 2, the lattice
parameter increased linearly with the elevation of temperature, however, the slope is roughly equivalent to that in single austenite
condition (Ms~520°C). In contrast, the lattice parameter of austenite in steps 3 and 4 are basically overlapped expressing the same
linear relationship between the lattice parameter and temperature, and the slopes are smaller than that in the single austenite region.
During heating, a hydrostatic compressive stress will be subjected to austenite from the surrounding martensite, because the latter
possesses a smaller CTE. The lattice parameter of austenite evolution in step 3 and 4 is consistent with the condition under thermal
stress, but that in step 2 is anomalous. The slope of the lattice parameter of martensite vs. temperature in step 2 is smaller than
those in steps 3 and 4, showing an opposite variation to that in austenite.
Fig. 4 (a) Temperature history and changes in volume fraction of martensite. Changes in lattice parameters of (b) austenite and
(c) martensite, and (d) total stress.
Using the stress and defects free lattice parameters (𝜀) as the reference, the lattice strains of austenite and martensite were
calculated. Then, the lattice stress is given by,
!
𝜎＝ "#$% 𝜀
where, E and υ refer to the Young’s modulus and the Poisson’s ratio, respectively. Therefore, the total stress 𝜎& can be calculated
by the volume fraction weighted average method as follows,
)
𝜎& = 𝑓 '( ∙ 𝜎 '( + (1 − 𝑓 '( ) ∙ 𝜎
)
where, 𝜎 and 𝜎 '( refer to the lattice stresses of austenite and martensite, respectively. The 𝜎& as a function of time is shown
in Fig. 4(d). Despite the total stress is expected to be zero, 𝜎& deviated from zero with the progress of martensitic transformation

in step 1, and was regained to zero after tempering in step 2. The steps 3 and 4 satisfied the stress balance requirement well. The
variation tendency of total stress during steps 1 and 2 is similar to that of the dislocation density in the microstructure, where the
dislocations were introduced by the martensitic transformation and annihilated in the subsequent tempering. It implies that the
change in lattice parameter is not only affected by stress but may be also related to the crystal defects in the microstructure. More
details on the relationship between the lattice parameter and lattice defects will be shown in the presentation.
Acknowledgement
This work was primarily supported by the Elements Strategy Initiative for Structural Materials (ESISM) in Kyoto University. The
authors would like to thank Prof. Goro Miyamoto of Tohoku University, Japan for providing the alloy. The neutron diffraction
experiments at the Materials and Life Science Experimental Facility of the J-PARC were performed under a general program (Project
No. 2018L0400).
References
1) Y. Tanaka, K. Shimizu: Trans. JIM 21 (1980) 42-51.
2) M. Hayakawa,M. Oka: Acta metall., 31(1983), 955-959.
3) M. Villa, F. Niessen, M.A.J. Somers: Metall. Mater. Trans. A 49 (2018) 28-40.
4) S.Y.P. Allain, S. Gaudez, G. Geandier, J.C. Hell, M. Gouné, F.Danoix, S. Michel, A. Samy, A. Poulon-Quintin: Mater. Sci. Eng. A
710(2018)245-250.

Automated sample preparation and precipitate characterization in TEM for HSLA steel
Alexander Bright1, *, Hiromi Sekiguchi1 and Roger Maddalena2

1
Thermo Fisher Scientific, 140-0002 Tokyo 4-12-2 Higashi-Shinagawa, Shinagawa-ku, Japan
2
Thermo Fisher Scientific, Zwaanstraat 31G 5651 CA Eindhoven, Netherlands
*email: alex.bright@thermofisher.com
Keywords: HSLA steel, precipitates, electron microscopy, automation
At the end of the hot rolling process, microalloyed steel will form nanoscale precipitates of compounds such as
NbC and TiN. These precipitates have the potential to improve properties by grain refinement and precipitation hardening.
Precipitates with smaller size and higher number density typically yield higher strength. The rate of cooling after hot rolling
will control the precipitation and coarsening of these particles. One of the challenges is to obtain a statistically meaningful
distribution of their size, shape and composition as up to now this has only been possible through tedious, manual analysis.
In this study two electron microscopy workflows are presented. In the first workflow, a FIB-SEM dual beam is used
to prepare a site specific TEM lamella with a highly automated process. Thin foil sections of roughly 25 square microns can be
prepared in 2-3 hours. In the second workflow, a TEM is used to acquire tile-by-tile images and chemical information in a fully
automated process, even for overnight, unattended analysis. Lamellae prepared by focused ion beam have advantages
compared to the carbon replica technique. For example, particle location is maintained relative to a grain boundary, and
particles are not lost or destroyed during sample preparation.
Instead of characterizing just a few precipitates per day manually, the automated TEM can process a statistically
relevant number of particles (thousands) in an overnight run. With these workflows, the time to develop a new steel product can
be reduced and R&D manpower can be freed up for new responsibilities.
Figure 1: S/TEM image of FIB-prepared steel lamella (left) and STEM-in-SEM image of nanoparticles in the steel matrix.

A precise measurement of grain boundary segregation in steel by
STEM-EDS and ζ-factor method
Yuya Murata1*, Taku Moronaga2, Kazushi Hayashi1, Toru Hara2
1
Applied Physics Research Laboratory, Kobe Steel, Ltd., 1-5-5, Takatsukadai, Nishi-ku, Kobe, 651-
2271, Japan
2
Research Network and Facility Services Division, National Institute for Materials Science, 1-2-1,
Sengen, Tsukuba, 305-0047, Japan
*Email: murata.yuya@kobelco.com
Keywords: steel, grain boundary segregation, STEM-EDS, ξ-factor method
Aim and scope

It is well known that grain boundary segregation of solute atoms induces intergranular
embrittlement in alloys and steels. Grain boundary segregation has been measured by Auger
electron spectroscopy (AES), 1 atom probe tomography, 2 and scanning transmission electron
microscopy (STEM) with energy-dispersive X-ray spectroscopy (EDS)3,4 and/or electron energy-
loss spectroscopy. However, grain boundary segregation measurement in AES is known to have
some uncertainties. AES can be applied to only grain boundary where intergranular fracture
occurs, but segregated solute atoms are not always distributed equally in the two surfaces.5 On
the other hand, STEM-EDS result includes a counting error of X-ray intensity from trace elements,
and a systematic error by absorption of X-ray from solute atoms by matrix atoms.
To overcome these issues, we applied an aberration-corrected STEM with an ultra-large solid-
angle EDS system to improve the spatial resolution and sensitivity. In addition, ζ-factor method,
proposed by Watanabe3 was applied to improve the accuracy. We applied the improved grain
boundary segregation measurement of trace elements in steels.
Materials and methods

We investigated two steel alloys, Fe-1.48wt%Mn-0.01wt%P, and Fe-1.44wt%Mn-0.01wt%P-
2.23wt%Cr, referred to as NC and CR, respectively. The samples were heated at 1273K for 1 hour
and furnace cooled at -1K/min, resulting in a ferrite structure with an average grain size of 200
µm. Then, the samples were heated in two different conditions for segregation, isothermal heating
and step heating. In the isothermal heating, the Fe-Mn-P sample was heated at 773K or 973K, the
Fe-Mn-P-Cr sample was heated at 773K for 500 hours, and water quenched. In the step heating,
both samples were heated at 866K for 1 hour, 811K for 15 hours, 797K for 24 hours, 769K for 60
hours, and 741K for 100 hours. The grain distribution was observed by electron backscattering
diffraction, and a thin foil for STEM was taken from a high-angle grain boundary with a grain

boundary orientation of around 50° from each sample by focused ion beam.
The grain boundary segregation was measured by an aberration-corrected STEM JEOL JEM-
ARM300F equipped with a EDS detector with a solid-angle of 1.146 sr. This large solid-angle
detection system provides highly efficient and high-resolution compositional analysis. EDS maps
were taken with an electron beam acceleration voltage of 300 kV, an electron beam current of
about 0.5 nA, an electron beam width of about 1 nm, an area of 100 nm × 100 nm, and
measurement points of 512 × 512. The acquisition time was 3-5 hours. A drift correction was
executed in every 5 seconds.
The X-ray intensity obtained at each measurement point was converted to the composition by ξ-
factor method. The advantage of ξ-factor method to conventional Cliff-Lorimer method is
correction of an error caused by an absorption of X-ray from solute atoms by matrix atoms, based
on estimation of the sample thickness at each point. The conversion factor in ξ-factor method
must be determined from a standard sample with known composition, density, and thickness, for
each EDS facility. In this study, we used the conversion factor determined with a standard sample
SRM2063a issued by the National Institute of Standards and Technology. The error of the
composition and the minimum detectable composition were also calculated by ξ-factor method,
based on the counting error of the obtained X-ray intensity and the error of the conversion factor
in ξ-factor method. The errors in this report represent a 99.7% confidence limit (±3σ).
Results
The composition maps of the solute atoms of the Fe-Mn-Cr-P sample treated by isothermal
heating at 773K are shown in Fig. 1. The composition of the solute atoms increases at a thin area
with a width of about 5 nm, which seems to be a grain boundary. The absorption-correction term
was calculated from the sample thickness at each measurement point. In this sample, the range of
the absorption-correction term for P distributed in 1.25-1.4.
The grain boundary segregations Γ (atom/nm2) with its errors, and the minimum detectable Γ are
shown in Table 1. The values were calculated from the composition, the composition error, and
the minimum detectable composition, in the grain boundary area and the grain area.3,6,7 In order
to improve the accuracy, the 14000 data points were binned in the grain boundary area and the
grain area with a width of 5 nm each, equivalent to an acquisition time of about 550 seconds. In
a reasonable acquisition time, we could obtain the error and the minimum detectable Γ lower than
the ones in the previous reports, owing to the large solid-angle of the EDS detector used in this
study. Table 2 showed that the Γ of P and Mn decrease with increasing temperature and Cr addition.
The grain boundary segregation energy −𝛥𝑔𝑏 calculated from the Γ of P and Mn according to
equation (1) is shown in Table 2.8
𝛤⁄(𝛤 𝑚𝑎𝑥 − 𝛤) = 𝑥 𝑒𝑥𝑝(− 𝛥𝑔𝑏 ⁄𝑅𝑇) (1)

𝛤 𝑚𝑎𝑥 is the grain boundary segregation sites in nm2. As 𝛤 𝑚𝑎𝑥 , we assumed an atomic density of a
Fe(100) plane (12.3 atom/nm2). 𝑥 is the atomic fraction in the bulk. The −𝛥𝑔𝑏 for P obtained by
STEM-EDS in this study stays in the range of the values by AES measurements reported in the
previous literatures, although the range is wide (21-63 kJ/mol).1,8
The Γ and the ductile-brittle transition temperature (DBTT) in Charpy impact test of the samples
treated by step heating are shown in Table 3. As seen in the samples treated by isothermal heating,
the samples treated by step heating also showed that the Γ of P and Mn decrease with Cr addition,
and it was accompanied by decrease of DBTT. This trend coincides with the previous reports in
which P is a significant embrittling element, Mn is also embrittling but relatively weak, and the
influence of Cr is much smaller compared to the other two elements.1 Assuming that the influence
of P is dominant, we estimated an embrittlement sensitivity of P, i.e., a ratio between a change in DBTT
and a change in a grain boundary segregation. The embrittlement sensitivity is typically reported in
unit of Kelvins per atomic % of grain boundary segregation. The Γ (atom/nm2) of P was converted
to at% with the assumption of 𝛤 𝑚𝑎𝑥 above. Then, the embrittlement sensitivity was calculated to
be 17 K/at%. This value falls in the range of the ones reported for the various steels based on AES
measurements.1
Conclusion
We achieved grain boundary segregation measurement of trace elements in steels with the error
and the minimum detectable value lower than the ones in the previous reports, owing to the large
solid-angle of the STEM-EDS detector and ζ-factor method. We confirmed that the P grain
segregation measured by the improved method falls in the range in the previous reports based on
AES, in terms of its temperature dependence and the influence to the embrittlement property.
In future, the improved segregation measurement should be applied to grain boundaries with more
defined characters, in alloys with constant plastic flow resistance, in order to further reduce the
uncertainty in the investigations of the segregation and the embrittlement properties.
Figure 1
Composition maps of the CR sample treated by isothermal heating. The area is 100 nm × 100 nm.

Table 1 Grain boundary segregation Γ (atom/nm2) of samples treated by isothermal heating.
alloys Temperature (K) Γ (atom/nm2) minimum detectable Γ (atom/nm2)

Mn P Cr Mn P Cr
NC 773 9.6±0.8 2.2±0.1 - 0.08 0.04 -
973 2.9±0.6 0.7±0.1 - 0.09 0.08 -
CR 773 8.9±0.8 1.1±0.1 2.9±0.7 0.07 0.07 0.04
Table 2 segregation energies of samples treated by isothermal heating.

alloys Temperature (K) Segregation energy (kJ/mol)
Mn P
NC 773 35 45
973 24 47
CR 773 33 41
Table 3 Γ (atom/nm2) and DBTT(K) of samples treated by step heating.

alloys Γ (atom/nm2) DBTT (K)
Mn P Cr
NC 8.8±0.4 1.9±0.1 - 150

CR 7.2±0.3 1.0±0.1 1.9±0.3 25
Acknowledgement
The authors thank Prof. M. Watanabe of Lehigh University for providing the SRM2063a standard
sample and the analysis software for ξ-factor method. This study was carried out as a part of
Materials Open Platform steel project at National Institute for Materials Science in Japan.
References
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J. R. Rice and J.-S. Wang, Mater. Sci. and Eng. A107, 23 (1989).

Mechanical stability of austenite in advanced high strength steels
Jie Luo1 and Christopher Hutchinson1, *
1 Department of Materials Science and Engineering, Monash University, Melbourne, 3800, Australia
*email: crh@monash.edu
Keywords: austenite stability, medium-Mn steels, deformation-induced martensitic transformation, retained austenite,
strain partitioning, digital image correlation
Steel researchers continually strive to develop improved high-strength high-elongation structural components with applications
for the industrial world, especially in the automotive industry. This drives the development of sheet steel from conventional High
Strength steels (HSS) to the 3rd generation Advanced High Strength Steels (AHSS). Throughout this development, a key design
consideration is to take advantage of the transformation-induced plasticity (TRIP) effect arising from the deformation-induced
martensitic transformation from metastable austenite. The dynamically evolving microstructure during deformation can both
increase the base strength of the material and also significantly improve the strain hardening rate. These two contributions are
important requirements for designing high-strength high-elongation alloys.
Even though researchers have long realized the importance of understanding the TRIP effect, many important
questions governing the the mechanical stability of austenite remain unresolved. This is because of the complexities involved in
deconvoluting the different factors affecting the stability. It is known that the mechanical stability of austenite depends on the
chemical composition (1-5), grain size (6–9), and morphology(10–12) of the grains and also the constraints from the surrounding phases
(13–16)
. However, deconvoluting these different effects is not straightforward, and few studies dedicated to this deconvolution
exist. In addition, there is a lack of systematic characterization combining both macroscopic and local measurements of the
transformation. The variation between local and average measurements of strain-induced martensite can be significant due to
stress and strain partitioning between phases and an understanding must be achieved at both scales of the microstructure.
Recently, microscopic-digital image correlation (micro-DIC) combined with scanning electron microscopy (SEM)
has been proven as a useful technique for studying the local deformation behaviors with sub-micron resolution(17–22). In our study,
we couple micro-DIC with quasi in-situ electron backscattered diffraction (EBSD) testing. The patterning we chose for micro-
DIC is SiO2 nanoparticles (22). This speckle pattern does not interfere with the EBSD data acquisition, and the speckle density is
sufficiently high to provide good spatial resolution in the local strain measurements.
In this talk, we discuss the grain size effect on austenite mechanical stability in an intercritically annealed Fe-0.1C-5Mn
(wt. %) steel prepared under conditions where the composition of the austenite islands is the same and spatially uniform withing
the austenite. At each macroscopic deformation level, we obtain both the EBSD map (Figure 1(a), revealing the microstructure)
and DIC strain map for multiple regions. We use the open-source python routines (23) to conduct the data analysis. An example
coupling the DIC and the EBSD datasets is shown in Figure 1(b).
(a) (b)
Tensile direction
)
TD
ND RD
Figure 1 (a) EBSD map showing the phase contrast of the 120 hour-intercritically annealed 0.1C5Mn steel after 1st strain level. (b) The EBSD
map in (a) overlapped onto the DIC strain map for the same area.

We track the local strain and microstructure evolution of all the austenite grains in multiple regions as a function of
macroscopic strain. By plotting the grain size of these austenite grains versus the local strain they experienced before they
transformed to martensite, we can observe that the smaller the grain, the higher the local strain accumulates in the grain before it
transforms to martensite (Figure 2(a)). We can further categorize the austenite grains into three different groups based on their
grain orientations. This trend can still be observed in each grain population (Figure 2 (b), (c) and (d)).
(a) 111 (b)

IPF coloring || RD
Iron FCC
001 101
(c) (d)
Figure 2 (a) The grain size versus the local effective shear grain average strain (after which the austenite grain transforms to martensite) for all
the austenite grains examined in the studied 0.1C5Mn steel. The grains shown in (a) can be categorized into three groups based on their grain
orientations, i.e. (b) grains of which the <111> direction is (nearly) parallel to the rolling direction (RD), (c) grains of which the <101> direction
is (nearly) parallel to the rolling direction (RD) and (d) grains of which the <001> direction is (nearly) parallel to the rolling direction (RD)
In this talk, we discuss this approach and the insights that can be obtained in the effect of different variables on the mechanical stability
of austenite in advanced high strength steels.

References
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8) Y. Matsuoka, T. Iwasaki, N. Nakada, T. Tsuchiyama, and S. Takaki, ISIJ Int. 53, 1224 (2013).
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Austenite in Transformation-Induced Plasticity Multiphase Steels (2001).
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(2020). https://doi.org/10.5281/zenodo.3688097.

Austenite Reversion in Additive Manufactured Ultra High Strength Steels
Yingjie Yao1, Zhigang Yang1, Chi Zhang1, Hao Chen1, *
1
Key Laboratory for Advanced Materials of Ministry of Education, School of Materials Science and Engineering, Tsinghua
University, Beijing 100084, China
*email: hao.chen@mail.tsinghua.edu.cn
Keywords: additive manufacturing, maraging steel, cellular microstructure, austenite reversion
1. Introduction
Sub-micron cellular structure is a unique microstructure in additive manufactured (AMed) alloys. Abundant efforts
have been made to reveal the physical origin of cellular microstructures and their influence on mechanical response of AMed
materials. However, these researches are mainly based on austenitic stainless steels1,2,3), aluminium alloys4) and Co-Cr-Mo alloys5),
which are almost free of solid-state phase transformations. The effect of cellular microstructure on solid-state transformation and
their potential role in microstructure architecting are rarely explored.
In this work, the 18Ni300 maraging steel is fabricated by selective laser melting (SLM) and post-fabrication heat
treatment. The formation mechanism of cellular microstructures and the role of cellular microstructure in austenite reversion is
demonstrated by microstructure characterization and thermo-dynamic modeling.

Almost pore-free 18Ni300 blocks (composition shown in Table 1) with cellular microstructures are SLMed by a
Renishaw AM250 SLM system equipped with a pulsed laser source and a reduced build volume. All the heat treatments are
conducted by a Muffle furnace. The aging treatments are at 480 ℃ for 5 min ~ 20 h, and for some samples, a solution treatment
(900 ℃, 1 h) is applied before aging to eliminate the cellular microstructures.The volume fraction and spatial distribution of
phases are studied by SEM and EBSD. STEM is used to illustrate the spatial distribution of alloying elements in sub-micrometer
scale.The thermodynamic calculations are performed by Thermo-Calc software (database: TCFE7), and the phase-field
simulations are conducted by finite element solution environment FlexPDE ( database: TCFE7 and MOBFE2).
Table 1: The chemical composition ( in wt.%) of 18Ni300 powder used in this research
Fe Co Ni Ti Mo
Bal. 9.2 18.7 1.0 4.8
3. Results
Sub-micrometer cellular microstructures are found in as-SLMed samples. The cell boundaries are enriched in Ti and
Mo. Unlike materials with almost no solid-state phase transformations, no dislocation networks along the cell boundaries are
found in as-SLMed samples. The elimination of dislocation networks is supposed to be due to cyclic martensite ↔ austenite
transformations.
The cellular microstructure shows its crucial effect on promoting the austenite reversion during aging. Only small
amount (less than 3 vol.%) of austenite is detected in the as-SLMed samples (SLM samples). When aged at 480 ℃ (SLM-Age
samples), most cell boundaries transform into reverted austenite, and the austenite fraction exceeds 10 vol.% within 1 hour. The
austenite on the cell boundaries formed a distinctive 3D network. In contrast, conventional 18Ni300 steel and SLMed samples
aged after the solution treatment (Sol-Aged samples) show negligible austenite reversion.

Figure 1: SEM image (left) and the corresponding inverse pole figure of austenite (right) of SLM-Aged sample (aged for 5 h)
Thermodynamic calculations and phase-field simulations clarify the mechanism of the fast austenite reversion in
SLM-Age samples. The high Ti and Mo content can increase the driving force for austenite reversion effectively. Further phase-
field simulations show that when austenite grows along the cell boundaries, the austenite-martensite interface migrates quickly in
a massive manner. When the austenite-martensite interface moves towards cell interiors whose composition is almost the same
as the bulk composition, the interface will migrate sluggishly with significant element partitioning across it. The latter case can
also describe the austenite reversion at 480 ℃ in Sol-Aged samples and conventional 18Ni300 maraging steels.
4. Conclusions
Sub-micro cellular microstructure presents in SLMed Maraging steels. The cell boundaries are found to be rich in Ti
and Mo, but free of dislocation networks. These cells can significantly promote the austenite reversion when the SLMed samples
are aged at 480 ℃. During aging, the reverse austenite prefers to grow along the cell boundaries for the Ti and Mo enrichment in
these regions increases the driving force of austenite reversion effectively. When austenite-martensite interface moves along cell
boundaries (with high Ti, Mo), the interface moves in a massive manner with only slight element redistribution. When the
austenite-martensite interface moves towards regions with the bulk composition, the interface migration is sluggish accompanied
with notable element partitioning.
References
1) Y.M. Wang, T. Voisin, J.T. McKeown, J. Ye, N.P. Calta, Z. Li, Z. Zeng, Y. Zhang, W. Chen, T.T. Roehling, R.T. Ott, M.K. Santala,
P.J. Depond, M.J. Matthews, A.V. Hamza and T. Zhu, Nat Mater 17(1) (2018) 63-71.
2) K.M. Bertsch, G. Meric de Bellefon, B. Kuehl and D.J. Thoma, Acta Materialia 199 (2020) 19-33.
3) T. Voisin, J.-B. Forien, A. Perron, S. Aubry, N. Bertin, A. Samanta, A. Baker and Y.M. Wang, Acta Materialia 203 (2021).
4) J. Wu, X.Q. Wang, W. Wang, M.M. Attallah, M.H. Loretto and Acta Materialia 117 (2016) 311-320.
5) Z.W. Chen, M.A.L. Phan and K. Darvish, Journal of Materials Science 52(12) (2017) 7415-7427.

Enhanced carbon enrichment in austenite through introducing pre-existing austenite as a
‘carbon container’ in 0.2C-2Mn steel: the significant impact on microstructure and
mechanical properties
B. Hu 1, H. Guo 1, *, R.D.K. Misra 2, C.J. Shang 1
1
Collaborative Innovation Center of Steel Technology, University of Science and Technology Beijing, Beijing 100083, China
2
Laboratory for Excellence in Advanced Steel Research, Department of Metallurgical, Materials and Biomedical Engineering,
University of Texas at El Paso, TX 79968, USA
*email: guohui@mater.ustb.edu.cn
Keywords: Pre-annealing, Cementite, Austenite stability, Microstructure
Multi-step intercritical heat treatment has been introduced in low carbon low manganese steels in some studies to obtain
a considerable amount of stable retained austenite and enhance mechanical properties 1,2). Retained austenite is usually
introduced in microstructure 2) when the sample is subjected to the first intercritical annealing which was also called
pre-annealing 3). It was reported that the amount of cementite precipitated during heating was reduced when retained austenite
was a constituent of the initial microstructure 4,5). However, the underlying reason continues to be unclear to the best of our
knowledge. The objective of the present study is to elucidate the precipitation and dissolution of cementite during annealing
when the initial microstructure with or without retained austenite was introduced as a constituent by pre-annealing. The
microstructure evolution during the heat treatment and the change of the stability of retained austenite will also be
investigated.
The chemical composition of experimental steel is 0.2C -2.18Mn -1.01Ni -0.91Cu -1.11Al -0.58Si -0.032Nb -0.255Mo.
The steel was melted in a vacuum induction furnace and forged into ingots with a thickness of 80 mm. The ingot was
homogenized at 1200˚C for 2 h in a muffle furnace, and then hot rolled to 12 mm plate followed by quenching to room
temperature. The Ac1 and Ac3 temperatures of experimental steel were determined to be 680˚C and 874˚C, respectively, by
using thermal dilatometer (DIL805A). In the present study, two types of heat treatment process were carried out. In type I,
samples were intercritically annealed at 690˚C for 30 min, 60 min and 120 min, respectively, and then air cooled to room
temperature, which were referred henceforth as IA30, IA60, and IA120, respectively. In type II, the sample was first
pre-annealed at 740˚C for 30 min and quenched to room temperature, referred as sample P. Then, sample P was annealed at
690˚C for 30 min and cooled to room temperature in air, labeled as P-IA30. Microstructure was observed by scanning
electron microscope (ZEISS ULTRA-55, SEM) at an accelerated voltage of 15 kV and transmission electron microscope
(FEI F20, TEM) equipped with an energy dispersive X-ray spectroscopy at an acceleration voltage of 200 kV. Specimens for
SEM observations were mechanically polished and etched by 3% nital solution. Specimens for TEM observations were
mechanically ground to 50 μm and punched into small disks of 3 mm diameter. Then, small disks were electropolished using
a solution of 5% perchloric acid and 95% ethanol (in vol.) at a voltage of 22 V and a temperature of -25˚C. The size and
distribution of retained austenite were studied by electron back scatter diffraction (EBSD) at an acceleration voltage of 20 kV
and a step size of 50 nm. Specimens for EBSD observation were mechanically polished and electro-polished using a mixed
solution of 85% ethanol, 10% perchloric acid and 5% glycerine (in vol.) at 20 V for 15 s to remove the mechanically damaged
surface layer. HKL Channel 5 software was used to process the EBSD data.
The microstructure of hot rolled sample was martensite, while the microstructure of sample P was composed of ferrite,
martensite and retained austenite. The statistical analysis indicated that the width of reversed austenite was 300 ± 97 nm. The
reversed austenite formed at 740˚C was not stable and partly transformed into martensite. The XRD results showed that the
volume fraction of retained austenite in sample P was about 8%, while retained austenite could be hardly detected in hot rolled
sample. Microstructure of samples subjected to different heat treatments characterized by SEM is presented in Fig. 1.
According to previous analysis, the microstructure of sample IA30 was composed of reversed austenite and ferrite, as shown
in Fig. 1a. Both granular and lath-like reversed austenite were observed. There were a number of small particles of size
ranging from ~50-100 nm dispersed in the matrix, which are considered as cementite based on previous studies 5,6). With the
increase of annealing time, the size of reversed phase increased and the fraction of cementite decreased. After annealing for
120 min, cementite was hardly observed in the microstructure. The microstructure of sample P-IA30 was mainly comprised
of reversed austenite and ferrite. Majority of reversed austenite was lath-like or small rod-like and very few cementite particles

were observed in sample P-IA30, which was significantly different from the sample IA30. This means that pre-annealing may
influence cementite precipitation during the subsequent heat treatment.
Band contrast images with retained austenite and cementite in samples subjected to different heat treatments were
compared. With the increase of annealing time, the volume fraction of retained austenite increased. Sample P-IA30 had least
volume fraction of retained austenite, according to the EBSD results. The equivalent diameter distribution of retained austenite
was counted. The grain size of retained austenite increased from 335 nm to 408 nm with the increase of annealing time from
30 min to 120 min. The grain size of retained austenite in sample P-IA30 was slightly smaller than that in sample IA30. The
volume fraction of retained austenite was quantitatively analyzed by XRD. The pre-annealing process slightly increased the
volume fraction of retained austenite compared to the sample only annealed at 690˚C for 30 min. Cementite particles were
observed in sample IA30 under TEM and TEM-EDS measurement showed that Mn content of these particles was up to 15.0
± 0.7 wt.%, which was close to the Mn content in cementite calculated by Thermo-Calc (15.5 wt.%) and significantly greater
than that in retained austenite. The number of cementite particles in sample P-IA30 was significantly less compared to sample
IA30 based on SEM and TEM studies. TEM-EDS results showed that there was almost no difference in elemental
concentration in retained austenite in the two samples.
The lattice parameter of austenite or ferrite can be calculated from the equation (1):
(1)
where λ (=0.15418 nm) is the wave length of X-ray, θ is the diffraction angle of (hkl) peak. The carbon concentration in
austenite can be calculated by equation (2):
(2)
where the atomic symbols represent the concentration of carbon and alloying elements in austenite in weight percent. Mn and
Ni concentration in austenite were measured by TEM-EDS, while the Si, Al and Cu content in austenite were given by
Thermo-Calc simulation results. No Mo was detected in austenite based on TEM-EDS results. The carbon concentration in
austenite calculated based on above equations were 0.57 wt.% for sample IA30 and 0.68 wt.% for sample P-IA30,
respectively. The carbon concentration in ferrite was calculated using equations (3) and (4):
(3)
(4)
where xMn and xC are weight percent of Mn and carbon in ferrite, respectively. The calculated Mn concentration in ferrite was
1.31 wt.% in sample IA30 and 1.34 wt.% in sample P-IA30, respectively. The carbon concentration in ferrite was calculated
to be 0.011 wt.% for sample IA30 and 0.014 wt.% for sample P-IA30, respectively. The total mass fraction of carbon enriched
in austenite were 0.110 wt.% for sample IA30 and 0.156 wt.% for sample P-IA30, respectively, which indicated that
pre-annealing was beneficial for carbon enrichment in austenite.
In order to verify whether cementite precipitated in this study during the heating period, a sample was heated to 690˚C
and then quenched to room temperature without isothermal holding. The microstructure of this sample is presented in Fig. 2.
A number of cementite particles were observed along the lath boundaries and within the martensite lath. It is reasonable to
believe that cementite precipitated during heating the sample to 690˚C in this study, which did not dissolve completely even
after annealing for 30 minutes at this temperature. And dilatometric curve showed that cementite formed at ~450˚C during
heating at a heating rate of 10 ˚C/s. TEM-EDS results showed that Mn concentration in cementite was ~10.1 ± 3.2 wt.%,
which was lower than that of sample IA30. Given that the cementite can rapidly grow during heating, which is driven by rapid
partitioning of carbon from martensite into cementite, then Mn would further partition from martensite into cementite during
the early stage of annealing. With the increase of annealing time, cementite dissolves and is accompanied by austenite
formation due to thermodynamic constraint. The austenite stability can be assessed by martensite transformation temperature
(MS). MS of samples IA30, IA60, IA120 and P-IA30 was calculated to be 28˚C, 15˚C, 50˚C and -14˚C, respectively. It is
reasonable to conclude that the retained austenite in sample P-IA30 has a higher stability, which may result in a sustained

TRIP effect to enhance the ductility which is proved by the mechanical property test.
In summary, the reversed austenite obtained by pre-annealing acted as a “carbon container”, and received carbon from
cementite dissolved during pre-annealing. The reversed austenite was partly retained at room temperature and the retained
austenite could further absorb carbon from martensite. As a result, the precipitation of cementite was significantly reduced
during subsequent intercritical annealing and austenite was enriched with more carbon compared to the situation without
pre-annealing. In addition, the size of retained austenite was refined by pre-annealing, which enhanced the stability of
austenite and contributed to superior ductility of steel.
Acknowledgement
This research was funded by the Key Research and Development Program of Shandong Province, China (No. 2019JZZY020238).
References
1) Z.J. Xie, S.F. Yuan, W.H. Zhou, J.R. Yang, H. Guo, C.J. Shang, Materials & Design 59 (2014) 193-198.
2) W. Zhou, H. Guo, Z. Xie, X. Wang, C. Shang, Materials Science and Engineering: A 587 (2013) 365-371.
3) D.T. Han, Y.B. Xu, F. Peng, Y. Zou, R.D.K. Misra, Journal of Materials Science 55(10) (2019) 4437-4452.
4) N. Yan, H. Di, R.D.K. Misra, H. Huang, Y. Li, Materials Science and Engineering: A 753 (2019) 11-21.
5) X.L. Wang, Z.Q. Wang, A.R. Huang, J.L. Wang, X.C. Li, S.V. Subramanian, C.J. Shang, Z.J. Xie, Materials Characterization 169
(2020).
6) X. Zhang, G. Miyamoto, Y. Toji, S. Nambu, T. Koseki, T. Furuhara, Acta Materialia 144 (2018) 601-612.
Fig. 1. SEM micrographs of (a) IA30, (b) IA60, (c) IA120 and (d) P-IA30 samples.

Fig. 2. Microstructure of quenched sample after heating to 690˚C. (a) SEM micrograph, (b) TEM
micrograph.

Heterogeneity driven enhanced tensile properties in martensitic steels
Ji Hoon Kim1 , Guiyoung Gu1, Seok Hwan Hong1, Minseo Koo2, Eun-Young Kim2 and Dong-Woo Suh1,*
1
Graduate Institute of Ferrous and Energy Materials Technology, POSTECH, 37673 Korea
2
Technical Research Laboratories, POSCO, Gwangyang, 57807 Korea
*email: dongwoo1@postech.ac.kr
Keywords: steel, heterogeneity, tensile property, austenite, martensite
Heterogeneity attracts a deep interests as an alternative concept for microstructure control in structural materials1). It is because,
the heterogeneous microstructure, if precisely controlled, can present extraordinary properties which are difficult to be
expected in conventional monolithic microstructure. The advantages in structural properties led by heterogeneity is believed to
be driven by synergetic effect of mixed domains with dissimilar characteristics. In that sense, combining more than one
heterogeneous characteristics can open a high chance for the development of steels having mutually exclusive properties. In
the present study, we attempted to disclose the influence of chemical heterogeneity in dissimilar microstructure scale in
martensitic steel. It revealed that the combined heterogeneity in chemistry and size can contribute to the enhanced
combination of strength and ductility in martensitic steel, compared to that in conventional one. Detailed analysis on the effect
of chemical heterogeneity in micro and nano-scale demonstrates the importance of sophisticated control of heterogeneity in
various microstructure scales for the development of innovative structural materials.
Chemical composition of investigated alloy was 0.18 wt.% C based low carbon steel. First intercritical annealing at a
temperature, where ferrite, austenite and cementite coexist, created a multi-scale chemical hegerogeneity of Mn distribution
thanks to the dissimilar Mn solubility in each phase. Then second annealing was conducted for austenitization, which
generated martensitic microstructure with micro-scale and nano-scale heterogeneities, resided in the Mn-enriched region
originating from the initial austenite and cementite. Microstructure characterization was conducted by using a SEM with
EBSD and TEM observations and austenite fraction was evaluated by using magnetic saturation method. Tensile test was
performed to examine the influence of heterogeneity-driven characteristic microstructure on the mechanical properties of
martensite.
Fig. 1 illustrates a schematic diagram of the microstructure evolution during the two-step heat treatment for the generation
multi-scale heterogeneity of Mn distribution, compared with the conventional heat treatment to generate martensitic
microstructure. Intercritical annealing successfully introduced multi-scale heterogeneous Mn distribution (Fig. 2), which ends
up with characteristic features in the final microstructure.
Fig. 1 Schematic diagram of microstructure evolution during the heat treatment

Fig. 2 Multi-scale heterogeneity of Mn evolved after intercritical annealing 2)
Micro-scale heterogeneity before the second annealing resulted in soft and hard region in the martensitic microstructure led by
difference solid solution hardening effect of Mn, which produced strain partitioning and back stress, promoting the strength of
steel. On the other hand, the nano-scale heterogeneity generated the tiny austenite particles after the second annealing, of
which extraordinary stability provided a persistent work hardening by TRIP effect, contributing improvement of ductility. It
made it possible to achieve the simultaneous improvement of tensile strength and ductility in martensitic steel, which have
been regarded as mutually exclusive properties (Fig. 3).
Fig. 3 Influence of chemical heterogeneity of Mn on tensile behaviors and work hardening 2)
Acknowledgement
This work was performed under the support of POSCO
References
1) X. Wu, M. Yang, F. Yuan, G. Wu, Y. Wei, X. Huang and Y. Zhu: PNAS 112 (2015) 14501-14505.
2) J. H. Kim, G. Gu, M.H. Kwon, M. Koo, E. Y. Kim, J. K. Kim, J. S. Lee and D. W. Suh: Acta Mater. 201 (2022) 117506.

First-principles calculation of the atomic interaction and tetragonality in an Fe-C system
Hideyuki Ohtsuka1,* and Kaneaki Tsuzaki2
1
Cryogenic Center for Liquid Hydrogen and Materials Science, National Institute for Materials Science,
Tsukuba, Ibaraki 305-0047, Japan
2
*email: ohtsuka.hideyuki@nims.go.jp
Keywords: first-principles calculation, atomic interaction, tetragonality, martensite, Fe-C interaction, C-C interaction
1. Introduction
The atomic interaction affects the microstructures and mechanical properties of materials. One of the most important factors that
has an influence on the atomic interaction is the chemical bonding between atoms. Whether bonding or antibonding is formed
between atoms determines the attractive or repulsive interaction between the atoms. Tetragonality is closely related with the
atomic interaction and is one of the most important research topics of Fe-C martensite, which is a vital microstructure of high-
strength steels. Many researches have been conducted for the tetragonality of Fe-C martensite[1]. In spite of these researches, we
still have some unsolved issues, such as, how alloying elements affect the tetragonality, how carbon configuration affects the
tetragonality and total energy, and what is the atomic interactions in Fe-C systems. In this study, the total energy for various Fe-C
systems is evaluated by the first-principles calculation and the tetragonality value is determined. The dependence of energy on
the configuration of carbon atoms is investigated and the effects of Al, Ni and Mn addition on the tetragonality of Fe-C martensite
are calculated. The degree of bonding and antibonding between Fe-C and C-C interactions is evaluated, and based on these
calculation results, the origin of atomic interactions in Fe-C system is discussed.
2. Calculation
The plane-wave base Vienna Ab-initio Simulation Package (VASP) with the pseudo potential method was used for the
calculation[2,3]. The density functional theory was applied using the projector-augmented wave (PAW) method based on the
generalized density gradient approximation (GGA-PBE) with spin polarization. Three kinds of supercells, a 2 × 2 × 2 supercell
with 15 Fe atoms and 1 substitutional atom (Al, Ni or Mn) and 1 interstitial carbon (k-point mesh is 8 × 8 × 8), a 3 × 3 × 3 supercell
with 54 Fe atoms and 1 or 2 interstitial carbon atoms (k-point mesh is 6 × 6 × 6) and 4× 4 × 4 (k-point mesh is 4× 4 × 4 ) supercell
with 128Fe atoms and 1 interstitial carbon atom were used for the calculation. These supercells are abbreviated as Fe15M1C1 (M=
Al, Ni or Mn), Fe54C1, Fe54C2, Fe128C1, respectively. The cut-off energy is 400 eV. Both the shape and size of the supercell are
varied during calculation. The degree of bonding and antibonding was quantitatively evaluated by COHP (Crystal Orbital
Hamilton Population) analysis using the software “LOBSTER”[4,5].
3.Results and discussion

The tetragonality of martensite in Fe-C alloys has been measured experimentally in a large number of studies and a considerable
amount of data clearly indicates that the tetragonality is proportional to the carbon content. In order to confirm that the first-
principles calculation can reproduce these data, the tetragonality of Fe-C is calculated in supercells with three different carbon
content, such as Fe54C1, Fe128C1 and Fe54C2. The total energy and tetragonality were calculated for these supercells, the structure
with minimum energy was obtained and its tetragonality was accepted as the calculated tetragonality value. The calculated
tetragonality agrees very well with the experimental value. Here, the first two supercells contain a single carbon atom only and
all the octahedral sites have the same energy and the tetragonality can be uniquely determined. However, the last supercell contains
two carbon atoms and the total energy differs according to the carbon atom configuration. In order to determine the tetragonality
value of Fe54C2 system, the total energy and tetragonality value were calculated for all the carbon atom configurations. Figure 1
[6] shows the formation enthalpy for Fe54C2 as a function of the distance between two carbon atoms. The number in parentheses

indicates that the symbol represents that number of data points, but it
is presented as a single point on this figure. The formation enthalpy is
quite high when the C-Fe-C structure is formed (open triangle), or two
carbon atoms are at the first or second nearest neighbor position with
each other. The solid circle in the far right corresponds to the
minimum energy position which shows that the tetragonality value
for Fe54C2 is 1.036. In Fig.1, a clear boundary can be seen between the
open and solid circles (broken line). When the energy is over 18.3
meV/atom, the tetragonality is approximately 0.981 (open mark) and,
when it is less than this value, the tetragonality is approximately 1.036,
(solid mark) which agrees well with the experimental data. The
existence probability under the assumption of a Boltzmann
Fig.1 Formation enthalpy for Fe54C2 as a function of distribution is calculated and is high in this case. In other cases, the
distance between two carbon atoms. Open circles: formation enthalpy is relatively high and the existence probability is
c/a=0.981, solid circles: c/a=1.036, open triangle: c/a = almost zero. For the open marks, the Fe-C-Fe pair, which is
1.090. The solid and open symbols are in the relatively composed of a carbon atom and its two nearest neighbor Fe atoms, is
lower and higher energy regions, respectively, and the perpendicular to the second Fe-C-Fe pair. On the other hand, for the
arrows indicate exceptional cases. The numbers in solid marks, the first Fe-C-Fe pair is parallel to the second pair. This
parentheses indicate that a single symbol includes that parallel configuration shows the ordering of carbon atoms at c axis in
number of data points[6]. Fe-C martensite. The effect of alloying elements on tetragonality was
studied, and the calculation shows that addition of Al and Ni increases
but Mn decreases the tetragonality value. The strain energy, which is the difference between the energies of distorted Fe54C1
system and undistorted Fe54C1 systems, is calculated. It was shown that the strain energy is very high when two carbon atoms are
in the first nearest neighbour sites with each other and carbon atoms have a strong repulsive interaction. This has been reported in
the previous papers, but other than the strain energy, the chemical bonding between carbon atoms is very important. From the
analysis of chemical bonding between atoms in Fe-C system using the software LOBSTER, it was found that bonding is formed
between Fe and C atoms. On the other hand, antibonding is formed between C atoms. It is considered that C-C interaction is
repulsive and this is confirmed from the high formation energy of Fe-C system in which C atoms are at the nearest neighbor site
with each other. This strong repulsion is considered to be due to the strain energy and the antibonding between C atoms.
4. Summary
The total energy and tetragonality of Fe-C systems have been evaluated using the first-principles calculation and the effects of
carbon configuration on the total energy and tetragonality have been discussed based on the atomic interaction. The tetragonality
of the Fe-C system obtained from the first-principles calculation agrees well with the experimental results. When the Fe-C-Fe
pairs are parallel, the calculated tetragonality value becomes large and agrees with the experimental value. Al or Ni increases and
Mn decreases the tetragonality. The bonding is formed between Fe and C atoms, but the antibonding is formed between C atoms.
This antibonding is the one of the reasons why the C-C interaction is repulsive.
REFERENCES
[1] H.Ohtsuka and K.Tsuzaki: ISIJ International, 61(2021), 2677-2686.
[2] G.Kresse and J.Furthmuller: Phys. Rev., B54(1996), 11169-11186.
[3] G.Kress and D.Joubert: Phys. Rev., 59(1999), 1758-1775.
[4] R.Dronskowski and P.E.Bl Ö chl: J. Phys. Chem., 97(1993), 8617.
[5] S. Maintz, V. L. Deringer, A. L. Tchougreeff, R. Dronskowski: J. Comput. Chem., 34(2013), 2557.
[6] H.Ohtsuka, V. A. Dinh, T. Ohno, K. Tsuzaki, K. Tsuchiya, R. Sahara, H. Kitazawa and T. Nakamura et al.:
ISIJ International, 55(2015), 2483-2491.

Investigating the formation of bainite in the presence of martensite
Maria J. Santofimia1,*, Alfonso Navarro López1, Ashwath M. Ravi1-2, Daniel dos Santos Avila1, Sharmistha Dhara1,
Javier Hidalgo Garcia1, Stefan van Bohemen2, Jilt Sietsma1
1
Department of Materials Science and Engineering, Delft University of Technology, 2628CD Delft, The Netherlands
2
Tata Steel Research Development and Technology, 1970 CA IJmuiden, The Netherlands
*email: M.J.SantofimiaNavarro@tudelft.nl
Keywords: steel, microstructure, martensite, bainite.
Multiphase microstructures combining a strong phase such as martensite and bainite, with the more ductile retained
austenite, are key for the simultaneous increase of strength and ductility in advanced high strength steels. Steels combining bainite
and retained austenite can be produced through austenitisation followed by an isothermal treatment at a temperature in the bainitic
range. Alloying with silicon, with a low solubility in cementite, prevents that the carbon diffusion into the austenite during bainite
formation leads to significant carbide precipitation. Instead, austenite becomes rich in carbon and (meta)stable at room
temperature. Steels with higher hardenability can lead to combinations of martensite and retained austenite through the quenching
and partitioning process, in which an austenitic microstructure is partially transformed into martensite, while further annealing
leads to the partitioning of carbon from martensite to austenite. Also in this case, the carbon enriched austenite remains
(meta)stable at room temperature.
Investigations on the quenching and partitioning process showed that, in some alloys, the process of carbon partitioning
can be affected by the formation of bainite. Both processes (carbon partitioning from martensite and bainite formation) lead to
carbon enrichment of the austenite, although only the second leads to a significant change on the volume fractions of phases in
the microstructure. Further investigations showed that bainite formation seemed promoted and even accelerated by the presence
of martensite, when compared with bainite kinetics at the same conditions but in absence of martensite [1-3]. Moreover, bainite
can even form isothermally below the martensite start temperature [4]. Literature showed that these were not new observations,
and that the acceleration of bainite kinetics in the presence of martensite was considered a “well stablished phenomenon” already
in the year 1959 [5].
The present work presents ten years of investigations on the formation of bainite in the presence of martensite at the
University of Delft. The main aim of this research was the application of this phenomenon for the development of new advanced
high strength steels through shortened processing routes presenting controlled combinations of martensite, bainite and retained
austenite. This implied investigations at the level of microstructural characterisation, microstructure control and modelling, and
analysis of mechanical properties.
Investigated steels were composed in its majority by 0.2 C-3.5Mn-1.5Si (in wt.%), with different additions of Mo and
Al, among other elements. Heat treatments were applied with a Bähr 805A dilatometer. Thermal treatments included full
austenitisation followed by the formation of bainite in presence of different fractions of martensite. The analysis of the dilatometry
curves allowed the identification of an increase in the nucleation rate of bainite in presence of martensite at the very initial stages
of the transformation [6]. The identification of martensite and bainite after the application of this type of heat treatments is difficult
[7-8], due to the partial tempering of martensite during the isothermal treatment, which makes it resemble as bainite in the final
microstructure. However, some specific features belonging to bainite or martensite were identified [9]. Figure 1 displays a
microstructure isothermally formed below the martensite start temperature in a low carbon steel.
Modelling the formation of bainite in presence of martensite requires good understanding of bainite formation.
However, the nature of the bainitic transformation is still a topic of much discussion in the scientific community. Nevertheless,
the displacive approach has been proved to efficiently predict the kinetics of bainite formation in low carbon steels at relatively
low temperatures. This approach assumes that bainite formation is controlled by the successive displacive nucleation of individual
bainitic subunits, while carbon partitioning into the surrounding austenite occurs soon afterwards. Based on this approach, Ravi
et al. [10] developed a kinetic model for the kinetics of bainite formation able to distinguish nucleation at austenite grain
boundaries and at bainite/austenite interfaces. In Ravi et al. [11], the mentioned model was applied to elucidate the influence of
martensite presence on bainite kinetics by also introducing the role of martensite/austenite interfaces as possible nucleation sites.

The overall bainite formation rate at a given moment in presence of pre-existing martensite is modelled as:
𝑑𝑓 𝑑𝑓 𝑑𝑓 𝑑𝑓
𝑑𝑡
= ( 𝑑𝑡 ) + ( 𝑑𝑡 ) + ( 𝑑𝑡 ) ,
𝑀 𝐺 𝐴
where (df/dt)M gives the rate of bainite formation due to nucleation at martensite/austenite interfaces, (df/dt)G gives the rate of
bainite formation due to nucleation at austenite grain boundaries and (df/dt)A gives the rate of autocalaytic bainite formation.
Figure 1. Microstructure of a low carbon steel alloyed with 1.5 wt.% Si after bainite formation below the martensite start
temperature: (a) scanning electron micro micrograph. (b-c) electron backscatter diffraction analysis of one prior austenite
grain from the location shown in (a). Specifically: (b) inverse pole figure map (only BCC structure), (c) phase distribution
map (BCC: green; FCC: red), and (d) kernel average misorientation map.
Comparison with experiments showed that the formation of bainite at martensite/austenite interfaces facilitates further
bainite nucleation by the creation of new bainite/austenite interfaces, being this influence dependent on the fraction of pre-existing
martensite. Further, the overall rate of bainite formation was found to quickly decrease as the available martensite/austenite
interfaces are consumed and carbon enrichment of austenite increases due to carbon partitioning from martensite to austenite.
The influence of the pre-existing martensite on the mechanical properties of steels developed by this approach was
found to depend on its phase fraction and tempering degree [12]. In general, the prior formation of martensite leads to an increase
in strength due to the refinement of the resulting microstructure and the presence of carbon in solid solution. However, relatively
long isothermal treatments lead to an increase on the bainite fraction but also to the tempering of the pre-existing martensite. In
this case, the microstructures display a lower strain hardening, possibly due to softening of the pre-existing martensite due to
carbon segregation (reduction of tensile strength) and the presence of carbide precipitation (increase of yield strength). Further
investigations have demonstrated that steels in which bainite has been formed in presence of a small fraction of martensite (less
than 0.05) can lead to similar strength and ductility combinations than in absence of pre-existing martensite, while the addition of
pre-existing martensite has the advantage of significantly reducing the whole processing time [13].
The presented investigations helped to clarify the effect of the presence of martensite on the kinetics of bainite
formation, and contributed to the industrial applicability of this phenomenon for the development of new advanced high strength
steels. However, some fundamental questions remain unanswered. One of them is what is the specific mechanisms leading to the
observed acceleration of bainite kinetics. Although its relation with the introduced martensite/austenite interfaces in the system is
clear, the question whether bainite nucleation is induced by the interface itself or by the dislocations next to it remains.
Acknowledgement
This work has been performed in the framework of several projects. Firstly, under the support of Netherlands Organization for Scientific
Research (NWO) and the Dutch Foundation for Applied Sciences (STW) through the VIDI-Grant 12376, and under the support of the
European Research Council under the European Union’s Seventh Framework Programme (FP/2007–2013)/ERC Grant Agreement n.
[306292]. Currently, this topic is being further investigated under the support of the National PPS-HTSM Program and of the Research
Fund for Coal and Steel for funding this research under the contract RFCS-02-2019 (Project No. 899251).

References
1) W. Gong, . Tomota, S. Harjo, Y. H. Sua and K. Aizawa, Acta Materialia 85 (2015) 243
2) H. Kawata, K. Hayashi, N. Sugiura, N. Yoshinaga and M. Takahashi, Materials Science Forum 638-642 (2010) 3307
3) Y. Toji, H. Matsuda and D. Raabe, Acta Materialia 116 (2016) 250
4) S. M. C. van Bohemen, M. J. Santofimia and J. Sietsma, Scripta Materialia 58 (2008) 488
5) S. Radcliffe, E. Rollason, J. Iron Steel Inst. 191 (1959) 56
6) A. Navarro-Lopez, J. Sietsma and M. J. Santofimia, Metallurgical and Materials Transactions A 47 (2016) 1028
7) D. Kim, J. G. Speer and B. C. De Cooman, Metallurgical and Materials Transactions A 42 (2011)1575
8) S. Samanta, P. Biswas, S. Giri, S. B. Singh and S. Kundu, Acta Materialia 105 (2016) 390
9) A. Navarro-Lopez, J. Hidalgo-Garcia, J. Sietsma and M. J. Santofimia, Materials Characterization 128 (2017) 248
10) A. M. Ravi, J. Sietsma and M. J. Santofimia, Acta Materialia 105 (2016) 155
11) A. M. Ravi, A. Navarro-Lopez, J. Sietsma and M. J. Santofimia, Acta Materialia 188 (2020) 1
12) A. Navarro-Lopez, J. Hidalgo-Garcia, J. Sietsma and M. J. Santofimia, Materials Science & Engineering A 735 (2018) 343
13) A. Navarro-Lopez, J. Hidalgo-Garcia, J. Sietsma and M. J. Santofimia, Materials and Design 188 (2020) 108484

Negative strain rate sensitivity in steels
Mingxin Huang, Chengpeng Huang

Department of Mechanical Engineering, The University of Hong Kong
Abstract:
Understanding the deformation behavior of metals over a wide range of strain rates is of critical
importance in a variety of engineering applications, such as vehicle collision, projectile penetration,
explosion shock, and so on. Decades ago, studies on the strain rate dependent deformation behavior
of various metals, including bcc metals (e.g. Pure Iron), fcc metals (e.g. Copper, Nickel), and hcp
metals (e.g. Titanium), were reported, and the results show that all of these metals exhibit positive
strain rate sensitivity. Here, we investigated the strain rate dependent mechanical behavior of several
steels, including bcc steels (e.g. IF steel and PHS steel), fcc steels (e.g. TWIP steel and 316L steel),
and multiphase steels (e.g. Q&P steel and medium Mn steel). We found that the strain rate dependent
deformation behavior of most of these steels differs from that of the pure metals previously mentioned,
which exhibits abnormally negative strain rate sensitivity. The underlying mechanism has been
extensively investigated. This discovery will have a significant impact on the use of steels as structural
materials in components that are likely to be subjected to high strain rate impact, such as automobile
anti-collision beams.

Near atomic-scale comparison of passive film
on a high-Cr high-Mn steel with those on typical stainless steels
Jae-Bok Seol1) 2), Kwang-Kyu Ko1) 2), Hyo-Ju Bae1) 2),

Muhammad Ishtiaq1) 3), Hyo-Kyung Sung1) 2), Jung-Gi Kim1) 2)
1) Center for K-metal

2) Gyeongsang national university
3) University of the Punjab
Abstract:
The structural and chemical features of passive films formed on a high Cr-added high-Mn (18 wt%)
twinning-induced plasticity (TWIP) steel and 304L, 316L austenitic stainless steels, i.e., 304L, 316L,
were revealed using Cs-corrected scanning transmission electron microscopy (STEM) and atom probe
tomography (APT). Based on these results, we investigated the cause of lower passive ability of the
high Cr-added TWIP steel than the typical stainless steels. Moreover, based on the chemical difference
of passive films between the 316L and the 304L, we suggested the primary cause of the improved
pitting resistance of 316L than 304L.
To increase the corrosion resistance of typical high-Mn TWIP steel series, high amount of Cr (17wt%)
was added to typical 18 (wt%) TWIP steel, i.e., HCr-HMnS. When comparing the passive abilities of
the HCr-HMnS, 304L and 316L by potentiodynamic polarization curves, the thickness and chemical
compositions of the material passivation films were performed via Cr-corrected STEM and APT.
Although the passive films of all the samples with similar Cr concentrations had the same thickness,
unprecedented hexagonal wurtzite MnO inside the passive film of HCr-HMnS specimen was
susceptible to corrosion cracking; this was not observed in the passive films of typical stainless steels.
This MnO caused crack formation during potentiodynamic polarization test, suggesting that reducing
the harmful MnO by adding Mo and Ni facilitates the development of high-Mn base stainless steels.
Furthermore, higher MoO2 composition of the passive films on 316L than 304L might would result
in primarily the improved pitting resistance. We propose that Mo and Ni, which can reduce the MnO-
density, may be beneficial for developing high-Mn base stainless steels..

MECHANICAL PROPERTUES of SINGLE VARIANT MARTENSITE from FERRITE
+ Mn-RICH CEMENTITE STRUCTURE in 0.1C-2Si-5Mn STEELS
Shiro Torizuka*, Oya Ryusuke, Yusuke Suzuki and Atsushi It
1
Graduate School of Engineering, University of Hyogo, Himeji, Hyogo 671-2210, Japan
*email: torizuka@eng.u-hyogo.ac.jp
Keywords: steel, Mn, martensite, ferrite, cementite, ultrafine, variant
1. INTRODUCTION
Microstructure of martensite contains packets, blocks, and laths. The structure consisting of several packets and many blocks
with various orientations (variants) are usually transformed from one of the prior austenite (γ) grains. Martensite with single-
packet and multi-block structure is formed when the prior austenite grain becomes fine. Further refinement in the austenite grain
size results in the formation of single-block (single-variant) martensite. In this study, we examined the structure and mechanical
properties of the martensite formed from various grain size prior γ obtained from ultrafine ferrite + Mn rich cementite steels with
the chemical composition of 0.1-0.2%C-2%Si-5-7%Mn. Particularly, the purpose of this study is to form a single-variant
martensite with a reduction in the prior γ grain size and to investigate the mechanical properties of the single-variant martensite1).
2. EXPERIMENTAL
First, a 20 kg ingot of steels were prepared by vacuum-melting with the chemical composition of 0.1-
0.2%C-2%Si-5-7%Mn . Subsequently, the ingots sample were subjected to hot forging at 1200 °C.
Then, multi-pass warm caliber-rolling was performed at 550℃. The resulting structure was an
ultrafine ferrite + MN rich cementite structure. Second, these bars with ferrite + Mn rich cementite
structure were heated and soaked at 700, 750, 800, 900, and 1200 °C for 1 h and air
Fig. 2 Single variant
cooled. Variant analysis was carried out to the microstructures obseved by EBSD to martensite in 0.1C-2Si-5%Mn
clear the prior austenite gtain size. Transmission X-ray diffraction (XRD) experiments steels heat treated at 750 ℃1).
on 0.5-mm-thick specimens were carried out using the synchrotron radiation
facility at SPring-8. A quantitative analysis of the retained  was carried out
using the results.
3. RESULTS AND DISCUSSION

Figure 1 shows ultrafime martensite structure in 0.1C-2.0Si-5.0%Mn steels
obtained by annealing at 750 ℃. Variant analysis revealed that the grain (★)
was a single variant martensite1).
Figure 2 shows the tensile strength increased from 1270 MPa to 1500 Fig. 2 Nominal stress-strain curves of
MPa, and the uniform elongation increased gradually from 6.2 to 0.1C-2Si-5%Mn steels heat treated at
7.1%, with a decrease in the heat-treatment temperature from 1200°C 700, 750, 800, 900 and 1200℃1).
to 750°C1). In the case of the sample heat-treated at 750°C, the
strength-ductility balance was found to be 10600 MPa%. Both the strength and uniform elongation improved
simultaneously with a decrease in the heat treatment te mperature from 1200°C to 750°C. Reduction in prior
γ grain size from about 150 μm to 2 μm resulted in an improvement in the strength-ductility balance from
about 8,000 MPa % to to 10,000 MPa%. The single-variant martensite has better mechanical properties than
that of usual martensite.
Acknowledgement
This work was performed under the support of SIP Project.
References
1. Shiro Torizuka, Ryusuke Oya, Kartik Prasad, and Atsushi Ito, Materials Performance annd Characterization,
DOI: 10.1520/MPC20200187.

Delamination in wire-drawn pearlitic steels
Masaki Tanaka1,2,*, Toshiyuki Manabe3, Tatsuya Morikawa1, Shigeto Yamasaki1
1
Department of Materials, Kyushu University, Fukuoka 819-0395, Japan
2
Center for Elements Strategy Initiative for Structural Materials, Kyoto University, Kyoto 606-8581, Japan
3
Technical Research & Development Bureau, Nippon Steel Corporation, Kitakyushu, Fukuoka 804−0001, Japan
*email: tanaka.masaki.760@m.kyushu-u.ac.jp
Keywords: wire-drawing, pearlite, cementite, lamellae, fracture
Pearlite exhibits a lamellar structure comprising alternating layers of ferrite and cementite. In the wire manufacturing
process, the widths of the cementite lamellae are gradually reduced, resulting in heteronanostructures on the submicron scale. The
increase in strength obtained during the wire-manufacturing process is explained by the decrease in the lamellar spacing, which
occurs as the wire is drawn[2]. Wire-drawn pearlitic steels have high strength and resistance to delayed fractures[3]; however,
they experience delamination—a type of vertical cracking—during torsion tests. A delamination mechanism has not been
definitively identified, although controlling factors have been suggested. Therefore, the mechanisms underlying the delamination
are discussed in this paper, with a focus on the plastic-deformation capability of ferrite in the pearlite structure.
Factory-produced piano wires were employed as a testing material (SWRS82B). After hot rolling, the diameter of the wires
was reduced to 9 mm. The wires were then kept in a tubular furnace at 1223 K for 240 s and then subjected to lead patenting at 833 K
for 60 s to obtain a full pearlite microstructure. The patented material was drawn until the diameter reached 3 mm. Delamination is
promoted by an increase in the wire-drawing strain; however, as the amount of wire-drawing strain in this study was small, the sample
did not exhibit delamination during drawing. Therefore, the drawn sample was aged at 423 K for 3.6 ks to induce delamination during
torsion. Torsion testing was conducted using self-made equipment, in which both ends of the rod material were held by chucks placed
160 mm apart. Then, one side was firmly affixed in a chuck, and the other side was rotated at a fixed speed. The torsion test was conducted
at room temperature. The torque applied to the test specimen was recorded using a torque meter mounted to the rotating part, and the
number of rotations was calculated using the rotation speed. To control the scattering of the crack initiation points, a 0.2-mm-diameter
hole was formed at the centres of the torsion-tested specimens (80 mm from the grip points) using electrical-discharge machining.
Fig. 1 shows that the torque from the as-drawn specimen increased slightly owing to work hardening after yielding
and that the specimen fractured at a strain of 0.34. The elastic limit was increased for the aged specimen compared with the as-
drawn specimen, which was attributed to the ageing. The aged specimen exhibited almost no work hardening after yielding, and
it exhibited a sudden decrease in torque caused by the delamination. The aged specimen fractured at a shear deformation of 0.49;
it was not destroyed immediately after the onset of delamination.
In order to investigate the mechanism underlying the delamination, the microstructures immediately beneath the
normal fracture surface and beneath the delamination crack were
observed. First, a torsion test was performed, which was terminated
immediately after the drop of the torque, and the microstructure
directly beneath the delamination crack was observed using BSE
images. The observed surface was a C-section, as shown in Fig. 2(a).
The delamination crack propagated along both the longitudinal and
radial directions of the specimen. Fig. 2(a) shows a C-section for which
the drawing direction was the depth direction. The cementite lamellae
exhibited complex shapes. For the cementite lamellae at the wake of
the delamination crack, the contrasts vanished. Transmission electron
microscopy revealed that the cementite lamellae that were beneath the
delamination crack[4] before the rotation were no longer there. This
suggests that the decomposition of cementite is closely related to the
propagation of delamination cracks. The microstructure beneath the Fig.1 Torque-shear strain curves from as-
drawn and aged specimens, where the
normal fracture surface was also examined, to determine whether the drawing strain was 2.2 [1].
decomposition of cementite in this manner occurred only in the area

beneath the delamination cracks.
Fig. 2(b) shows a BSE image of the area immediately
beneath the normal fracture surface (L-section) outlined by a dotted
square in the schematic. The drawing direction was the longitudinal
direction of the sample (left–right), and the left edge of the schematic
was the normal fracture surface. Compared with the area immediately
beneath the delamination crack, there are two points of interest: (1)
the contrasts of the cementite lamellae remained clear throughout the
figure, and there was no decomposition of the cementite immediately
below the normal fracture surface; and (2) the cementite lamellae that
were lain along the drawing direction (left–right in the image) before
the torsion test rotated in the up–down direction. The considerable
rotation of the cementite lamellae is primarily attributed to the plastic
deformation of ferrite, because the yield stress of cementite is
significantly higher than that of ferrite[5]. These differences in the
plastic deformation behaviour of the specimens with normal fracture
and delamination indicated the following. In samples with normal Fig.2 (a) BSE image along a delamination crack
observed from the C-section. The area observed is
fractures, the torsion up to the fracture was due to the plastic pointed by a square in the schematic beside the BSE
deformation with lamellar rotation. In contrast, in the case where image. The contrast of cementite lamellae
disappeared along the crack. (b) BSE image just
delamination occurred immediately after yielding, plastic beneath the normal fracture surface observed from
deformation was accompanied by the decomposition of the cementite the L-section. Lamellae direction rotated from the
directly beneath the delamination crack. On the basis of these results, drawing direction [1].
we consider the mechanisms underlying the delamination.
To consider these effects, the state of stress, which
produced normal fracture or delamination, was considered. When
torque was applied to the specimen during a torsion test, as shown in
Fig. 3(a), shear stress was applied to the outermost surface of the
sample, as shown in the figure. The plane normal to the fracture
surface for normal fracture was parallel to the longitudinal direction.
Therefore, the dominant shear stress acting on the fracture surface
was perpendicular to the longitudinal direction, as shown in Fig. 3(b).
In contrast, the delamination cracks propagated parallel to the
longitudinal direction, as shown in Fig. 2(a). Therefore, the dominant
shear stress acting on the delamination cracks was parallel to the
longitudinal direction, as shown in Fig. 3(c). Furthermore, as shown
in the optical micrographs in Fig. 3(b), the delamination crack
exhibited complex shapes after a fracture.
References
[1] M. Tanaka, Y. Manabe, T. Morikawa, K. Higashida, ISIJ
International 60 (2020) 2596-2603.
[2] A.R. Marder, B.L. Bramfitt, Metall. Trans. A 7 (1976) 365-
372.
[3] D. Hirakami, T. Manabe, K. Ushioda, K. Noguchi, K. Takai,
Y. Hata, S. Hata, H. Nakashima, ISIJ International 56
(2016) 893-898. Fig. 3 State of stress at the specimen surface
[4] M. Tanaka, H. Saito, M. Yasumaru, K. Higashida, Scripta under the torsion as in the figure. (a) Shear
Mater. 112 (2016) 32-36.
stress under the torsion on the surface. (b)
Dominant shear stress causing normal
[5] M. Umemoto, Y. Todaka, T. Takahashi, P. Li, R. Tokumiya, K. fracture. (b) Dominant shear stress causing
Tsuchiya, Mater. Sci. Eng. A 375-377 (2004) 894-898. delamination crack propagation [1].

Fatigue life prediction of steels based on multiscale model synthesis
Kazuki Shibanuma
The University of Tokyo
Abstract:
This study presents a multiscale modelling strategy for accurately predicting the high-cycle fatigue
strengths of steels based on only microstructural information, tensile properties, and loading
conditions, without any adjustable material constants. In the proposed strategy, total fatigue life is
estimated from crack growth life alone. The entire model comprises three sub-models, for: (i) a
macroscopic finite element analysis, (ii) microstructure, and (iii) crack growth. The model was strictly
validated against the results of experiments performed on three different steels under various loading
conditions. Although the experimental fatigue life results exhibited wide variation, the predicted and
experimental data were accurately matched over the entire range. The results demonstrate that the
fatigue life of steels under high-cycle fatigue can be accurately predicted from crack growth life alone.
Furthermore, the proposed strategy is capable of effectively explaining the dependence of fatigue
strength on microstructure and loading conditions based on the fracture mechanics.

Delayed Fracture Behavior of Ultra-High-Strength Low-Alloy Steel
Processed by Warm Tempforming
Yuuji Kimura1,*, and Tadanobu Inoue1
1
*email: Kimura.Yuuji@nims.go.jp
Keywords: steel, thermomechanical treatment, ultrafine grained microstructure, strength, delayed fracture
Warm tempforming is a thermomechanical treatment that plastically deforms tempered martensitic structure at an
elevated temperature. We have developed the warm tempforming process with multi-pass caliber rolling as a method to create
ultrafine elongated grain (UFEG) structure with a strong <110>// rolling direction (RD) fiber texture in medium-carbon
low-alloy steels. It has been demonstrated that warm tempformed (TF) steel bars with UFEG structures have been
demonstrated to exhibit excellent mechanical performance.1) In this presentation, we report on the delayed fracture behavior of
0.4%C-2%Si-1%Cr-1%Mo steel (mass %) with UFEG structure processed by warm tempforming. The delayed fracture
property was evaluated by comparing the relationship between the critical hydrogen concentration for
hydrogen embrittlement and the concentration of hydrogen intrusion from an atmospheric corrosive
environment. 2) Delayed fracture behavior of the ultra-high-strength bolts produced from the TF steels in long-term outdoor
exposure tests is also be presented. 1, 3)
The quenched bars for 0.4%C-2%Si-1%Cr-1%Mo steel were tempered at 500 °C for 1 h and subsequently warm
tempformed by multi-pass caliber rolling with a rolling reduction of 762)~78%3), followed by air cooling (TF sample). The
details of the warm tempforming process were described elsewhere.1-3) The TF samples were annealed 570 °C for 1 h, where
Mo-rich precipitates significantly precipitated, 2, 4) and then water cooled (TFA sample).
The microstructures were observed by FE-SEM and TEM. FE-SEM/EBSP analysis was carried out at a step size
of 50 nm. Tensile tests were performed at a crosshead speed of 0.85 mm/min for JIS Z 2201-14A specimens with a diameter
of 6 mm and gauge length of 30 mm. Representative nominal stress-strain curves and tensile properties are presented in Fig. 1
and Table 1, respectively. 2) Data for the sample quenched and tempered at 500 °C for 1 h (QT sample) are also shown for
reference. While the TF sample exhibited discontinuous yielding, the TFA and QT samples exhibited continuous yielding.
Total elongation (EL) and reduction in area (RA) of the TF and TFA samples were higher than those of the QT sample
although the tensile strength, σB, of these samples were almost the same at 1.8 GPa.
Table 1 Tensile properties; yield strength, σ0.2,

tensile strength, σB, total elongation (EL) and
reduction in area (RA)
σ0.2 σB EL RA
Samples
(MPa) (MPa) (%) (%)
TF 1890 1860 13.2 44
TFA 1790 1840 14.7 47
QT 1530 1790 9.7 33
Fig. 1 Nominal stress-strain curves of the QT, TF and

TFA samples for 0.4%C-2%Si-1%Cr-1%Mo steel

Delayed fracture property was evaluated by slow-strain-rate testing (SSRT) and cyclic corrosion testing (CCT).
SSRT was carried out at a crosshead speed of 0.005 mm/min for notched bar specimens with a stress
concentration factor, Kt, of 4.9, as shown in Fig. 2. This Kt value simulates the stress concentration at the
unthreaded part of a high-strength bolt,3, 5) where a delayed fracture often occurs. The notched specimens were
charged with hydrogen at current densities of 0.2 to 17 A/m2 for 72 h in a 0.1 N NaOH aqueous solution or in a
3%NaCl + 0.3%NH4SCN aqueous solution, after which they were electroplated with Cd plating to avoid the
release of hydrogen during SSRT. The Cd plating was removed from the specimens following SSRT. CCT was
performed at a temperature of 30 °C for cylindrical specimens with a diameter of 5 mm and a length of 30 mm. The time
period of a corrosion cycle was 8 h consisting of a dry step at 50% relative humidity (RH) for 5.75 h, a wet step at 98% RH
for 1.75 h, and a salt spray step of a 0.5% NaCl solution for 0.5 h. Thermal desorption spectrometry (TDS) analysis with a
quadrupole mass spectrometer was performed to measure the hydrogen content within the specimens. Hydrogen desorbed up
to 300 °C was regarded as diffusible hydrogen.
Fig. 2 Shape and dimension of notched bar specimen with a stress concentration factor, Kt, of 4.9
Fig. 3 shows the microstructures of the QT and TF samples. 2) The QT samples exhibit tempered
martensitic structure characterized by equiaxed prior-austenite grains consisting of packets that are further
subdivided by fine blocks. On the other hand, the TF sample exhibits a UFEG structure with a strong
<110>//RD fiber texture. It is difficult to distinguish the boundaries of the prior-austenite grains and packets.
Film-like intergranular carbides as observed in the QT sample are not observed. The carbide particles in the TF
sample are spheroidized and most of the intergranular carbides are aligned along the RD. These carbide
particles are mainly cementite. A similar UFEG structure was observed in the TFA sample. The transverse grain
size in the UFEG structure and cementite particle distribution were measured to be almost the same between
the TF and TFA samples. However, the precipitation state of the Mo-rich precipitates in the TF sample was suggested to
be different from that in the TFA sample because the hydrogen absorption capacity in the TFA sample was larger than that in
the TF sample.
Fig. 3 Inverse pole figure maps for the RD and TEM images of of the QT and TF samples.
Inverse pole figure for the RD of the TF sample is also shown.

Fig. 4 shows the variations in the notch tensile strength, σNB, with the diffusible hydrogen content,
HD. The σNB was calculated by dividing the maximum tensile load by the initial minimum cross-sectional area
2)
at the notch. In all samples the σNB decreases with increasing the HD and hydrogen embrittlement is observed.
The σNB–HD relationship can be used to estimate the critical hydrogen content, HC, below which fracture does
not occur at the applied stress corresponding to σNB. Furthermore, the maximum concentration of diffusible
hydrogen that accumulated locally in the stress concentrated region near the notch root, HC* can be estimated
by substituting the HC value into the following equation:3-4, 5)
HC* = HC exp (–Δσh ΔVH/RT) (1)
where Δσh is the difference between the maximum hydrostatic stress in the vicinity of the notch root,
σm*, and the hydrostatic stress in the region far from the notch root, σp, ΔVH is the partial molar volume of
hydrogen in bcc–Fe (= 2×10−6 m3/mol), R is the gas constant (= 8.31 J/K/mol), and T is the testing temperature
(= 300 K). Fig. 5 shows the relationship between the peak value of the maximum principal stress, σmax*, in the
vicinity of the notch root and Hc*, calculated from the data points in Fig. 4.
Fig. 4 Relationship between the diffusible hydrogen Fig. 5 Relationship between the peak value of
content, HD, and notch tensile strength, σNB locally accumulated diffusible hydrogen
concentration, HC*, and the peak value of the
maximum principal stress, σmax*
On the other hand, the maximum concentration of diffusible hydrogen that accumulates locally in the
stress concentration region near the notch root from an atmospheric corrosive environment, HE*, can be
estimated by the following equation: 3-4, 5)
HE* = HE exp (–σm*ΔVH/RT) (2)
where HE is the maximum content of diffusible hydrogen intrusion from an atmospheric corrosive
environment. The respective HE values were estimated by CCT to be 0.3 mass ppm for the QT sample, 0.4 for
TF, 0.6 for TFA sample.
Fig. 6 shows the relationship between the applied stress, σa and the HC*/HE*. Based on this index, if
the value of HC*/HE* is 1 or less, it can be determined that a delayed fracture could occur. The HC*/HE* values
of the QT samples are less than 1 at σa of greater than 1.1 GPa, and thus the QT sample is prone to a delayed
fracture. By contrast, the TF and TFA samples are expected to be free from delayed fracture up to σa of 1.9 and
2.0 GPa, respectively. Therefore, it can be concluded that the delayed fracture resistance of the TF and TF
samples are significantly higher than that of the QT sample under the atmospheric corrosive environment,
considering the hydrogen uptake.
Ultra-high-strength bolts (JIS-M12-hexagon head bolts) with a σB of 1.7 and 1.8 GPa were produced
by warm forging the QT and TF steels, respectively.1, 3) Outdoor exposure tests of the bolted fasteners were

started on May 21, 2013 at the Japan Weathering Test Center Miyakojima test site (24°44' N, 125°19' E, 50 m
above sea level) to evaluate the delayed fracture behavior. 1, 3) The Miyakojima test site has a subtropical oceanic
climate with high temperatures and humidity, high solar radiation, and high levels of airborne salt, making it one of the most
severe corrosive environments in Japan. The TF bolts were fastened at an axial force of 122 kN (σa =1.45 GPa=0.85σ0.2) on
an electrogalvanized plate. Similarly, the QT bolts were fastened at an axial force of 89 kN (σa =1.05 GPa=0.7σ0.2). Fig. 7
shows the changes in cumulative ratio of fracture with exposure time. Twenty percent of the non-coated QT bolts and
80% of the electrogalvanized QT bolts broke within 28 days from the day after they were secured indoors to the start of the
outdoor exposure test. Furthermore, in the outdoor exposure test, the electrogalvanized QT bolts did not fracture, whereas
delayed fracture began to occur from day 98 for the non-coated QT bolts and from day 555 for the Geomet coated bolts. Thus,
although the delayed fracture behavior of the QT bolts varied depending on the surface treatment conditions, delayed fracture
could not be suppressed. In contrast, no delayed fracture occurred in the TF bolts after 3220 days (as of March 15, 2022),
despite the fastening force of the TF bolts was 1.4 times greater than that for the QT bolt. This outdoor exposure test is
still ongoing. Therefore, the excellent delayed fracture resistance of 1.8 GPa-class TF bolts was confirmed by long-term
outdoor exposure tests.
Fig. 6 Changes in HC*/HE* as a function of the Fig. 7 Changes in cumulative ratio of fracture
applied stress, σa. with exposure time
The warm tempforming using multi-pass caliber rolling at 500 ℃ resulted in the formation of an ultrafine
elongated grain (UFEG) structure with a strong <110>//RD fiber texture and a dispersion of fine spheroidized carbide
particles for 0.4%C-2%Si-1%Cr-1%Mo steel. When the warm tempformed (TF) sample was annealed at 570 ℃ for 1 h
(TFA sample), the hydrogen absorption capacity was enhanced significantly due to nanoscale Mo-rich precipitates in the
UFEG matrix. The results of the slow-strain-rate test and cyclic corrosion test showed that TF and TFA samples with UFEG
structures had a high delayed fracture resistance at an ultra-high tensile strength of 1.8 GPa in an atmospheric corrosion
environment. Excellent delayed fracture resistance was further demonstrated by the long-term exposure test for the
ultra-high-strength bolts processed by warm forging the TF steels.
Acknowledgement
The study was partly supported by grants from the JSPS KAKENHI Grant Number 19H02468.
References
1) Y. Kimura and T. Inoue: ISIJ Int. 60 (2020) pp.1108-1126.
2) Y. Kimura, T. Inoue and E. Akiyama: Mater. Sci. Eng. A 703 (2017) pp.503-512.
3) Y. Kimura, T. Inoue, T. Nakata and M. Fukuda: Trans. Jpn. Soc. Mech. Eng. 84 (2018) 17-00493 (1-15).
4) Y. Kimura, T. Moronaga and T. Inoue: ISIJ Int. 62 (2022) pp.377-388.
5) Guide book for evaluation of delayed fracture property of high strength bolts, JSSC Tech. Rep. No. 91, (2010).

Hydrogen Embrittlement Behavior of Nanostructured SUS316LN
Austenitic Stainless Steel Produced by Heavy Cold-rolling
and High-pressure Torsion Straining
Yoshikazu Todaka 1,*, Nozomu Adachi 1, Hiromi Miura 1, Masakazu Kobayashi 1,
Chihiro Watanabe 2 and Yoshiteru Aoyagi 3
1
Department of Mechanical Engineering, Toyohashi University of Technology, 1-1 Hibarigaoka Tempaku-cho, Toyohashi,
Aichi 441-8580, Japan
2
Division of Mechanical Science and Engineering, Kanazawa University, Kakuma-machi, Kanazawa, Ishikawa 920-1192, Japan
3
Department of Finemechanics, Tohoku University, 6-6-01 Aramaki Aoba-ku, Sendai, Miyagi 980-8579, Japan
*email: todaka@me.tut.ac.jp
Keywords: austenitic stainless steel, mechanical property, hydrogen embrittlement, nanostructure, plastic deformation
Austenitic stainless steels (ASSs) are one of the most important materials and widely utilized as basic a structural
material. Much attention has been drawn in the past decades to strengthen the ASSs, and various approaches have been
developed, such as grain refinement. To achieve grain refinement down to nanometer-size, heavy cold-rolling and
high-pressure torsion (HPT) straining were performed in SUS316LN ASS (316LN). The heavy cold-rolling of 316LN to
92 % reduction produced characteristic heterogeneous nanostructure composed of twin domains, shear bands and low-angle
lamellae. 1) The 316LN after the HPT straining for 20 turns has homogeneous nanostructure with grain sizes of several tens
of nanometers. 2) The heterogeneous and the homogeneous nanostructured 316LN specimens showed the tensile strengths
of 1.8 and 2.0 GPa with the large fracture elongation of about 15 %. The effect of these nanostructures on the hydrogen
embrittlement behavior was investigated. 2) Thermal desorption spectroscopy showed that the electrochemical hydrogen-
charged 316LN specimens with these nanostructures had almost the same concentration of diffusible hydrogen. While the
tensile properties of the homogenous nanostructure were severely affected by diffusible hydrogen, it had less impact on the
tensile properties of the heterogeneous nanostructure, as shown in Fig. 1. Hydrogen embrittlement is suppressed in the
heterogeneous nanostructure because crack propagation seems to be hindered by twin domains.
3000 3000
(a) (b)
Uncharged Uncharged
Nominal stress, σ / MPa
Nominal stress, σ / MPa
2500 Hydrogen-charged 2500 Hydrogen-charged
2000 2000
1500 1500
1000 1000
500 500
0 0
0.00 0.05 0.10 0.15 0.20 0.00 0.05 0.10 0.15 0.20
Nominal plastic strain, ε Nominal plastic strain, ε

Fig. 1 Hydrogen embrittlement behavior of nanostructured 316LN specimens produced by (a) heavy cold-rolling
of 92 % reduction and (b) HPT straining for 20 turns. Hydrogen charging condition: Current density 10 mA/cm2,
Electrolyte solution 0.5 mol/L H2SO4 + 0.01 mol/LCH4N2S, Charging time 6 h, Room temperature.
Acknowledgement
This study was conducted under the financial supported by the Japan Science and Technology Agency (JST) under Collaborative
Research Based on Industrial Demand “Heterogeneous Structure Control: Towards Innovative Development of Metallic Structural
Materials” (Grant No. JPMJSK1413).
References
1) H. Miura, M. Kobayashi, Y. Todaka, C. Watanabe, Y. Aoyagi, N. Sugiura and N. Yoshinaga: Scripta Materialia 133 (2017) 33.
2) F.J. Mweta, N. Adachi, Y. Todaka, H. Sato, H. Miura, M. Kobayashi, C. Watanabe and Y. Aoyagi: MRS Advances, 6 (2021), 682.

Heterogeneous cleavage fracture of lath martensite induced by Bain strain
Yuki Kawahito1, Daisuke Fukui1, Naoki Miyazawa2, Nobuo Nakada2,*, and Susumu Onaka2
1 Graduate student, Tokyo Institute of Technology, 4259, Nagatsuta-cho, Midori-ku, Yokohama 226-8503, Japan
2 Department of Materials Science and Engineering, Tokyo Institute of Technology, 4259, Nagatsuta-cho, Midori-ku, Yokohama 226-
8503, Japan
*email: nakada.n.aa@m.titech.ac.jp
Keywords: martensitic transformation, Bain lattice correspondence, transformation-induced internal stress, Charpy impact testing
1 Introduction
In iron and steel, austenite (A) with face-centered cubic lattice (fcc) transforms to martensite (M) with body-centered cubic lattice (bcc)
or body-centered tetragonal lattice (bct), and the Bain lattice correspondence is established between them. Some of the authors[1] reported
that a small part of Bain strain remains even after lattice invariant deformation, and microscopic internal stresses are then distributed
among Bain groups in Fe–16mass%Ni alloy having lath martensite. It is thought that the stresses affect the mechanical properties of
martensitic steels. In this study, the {001} cleavage fracture under mode I condition was evaluated and its anisotropy was discussed in
terms of microscopic transformation-induced internal stress.
2 Experimental Section
An Fe–0.1mass%C–5mass%Mn alloy was used in this study. The test pieces were austenitized at 1373 K, followed by water quenching
to fully obtain as-quenched lath martensite. Charpy impact test was carried out at ambient temperature immediately after holding the test
piece at 77 K in liquid nitrogen. The crystal orientation was analyzed by means of electron backscattered diffraction (EBSD) technique.
At this time, martensite variants with <001>M roughly parallel to [100]A, [010]A, and [001]A of prior austenite were classified as Bain-1,
-2, and -3, respectively. Similarly to the previous study[1], in order to evaluate microscopic internal stress developed in lath martensite, a
cylindrical micropillar with 10 µm in diameter was fabricated within a Bain group of lath martensite using a field emission-type SEM
with a focused ion beam system (FIB/FE-SEM), and two-dimensional plane strain released by the fabrication was measured accurately
using digital image correlation method (DIC, GOM Collection Pro.).
3 Results
3.1 Transformation-induced Internal Stress in Lath Martensite
The FIB-DIC analysis revealed that the anisotropic elastic strain remained in a Bain group, and the average principal strains were
evaluated at e11 = e22 = –0.27% and e33 = 0.15%, where their directions are parallel to [001]M, [010]M and [100]M, respectively. According
to these values, it was calculated that the transformation-induced internal stresses were s11 = s22 = –744 MPa and s33 = –72 MPa, which
leads to a large stress deviation, s33–s11, ca.700 MPa. Considering that the same phenomenon was confirmed in the Fe–16mass%Ni
alloy[1], it should be thought that the transformation-induced internal stress attributed to the Bain strain is one of the characteristics of the
lath martensite regardless of the presence of solute carbon.
3.2 Anisotropy of {001} Cleavage Fracture in Lath Martensite

Fig. 1. is a vertical sectional image showing the vicinity of V-notch in the fractured specimen. (a) and (b) show IPF map and
corresponding Bain map indicating 3 Bain variants existing in lath martensite, respectively, and (c) is <001>bcc pole figure of martensite
variants in the objective prior austenite grain. The Bain map (b) reveals that the cleavage facet planes tend to be the {001}M trace and
grew within individual Bain groups. After about 1000 measurement points were selected along the fracture surface in the prior austenite
grain, it was identified whether they belong to the cleavage plane with the {001}M trace. After that, if it was a cleavage fracture, the
cleavage plane was classified into (100)M, (010)M, and (001)M according to Bain lattice correspondence with pole figure (c). The fraction
of {001}M cleavage fracture within each Bain group F was obtained according to the above procedure and then arranged by the resolved
normal stress sres generated in the normal direction of each {001}M, as shown in Fig. 2. Here, sres was calculated geometrically from the
bending normal stress sapp applied to the bottom of the notch. F increases linearly with increasing sres, which suggests the cleavage
fracture under mode I condition. It should be noted here that the two parallel linear relations between F and sres were independently

established in (001)M and (100)M, respectively. As a result,
F of (001)M is approximately 20% higher than that of
(100)M at a given sres. This clearly proved that cleavage
fracture occurs more frequently on (001)M than (100)M,
and that lath martensite shows clear anisotropy in
cleavage fracture.
4 Discussion
Comparing of F–sres line between (001)M and (100)M in
Fig. 2, it is found that higher sres, app. 600 MPa, is needed
to make cleavage fracture on (100)M compared with
(001)M at a given F. This difference in sres is close to the
deviation of internal stress in a Bain group, s33-s11, as
mentioned above. This suggests that the transformation-
induced internal stress has a large influence on the
cleavage {001} mode I fracture in martensitic steels.
5 Conclusions
1. The frequency of the {001}M cleavage fracture
increases with increasing the resolved stress normal
to the plane, which suggests that the cleavage
fracture occurs in mode I manner. In addition,
crystallographic orientation analysis based on Bain
lattice correspondence reveals that cleavage fracture
occurs more frequently on (001)M than on (100)M in
each Bain group.
2. The combination of micro-scale focused ion beam
and high-precision digital image correlation Fig. 1. The result of crystal orientation analysis for the area near
techniques proves that compressive internal stresses the bottom of the V-notch. (a) IPF and (b) Bain map and
were anisotropically developed in each Bain group (c) <001>bcc pole figure of martensite within the prior
while maintaining <001>M as principal axes. And austenite grain g1. The white lines in the map (a) indicate
the principal compressive stress parallel to [001]M is the trace of {001}bcc.
much lower than two others.
Acknowledgment
This work was supported by JST, PRESTO, Grant
Number JP20345123, Japan, and the Society of Hot Dip
Galvanized High Strength Bolt Engineering.
References
1) [1] D. Fukui, N. Nakada, S. Onaka: Acta Mater.,
196(2020), pp. 660-668.
Fig. 2. Relation between the fraction of cleavage fracture within

each Bain group F and the resolved normal stress sres.

Formation of inhomogeneous microstructure in martensitic steel during cooling
and its effect on yield strength
Shimpei Yoshioka1,*, Shinjiro Kaneko2, Tadachika Chiba1, Takako Yamashita2 and Yasunori Yamada3
1
Steel Research Laboratory, JFE Steel Corporation, 1 Kokan-cho, Fukuyama, Hiroshima 721-8510, Japan
2
Steel Research Laboratory, JFE Steel Corporation, 1 Kawasaki-cho, Chuo-ku, Chiba 260-0835, Japan
3
Steel Research Laboratory, JFE Steel Corporation, 1-1 Minamiwatarida-cho, Kawasaki-ku, Kawasaki, Kanagawa 210-0855, Japan
*email: shim-yoshioka@jfe-steel.co.jp
Keywords: steel, martensite, cooling rate, yield strength, grain refinement, carbon partitioning
1. Introduction
Applications of ultra high strength martensitic steel sheets for automotive structural parts are expanding due to their
outstanding yield strength which strongly affects crash performance. The yield strength of martensitic steel sheets should be
influenced by many microstructural factors. Although cooling rate during martensite transformation is one of the basic control
in producing martensitic steel, but there are few researches have reported about its effect on microstructure or strength of
martensitic steel sheets. Therefore, the objective of this study is to clarify the effect of cooling rate on formation of
inhomogeneous microstructure leading to yield strength of martensitic steel sheets.
The tensile properties and microstructures were investigated using martensitic steels with chemical compositions of
Fe-C-0.2%Si-2.0%Mn-0.02%Ti-0.002%B (wt%) produced in different cooling rate during martensitic transformation.
Water-quenched (WQ) steels were produced by quenching into water, and air-cooled (AC) steels were produced by air
cooling after annealing in γ region. Low temperature tempering was performed in both steels. Microstructures were
investigated by means of SEM, EBSD analysis and high accuracy FE-EPMA (C-analyzer)1).

SEM images of 0.2 wt% C steels in each cooling rate are shown in Fig. 1, and the microstructures of both steels
were fully martensitic structure. Although packet and block size of low carbon martensitic steels have been reported to be
getting coarser with decreasing cooling rate during martensite transformation2), the block size of AC steels were finer than that
of WQ steels in low carbon content range (0.05~0.20%C). The mechanism of grain refinement in AC steels was further
focused and investigated by means of variant pairing analysis, dilatometric tests and combined microstructural analysis using
scanning electron microscopy, electron backscatter diffraction analysis and C-analyzer. As a result, it was newly clarified that
slight bainite transformation and carbon partitioning during martensite transformation led to grain refinement in AC steels.
In contrast, yield strength of AC steels were lower than that of WQ steels even at the same carbon content.
Therefore, the main factor inducing difference in yield strength would be the other factors, because yield strength is generally
increased by grain refinement.
References Fig.1 SEM images of (a) water-quenched, (b) air-cooled steel.

1) T. Yamashita, Y. Tanaka, M. Nagoshi and K. Ishida: Sci. Rep., 6(2016), Article No. 29825, DOI: 10.1038/srep29825.
2) K. Tsuzaki, T. Maki: J. Japan Inst. Metals, Vol.45, No.2 (1981), 126.

Estimation of true hardness of as-quenched martensite without auto-
tempering
Osamu Idohara1,*, Youhei Hiyama1, Yoshitaka Misaka1, Setsuo Takaki1, Toshihiro Tsuchiyama2
1 Researchand Development Headquarters, Neturen Co., Ltd, Hiratsuka, Kanagawa, 254-0013, Japan
2 Department of Materials Science and Engineering, Kyusyu University, Nishi-ku, Fukuoka, 819-0395, Japan
*email: o-idohara@k-neturen.co.jp
Keywords: steel, as-quenched martensite, auto-tempering, true hardness, carbon
Introduction
The strength of as-quenched martensite increases with an increase of carbon content but untransformed
austenite retains in steels with carbon more than 0.6% because Mf temperature becomes lower than room
temperature1). On the other hand, in steels with high Ms temperature, auto-tempering occurs after
martensitic transformation and this leads to the decrease of hardness in as-quenched martensite2). Since
auto-tempering is attributed to the diffusion of carbon atoms during cooling, the degree of auto-tempering
can be evaluated by the integrated diffusion area; S (=∑Dt), where D and t are the diffusion coefficient of
carbon in bcc-Fe and holding time respectively. It is found that the degree of auto-tempering is so large in
steels with Ms temperature higher than 350℃3). In commercial martensitic steels, Ms temperature can be
estimated by the following equation as a function of chemical composition4).
Ms (℃) = 539-423C-7.5Si-30.4Mn-12.1Cr-17.7Ni-7.5Mo+10Co (1)
The above equation suggests that auto-tempering is significant in steels with carbon less than 0.45%. In
this study, steels with various carbon content (S25C, S35C, S45C, S55C) were used to estimate the
degree of auto-tempering in as-quenched martensite and true hardness of as-quenched martensite without
auto-tempering was proposed for martensitic steels with carbon less than 0.6%.The amount of retained
austenite is so little that the effect of retained austenite may be negrected with respect to the hardness of
specimens.
Experimental procedure
Material used in this study was commercial structural steels (S25C, S35C, S45C, S55C) having
different carbon content from 0.27% to 0.55%. Chemical composition and transformation temperature of
steels are listed in Table 1. Transformation temperature was measured by dilatometry during cooling
(60℃/s) using an induction heat treating simulation apparatus. Specimens with the dimension of 16mm
diameter and 3mm thickness were prepared for Vickers hardness testing. The specimens were solution-
treated at 890 ℃ for 30min in Nitrogen atmosphere and then quenched into 5%-NaCl cold water.
Subsequently they were tempered for 60 min at the temperature in the range of 150℃ through 600℃.
Vickers hardness testing was performed on the cutting section (3×16 mm) of specimens under the load
2.9N. Measurement was performed 5 times and the average value was adopted as the hardness of each
specimen.
Table 1 Chemical composition of steels used.

C Si Mn Cr Ni Ms (℃) M50 (℃) γ (%)
S25C 0.27 0.20 0.47 0.13 0.01 407 352 1.8
S35C 0.36 0.19 0.75 0.11 0.02 360 305 1.8
S45C 0.45 0.21 0.72 0.02 0.01 324 265 3.9
S55C 0.52 0.16 0.73 0.14 0.02 294 239 5.5

Experimental results and discussion
Fig. 1 shows the relation between
tempering temperature and Vickers hardness 9
under the condition of 1h tempering. In the 8 S55C
Vickers hardness, HV / GPa

temperature range above 200 ℃ , hardness 7 S45C
decreases monotonously with a rise of 6 S35C
tempering temperature. Here, it should be S25C
5
noted that large difference is found in the
temperature below 200 ℃ . Tempering 4
reaction is devided into four stages（A-D）: 3
A- stage (0-100 ℃ ) where clustering of 2
carbon atoms occurs through the short range 1 Tempering time: 1h
diffusion, B-stage (100-200 ℃ ) where 0
transitional carbide precipitates, C-stage 0 100 200 300 400 500 600 700
(200-300℃) where a compound carbide (θ Tempering temperature, （℃）
') precipitates, D-stage (300-400℃) where Fig. 1 Relations between tempering temperature
and Vickers hardness in specimens with 1h
θ ' changes to cementite ( θ ) and
tempering.
precipitation of θ completes. Above 400 ℃,
Ostward ripening of θ occurs 5). The
decomposition of retained austenite can be
negrected in this study because the amount
of retained austenite is so small as listed in
Table 1. Continuous softening occurs in
S45C and S55C but plateau is found in
S35C and S25C in the temperature below
200℃. The existence of plateou suggests
that auto-tempering occurs for these steels
during water-quenching.
The degree of tempering can be evaluated
quantitatively by the diffusion area; S
(=∑Dt) as mentioned above. In general,
diffusion coefficient D can be expressed by
the following equation as a function of Fig. 2 Relations between diffusion area S and
temperature T. Vickers hardness in specimens with 1h tempering.
Open marks show the true hardness of as-quenched
D =D0 exp (-Q/R/T) (2) martensite without auto-tempering.
D0, Q, R are the frequency factor, activation energy in atomic diffusion, gas constant (8.3145 J/mol/K),
respectively. In the tempering reaction at A-D stages, it is sure that carbon diffusion relates the tempering
reaction. Regarding the diffusion of carbon in bcc-Fe, D0 =5.7×10-6 [m2/s] and Q = 91000 J/mol were
obtained from reliable data6). Since the value of D is given as a function of tempering temperature T (Eq.
2), the diffusion area S is calculated putting t = 3600s in the case of 1h tempering. The data of Fig. 1 are
re-plotted in Fig. 2 as a function of diffusion area S in the temperature range below 400℃. Regarding
S45C, a smooth curve is obtained against the S-value so that it was selected as a standard tempering curve,
that is expressed by the following equation.
HV(S45C) = f(S) (3)

In the other steels, the following equation is applied to make the curve fit to the date in the range of large
S-value.
HV = A×f(S) (4)

Optimal value was selected for each steel;
A=0.84 in S25C, A=0.94 in S35C, A=1.06 in
S55C. Fitting curves are drawn in the figure
by bold lines and open marks correspond to
the hardness of as-quenched martensite
without auto-tempering HV*; 6.06 GPa in
S25C, 6.70 GPa in S35C, 7.62 GPa in S55C.
It is reconfirmed that marked auto-tempering
has occured in low carbon steels with high
Ms temperature even if water-quenching has
been done to obtain fresh martensite. Grange
et al. also reported data with respect to 1h-
tempered martensite in Fe-C alloys7).
Same process was applied to the Grange’s
data and the values of HV* ware determined Fig. 3 Relations between carbon content (%C)
in the same way. Relation between carbon and the true Vickers hardness of as-quenched
content and HV* is summarized in Fig. 3. The martensite without auto-tempering; HV*.
hardness of pure iron martensite, that was
estimated form the relation between carbon
content and hardness of as-quenched
martensite, is about 2.0GPa8). By connecting
all data smoothly, the following equation is
obtained:
HV* [GPa] = 2.0 + 7.8×(%C)1/2 (5)
In general, the amount of solid solution

strengthening is proportional to the square
root of chemical composition of allying
elements9). The above equation suggests that
solid solution strengthening by carbon is
dominant on the strength of as-quenched
martensite.
Fig. 4 summarizes the effect of carbon on Fig. 4 Effect of carbon content (%C) on the
the hardness of as-quenched martensite2)7)10)11). auto-tempering in water-quenched martensite.
The curve, that has been obtained by Eq. 5, is
also drawn by a bold line in the figure. It is
found that marked auto-tempering occurs in
low carbon steels (0.1-0.3%C). Of cource,
the degree of auto-tempering depends on the
cooling rate in quenching. For instance, in the
case of oil-quenching, the degree of auto-
tempering may reach to the B stage of
tempering and this should cause larger
softening.
Fig. 5 shows the relation between the
diffusion area S and the standardized hardness
Hs, that is expressed by the following
equation.
Hs = HV / HV* (6)
Fig. 5 Relations between diffusion area and the
It is interesting that all data follow an standardized hardness in martensite with 1h
identical curve in each steel except for tempering.
specimens with auto-tempering. Grange’s

specimens are of basic Fe-C alloy, while our specimens contains small amount of Si and Mn. The figure
proves that the effect of alloying element hardly appears in the temperature range below 400℃ but
significant above 400℃, where Ostward ripening of cementite controls the softening behavior. Such a
behavior is reasonable because tempering reaction is controlled by carbon diffusion in the temperature
below 400℃ but Ostward ripening of cementite is controlled by the diffusion of alloying elements
through the partitioning between matrix and cementite12). On the tempering where diffusion area is below
10-10m2, the amount of auto-tempering is estimeted by the following equation for commercial low alloy
martensitic steels.
Hs = 1.0 - 0.0052×{18+(log S)}2 (7)
In the case of quenching, S-value is given as an integrated diffusion area; ∑Dt based on a cooling
curve, thus the hardness of martensite with auto-tempering can be estimated applying Eq. 6 and 7.
Conclusion
It was confirmed that marked softening has occured in steels with carbon less than 0.4% even if water-
quenching has been done to obtain fresh martensite. True hardness of as-quenched martensite without
auto-tempering HV* is expressed by the follwing equation as a function of carbon content (%C).
HV* [GPa] = 2.0+7.8×(%C)1/2
The standardized hardness Hs (= HV / HV*) can be determined identically independent of carbon content
in steels under the same tempering condition. Regarding the martensitic steels with auto-tempering,
Vickers hardness can be estimated by the equation.
Hs = 1.0-0.0052×{18+(log S)}2
References
1) M.Maki:Materia Japan 54(2015) 557-563.
2) B.Hutchinson, J.Hagström, O.Karlsson, D.Lindell, M.Tornberg, F.Lindberg, and M.Thuvander:
Acta Materialia 59(2011) 5845-5858
3) S.Takaki, D.Akama and T.Tsuchiyama: Journal of the Japan Society for Heat Treatment, 56(2016)
340-344
4) N.Murai and T.Tsumura:Tetsu-to-Haganѐ 84(1998) 446-451
5) S.Nagakura:Denshikenbikyo 21(1986) 113-120
6) T.Kunitake: Materia Japan 3(1964) 466-476
7) R.A.Grange, C.R.Hribal and L.F.Porter:Metallurgical Transactions A, 8A(1977)1775-1785
8) Y.Imai and S.Sawada:Materia Japan 8(1969) 820-832.
9) H.Suto: Zairyou. 21(1972) 159-167.
10) M.Ueno, K.Nakamura, K.Ito and H.Minematsu: Tetsu-to-Haganѐ 68(1982) 155-161
11) G.R.Speich and P.R.Swann:J.Iron Steel Inst., 203(1965), 480
12) K.Sakuma, J.Kumagai and T.Nishizawa: Tetsu-to-Haganѐ 60(1974) 2153-2164

Grain refinement strengthening on Fe–18Ni low carbon lath martensite
Hiroyuki Kawata1,*, Yoshiaki Honda1, Katsuya Nakano2, Kengo Takeda1 and Kazuo Hikida3
1
Steel Research Laboratories, Nippon Steel Corporation, 20-1 Shintomi, Futtsu, Chiba, 293-8511, Japan
2
East Nippon R&D Laboratory, Nippon Steel Corporation, 1 Kimitsu, Kimitsu, Chiba, 299-1141, Japan
3
Setouchi R&D Laboratory, Nippon Steel Corporation, 1 Fuji-cho, Hirohata-ku, Himeji, Hyogo, 671-1181, Japan
*email: kawata.z84.hiroyuki@jp.nipponsteel.com
Keywords: steel, lath martensite, Hall-Petch relationship
1. Introduction
Lath martensite in steel is a beneficial structure to design high strength steels, e.g. dual phase steels and hot-stamping steels.
Although it is important to understand strengthening mechanisms of lath martensite for improving these high strength steels,
these mechanisms are unclear, because of its complex and hierarchical microstructure1). The increasing of carbon content in
lath martensite significantly increases the strength2), and carbon would increase the strength via several routes, as shown in Fig.
1. Typically, the solution hardening effect of carbon is regarded as the most effective route3,4). Similarly, grain refinement
induced by carbon increasing would be important factor in lath martensite strengthening. Morito et al. reported that the
effective grain of lath martensite5) is a block comprising laths that exhibit similar crystallographic orientations and the same
habit plane, and that a block size6) decreases with carbon increasing. The strengthening of lath martensite with carbon content
increasing depends on solution hardening and grain refinement strengthening; however, their proportions are unknown. In this
study7,8), we focused on the hardening effects in ultra-low- and low-carbon lath martensite structure.
Table 1 shows chemical compositions and martensite transformation start temperature of four Fe–18Ni. These alloys contain
several carbon contents between 4 and 570 mass-ppm. Alloy A contains 0.017 mass% titanium to trap 4 mass-ppm carbon
and 8 mass-ppm nitrogen as huge Ti(CN) particles The ingots melted by a vacuum induction furnace were hot-rolled over
900 °C. The grinded hot-rolled sheets with 3.0 mm thickness were austenitized at 800, 900, 1000 °C for 1.2 ks and quenched
by water. We applied an additional heat treatment, holding at 500 °C for 10.8 ks to alloy A for the growth of Ti(CN) particles.
Martensite transformation in these alloys occurred from 300 °C to room temperature; thus these alloys quenched did not
contain retained austenite evaluated via X-ray diffraction.
We observed high angle boundaries, whose misorientations were larger than 10 degree via a field-emission electron
microscopy (JEOL-6500F) with electron backscattering diffraction analysis system (OIM Data Collection ver. 7), as effective
grain boundaries corresponding to block boundaries in lath martensite structure5,6).
We evaluated tensile properties via tensile test with JIS 13B tensile test specimens (JIS Z 2201). The strain gage length was
50 mm, and the nominal strain rate was 3.3 × 10-3 s-1.
3. Results
Fig. 2 shows high angle boundary maps of lath martensite. The decreasing of austenitizing temperature decreased the grain
diameter (deff), corresponding to the average spacing of high angle boundaries, because deff depends on the austenite grain
diameter. At each austenitization temperature, the increasing of carbon content decreased deff, because packets became divided
by multi blocks in high carbon lath martensite6). In this study, we got lath martensite structures whose deff were from 6 to 30
µm.
Fig. 3 shows the relationship between deff and tensile properties, namely, yield point (YP), 0.2% proof stress (σ0.2%), 0.6%
proof stress (σ0.6%), and maximum tensile strength (TS) in each alloy. YP and TS correspond to the elastic limit and the onset
of plastic instability, respectively. In ultra-low-carbon alloy, Alloy A, YP, σ0.2%, σ0.6%, and TS did not depend on deff. These
stresses were completely constant in three samples austenitized at several temperatures. On the other hand, in Alloy D
containing 570 mass-ppm carbon, these stresses increased with deff refinement. This strengthening behavior seems to be
Hall-Petch relationship, σ = k·deff–1/2 + A5). Although this relationship similarly appeared in Alloys B and C, the strengthening
with grain refinement is clearer with the increasing of carbon content.

Fig. 4 shows the relationship between carbon content and Hall-Petch coefficients, k for each tensile property. These
coefficients in Alloy A were almost zero, and increased with the increasing of carbon content. This relationship between
Hall-Petch coefficient and carbon content is similar to Hall-Petch coefficient for YP in polygonal ferritic steel9). Takaki et al.10)
indicated that the dislocation behavior on grain boundaries in ferritic steel would be affected by the solute carbon. Thus, the
solute carbon in lath martensite affects the strengthening effectivity of grain refinement, and it suggested that this effect occur
with similar mechanism as in ferritic steel.
In Fig. 5, we compared the strengthening by carbon content, i.e. the increasing of σ0.6% from that in Alloy A, to the grain
refinement strengthening of σ0.6% with Hall-Petch coefficients shown in Fig. 4. The effect of carbon content corresponds to the
grain refinement strengthening, which was affected by the grain refinement and the increasing of effectivity of grain size with
increasing of carbon content. It suggested that the strengthening by carbon in low-carbon lath martensite structure depends on
the grain refinement strengthening, and the effect of solution hardening and the dislocation hardening induced during
transformation are negligible small, as shown in Fig. 6.
4. Summary
In this study, we evaluated the tensile properties of as-quenched martensite on ultra-low- and low-carbon Fe–18Ni alloys.
1. Tensile properties (YP, σ0.2%, σ0.6%, and TS) were constant in ultra-low-carbon alloy specimens containing several effective
grain size.
2. YP, σ0.2%, σ0.6%, and TS increased with grain refinement in low-carbon alloys. This strengthening behavior corresponded to
Hall-Petch relationship, and became clear with the increasing of carbon content.
3. Hall-Petch coefficient was almost zero in ultra-low-carbon alloy, and increased with the increasing of carbon content. This
behavior is similar to Hall-Petch coefficient for YP in polygonal ferritic steel.
4. The strengthening with carbon in low-carbon Fe–18Ni lath martensite mainly depends on the grain refinement
strengthening. The increasing of carbon content refined the effective grain, and increased the effectivity of grain refinement
strengthening.
References
1) E.C. Bain, H.W. Paxton : Alloying Elements in Steel, 2nd Ed., ASM, 1961, 33–36.
2) S. Morito, H. Saito, T. Ogawa, T. Furuhara, and T. Maki : ISIJ Int., 45, 2005, 91–94.
3) J.M. Chilton, and P.M. Kelly : Acta Metall, 16, 1968, 637–656
4) G. Krauss : Mater. Sci. Eng. A, 273–275, 1999, 40–57
5) S. Morito, H. Yoshida, T. Maki, and X. Huang : Mater. Sci. Eng. A, 438–440, 2006, 237–240
6) S. Morito, H. Tanaka, R. Konishi, T. Furuhara, and T. Maki : Acta Mater., 51, 2003, 1789–1799
7) H. Kawata, Y. Honda, and K. Takeda : Minerals, Metals and Materials Series, TMS2019 148th Annual Meeting &
Exhibition Supplemental Proceedings, 2019, 529–535
8) H. Kawata, Y. Honda, K. Nakano, K. Takeda, K. Hikida : ISIJ Int., 62, 2022, in press.
9) K. Takeda, N. Nakada, T. Tsuchiyama, and S. Takaki : ISIJ Int., 48, 2008, 1122–1125.
10) S. Takaki, D. Akama, N. Nakada, and T. Tsuchiyama : Mater. Trans. JIM, 55, 2014, 28–34
Fig. 1 Schematic flow of the strengthening mechanism by carbon in lath martensite structure.
Ms : martensite transformation start temperature, σγ : strength of prior austenite during martensite transformation,
ΔV : volume expansion during martensite transformation

Table 1 Chemical compositions and martensite transformation start temperatures of Fe–18Ni alloys used.
C N B Ni Ti Others Ms
Alloy
mass-ppm mass-ppm mass-ppm mass% mass% mass% °C
A 4 8 27 18.4 0.017 < 0.03 295
B 7 8 26 18.2 0.005 < 0.03 293
C 110 8 24 18.2 0.005 < 0.03 263
D 570 8 26 18.1 0.005 < 0.03 215
Fig. 2 High angle boundary maps of alloys A and D samples austenitized at 800 and 1000 °C.
black line : high angle boundary (θ : ≥ 10 degree), gray line : low angle boundary (θ : 5~10 degree)
Fig. 3 The relationship between inverse square root of the average effective grain diameter and tensile properties in lath
martensite structure. YP : yield point (elastic limit), σ0.2% : 0.2% proof stress, σ0.6% : 0.6% proof stress,
TS : maximum tensile strength (onset of plastic instability)

Fig. 4 The relationship between Hall-Petch coefficient Fig. 5 The strengthening from Alloy A with increasing of
and carbon content. carbon content, and the grain refinement strengthening.
Fig. 6 Modified schematic flow of the strengthening mechanism by carbon in lath martensite structure.
Ms : martensite transformation start temperature, σγ : strength of prior austenite during martensite transformation,
ΔV : volume expansion during martensite transformation

Effects of metal cation on corrosion of structural metals in aqueous environments
Masatoshi Sakairi1,*
1
Faculty of Engineering, Hokkaido University, Sapporo, 060-8628, Japan
*email: msakairi@eng.hokudai.ac.jp
Keywords: steel, aluminum alloy, metal cation, corrosion, surface analysis, electrochemistry
Structural metals such as carbon steels, stainless steels, and aluminum alloys are suffer from corrosion during usage.
The corrosion resistance of the structural metals in aqueous and atmospheric environments depends on the stability of passive
film. However, the passive films on the metals are destroyed by the chloride ions in chloride containing environments. It is
recognized that chloride ions are very much aggressive and destroy the oxide films1, 2), therefor, many researches have been carried
out focused on effects and role of chloride ions on corrosion behavior of structural metals3-5). The corrosion rate of structural
metals is changing in despite of similar concentrations of chloride ions in fresh water6-8). This may be due to difference of contained
metal cations. Some researchers stated that the corrosion inhibition of zinc and carbon steels is attained by the kind of metal
cations in aqueous medium at room temperature9-12). Tsuru13) also reported that Zn2+ dissolved from corrosion products on zinc
coated steel prevents further corrosion of steel substrate. The same observations14) have noticed while mild steel is exposed in the
aqueous solution with Zn2+. However it is not fully elucidated the metal cation effects on corrosion of structural metals. In this
presentation, recent authors group results related to effects of metal cations on corrosion behavior of carbon steel, stainless steel
and aluminum alloys will be explain.
Aluminum alloys
Aluminum alloys such as A3003 and A6061 are widely used because of the high strength/weight ratios, and they show
good corrosion resistance in most environments. As previously mentioned, the good corrosion resistance is explained by
protective oxide films, passive films, covering the aluminum alloy surface15-17). Generally, the corrosion rate of aluminum alloys
also depends on the concentration of chloride ions and it is considered that only little corrosion of aluminum alloys occurs in very
dilute chloride solutions such as tap waters. There are only few studies focused on corrosion of aluminum and aluminum alloys
in fresh water. However, corrosion of aluminum alloys sometimes does occur in fresh water and this causes leakage of water
when the alloy is used in containers and water supply tubes. As well know, fresh water contains very low concentrations of anions
and metal cations. It is considered that corrosion is affected by not only chloride ions but also metal cations, which are in the fresh
water. Otani et al. reported influences of metal cations in model fresh waters on the corrosion mechanisms of A3003 by metal
cation hardness theory and XPS surface analysis18, 19). Neutral model fresh waters used in the paper was 0.5 kmol m−3 H3BO3−
0.05 kmol m−3 Na2B4O7 with each one of six different salts; 1 mol m−3 KCl, 1 mol m−3 NaCl, 0.5 mol m−3 CaCl2, 0.5 mol m−3
MgCl2, 0.5 mol m−3 ZnCl2, and 0.5 mol m−3 NiCl2. Here, the metal cation hardness is based on the hard and soft acid and base
(HSAB) concept20). According to the Lewis rule concerning acid and bases, cations and anions act as acids and bases, respectively.
Acids and bases are classified into hard and soft according to the HSAB concept. The hardness of metal cations can be expressed
as follows :
" &
#X! + (ΣI# )$/& ) ,
X= 10
0
Where X M is the electronegativity of the metal atom, and In (eV) is the ionization potential from the neutral metal atom to the
given oxidized state, n. They withdraw the following results. 1) Corrosion pits of about 10 μm in diameter were observed in
solutions with soft metal cations such as Na+ and K+. The corrosion behavior of A3003 in the model tap waters changed with
metal cation hardness, X. 2) The corrosion potential increases and corrosion current decreases with increasing metal cation
hardness. 3) Hard metal cations were observed by XPS in the oxide films formed on A3003 after immersion in the model tap
waters containing these cations.
From several researches related to corrosion of A300318, 19, 21), it was established that Zn2+ is superior to inhibit the fresh
water corrosion of A3003 among the metal cations used in the studies. However, the minimum concentration of Zn2+ to inhibit
the corrosion of A3003 in model fresh water has not been determined. Establishing the minimum concentration of metal cations

is important to be able to use the metal cations in industrial environments as corrosion inhibitors. In addition, the morphology of
corrosion products formed on A3003 in model fresh water containing Zn2+ and the corrosion inhibition mechanism by Zn2+ also
have not been established. The corrosion morphology and composition of corrosion products formed on A3003 in model fresh
water with different Zn2+ concentrations were investigated by immersion tests combined with surface observations and analysis
using an Auger electron spectroscope (AES)22). The cross sectional AES observations showed that the thickness of the corrosion
product layer formed on A3003 decreases with increases in the Zn2+ concentration of the model fresh water. A cross sectional
AES point analysis suggested that the corrosion products formed on the A3003 in the Zn2+ containing model fresh water (Zn2+ >
0.1 molm-3) have a multilayered structure and that the inner of Zn-rich layer would have high corrosion protective properties.
A6061 alloy is one of the most popular aluminum alloys due to its extensive usages in the aqueous medium like as
marines’ fittings, brake pistons, hydraulic pistons, valve and valve parts, screw, machine parts, etc. The A6061 alloy contains
different elements including Mg and Zn. It is still not fully elucidate influence of metal cations on long-term immersion corrosion
at room temperature. Therefore, the research was carried out to clarify the corrosion natures of A6061 aluminum alloy in the
stated circumstances and propose a mechanism of corrosion depending on the experimental outcomes. To accomplish the
aspiration, a relative experimental condition was created, and the impact of metal cations on the corrosion of the alloy in a
simulated aqueous medium was investigated with scanning electron microscope (SEM), energy dispersive X-ray spectroscope
(EDS), X-ray photoelectron spectroscope (XPS), potentiodynamic polarization, and electrochemical impedance spectroscopy
(EIS)23). In the experiments, three different metal cation containing solutions were used as 1 molm-3 NaCl, 0.5 molm-3
MgCl2 and 0.5 molm-3 ZnCl2. The Cl- concentration of all solutions was 1 molm-3 and that is similar to that of
freshwater. From the research following conclusions were with draw. 1) The mass of the specimen was increased after different
interval of the immersion tests, and a lower mass change was observed in Zn2+ containing solution in all the cases. 2) SEM
observations showed deposited product on the Al alloy surface, and comparatively, smooth surface was observed of the specimen
immersed in the Zn2+ containing solution. 3) XPS and EDS examination results confirmed the composition of the products on
the alloy surface as aluminum hydroxide. 4) XPS results also confirmed that Zn2+ existed on the Al alloy as hydroxides after
immersion in theZn2+ containing solution. The Zn2+ formed a layer on the alloy surface that retarded the both the chloride attack
and the corrosion reactions of the alloy.
Carbon steels
Fresh water corrosion of mild steel has been investigated by many researchers because the corrosion has caused serious
problems in industries. Important factors for the fresh water corrosion of mild steel are the corrosive nature of dissolved oxygen
and the concentrations of anions such as Cl- and SO42-. On the other hand, there are reports that Zn2+ and Al3+ have corrosion
inhibiting ability24, 25). For this reason, the effect of metal cations on the corrosion of mild steel should be considered in fresh water.
However, there has been no study in which the quantitative effects of all metal cations on corrosion of mild steel in model fresh
water were investigated. The effects of metal cations on corrosion of mild steel in model fresh water were investigated by EIS,
immersion tests, and surface observation and analysis with SEM and XPS26). Following results were drown. The corrosion rate
of mild steel decreased with increase in the hardness of cations, X, in model fresh water except for solutions containing Mg2+ and
Zr2+. Therefor, The novel indicator, Y = X × ∆V, was introduced to explain the different degrees of protection of metal cations.
Where X is metal cation hardness and ∆V is molar volume difference between passive film and hydroxides of metal cations. XPS
analysis showed that hard metal cations are incorporated in the passive films of the mild steel, and hydroxides of metal cations
were formed on the mild steel after immersion for a short time. Hydroxides of metal cations that have large ∆V protect the passive
films of mild steel from penetration by chloride ions.
The effects of metal cations on the corrosion behavior of carbon steel SM490Y in 10 molm-3 Cl- model fresh water
were also investigated by immersion tests, electrochemical tests, and surface analysis27). In this experiment, three different metal
cation containing solutions were used as 10 molm-3 NaCl, 5 molm-3 MgCl2 and 5 molm-3 ZnCl2. Immersion tests and
electrochemical tests results showed that Zn2+ had a significant inhibition effect on corrosion of SM490Y. The results of EDS and
XPS showed that Zn2+ was incorporated in the oxide films by making a strong bond and formed zinc hydroxide or zinc oxide
which can cover the surface of carbon steel. It is suggested that Zn2+ forms a protective film which can efficiently prevent break
down of surface film by Cl- and inhibit the corrosion.

As previously mentioned, Cl- play a major role in corrosion because the corrosion protective oxide layer of mild steel
is easily destroyed by chloride ions in fresh water. The use of inhibitors is one method that has been reported to decrease the
corrosion of steels caused by Cl-. The influence of metal cations on the ability of gluconates to inhibit corrosion of mild steel in a
model fresh water was investigated by EIS and immersion tests28, 29). The EIS and immersion test results showed that the corrosion
inhibition of mild steel in model fresh water by gluconates was improved by metal cations that have a large value of corrosion
inhibitory effect of cation, Y. The X-ray photoelectron spectroscopy (XPS) analysis showed that metal cations that have larger Y
values are bonded on mild steel. It was thought that metal cations with large Y values and gluconates confer a synergistic inhibition
effect on the corrosion of mild steel in model fresh water.
Stainless steel
SUS304 is widely used in applications requiring high corrosion resistance. However, corrosion of stainless steel is a
serious problem in constructions such as liquid supply pipes and storage tanks, ships, and bridges. Corrosion of stainless steel
depends on the various environmental factors. One of the important factor is presence of anions (Cl- and SO42-) in the aqueous
solution. Cl- plays a major role in corrosion of stainless steel because the passive films are easily destroyed by this anion. The
effects of metal cations on corrosion of SUS304 in 0.5 kmolm-3 Cl- solution remain unknown and the corrosion inhibition
mechanism of metal cations with the passive films are not fully elucidated. The effects of metal cations on corrosion of SUS304
in 0.5M Cl- aqueous solution were investigated by immersion tests, electrochemical tests, SEM, atomic force microscope (AFM)
and XPS. In this study, three 0.5 kmolm-3 Cl- solutions with different metal cations were used as test solutions; 0.1 kmolm-3 MgCl2,
0.1 kmolm-3 ZnCl2, and 0.1 kmolm-3 AlCl3, and their Cl- concentration was adjusted to 0.5 kmolm-3 by NaCl. Therefor, 0.5 kmolm-
3
NaCl was used as a reference solution. The corrosion behavior of the stainless steel in the 0.5 kmolm-3 Cl- aqueous solution was
changed with X, and corrosion rates were closely correlated with X. Different surface morphologies were observed by SEM after
immersed in the solutions which were depended on the metal cations. Zn2+ and Al3+ contained solutions showed higher impedance
and higher charge transfer resistance as compared to other solutions. From the XPS results, Zn2+ and Al3+ were existed on the steel
as hydroxides and formed a layer by incorporating in the passive films through de-hydroxylation process. The layer of metal
cation would have good protecting ability against Cl- attack as well as corrosion reactions on the steel surface.
The corrosion behaviors of SUS 310 in model seawater (0.1 kmolm-3 MgCl2, 0.1 kmolm-3 ZnCl2, and 0.1 kmolm-3
AlCl3, and their Cl- concentration was adjusted to 0.5 kmolm-3 by NaCl) with different metal cations also investigated by
gravimetric tests and surface analysis31). Different corrosion rates were observed in different metal cationic solutions, and Zn2+
containing solution showed the lowest corrosion rate among used solutions. SEM observations showed the pits on the surface
that were different from each other. White pits were observed on the specimen immersed in the Zn2+ containing solution. XPS
results showed the presence of Zn2+ and Al3+ on the specimen immersed in the corresponding solution. Metal cations that have
large X, showed the tendency to form a fence layer on the specimen surface. The layer of metal cation would have good protecting
ability against Cl- attack as well as corrosion reactions on the steel surface.
Acknowledgement
Surface analysis of this work was conducted at Laboratory of XPS analysis, Hokkaido university, supported by “Nanotechnology
Platform” Program of the Ministry of Education, Culture, Sports, Science and Technology (MEXT), Japan.
References
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10) J. Telegdi, M. M. Shaglouf, A. Shaban, F. H. Ka'rma'n, I. Betro'ti, M. Mohai, and E. Ka'lma'n, Electrochim Acta, 46 (2001) 3791-
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11) T. Prosek, D. Thierry, and C. Taxe'n, and J. Maixner, Corros Sci, 49 (2007) 2676-2693.

12) H. Sun, S. Liu and L. Sun, J. Electrochem. Sci., 8 (2013) 3494-3509.
13) T. Tsuru, Zairyo-to-Kankyo, 59 (2010), 404-409.
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15) M. Schütze, D. Wieser and R. Bender, Corrosion resistance of aluminium and aluminium alloys, Dechema, Frankufurt, Germany,
Wiley-vch, 2010.
16) T. J. A. Richardson, Shreir's corrosion, Amsterdam, The Netherlands, Elsevier Science, 2010.
17) R. R. Winston, Uhlig's corrosion handbook. 3rd ed. Hoboken, New Jersey, ECS, Wiley, 2011.
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20) M. Misono, E. Ochiai, Y. Saito, and J. Yoneda. Inorg. Nucl. Chem., 29 (1967) 2685-2691.
21) K. Otani, M. Sakairi, and A. Kaneko, Mater Trans., 57 (2016) 1539-1546.
22) K. Otani, Md. Saiful Islam, M. Sakairi, and A. Kaneko, Surf. Inter. Anal., 51 (2019) 1207-1213 .
23) Md. S. Islam and M. Sakairi, Corros. Com. in press.
24) M. Kato, Boshoku Gijutsu, 31 (1982) 27–33.
25) S. Takasaki, Zairyo-to-Kankyo, 64 (2015) 114–120.
26) K. Otani and M. Sakairi, Corros. Sci., 111 (2016) 302-312.
27) L. Li and M. Sakairi, Tetsu-to-Hagane, 107 (2021) 1066-1073.
28) K. Otani, Md. Saiful Islam, and M. Sakairi, J. Electrochem. Soc., 164 (2017) C498-C504.
29) K. Otani, M. Sakairi, and Md. Saiful Islam, Corros. Rev.s, 36 (2018) 105-113.
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31) Md. S. Islam, M. S. Yasmin, and M. Sakairi, J. Mat. Sci. Res. Rev., in press.

3D Impedance Spectroscopy to Investigate Film Growth Rate of Chromate Film
Formed on Steel
Yoshinao Hoshi*
Department of Engineering, Graduate School of Engineering, Nagoya Institute of Technology, Nagoya, Aichi 466-8555, Japan
*email: hoshi.yoshinao@nitech.ac.jp
Keywords: steel, electrochemical impedance spectroscopy, 3D impedance, chromate film, film growth rate
An improvement of corrosion resistance of steel is required for the long-term use in the structural materials. The
chemical conversion coatings are one of the most effective methods for surface modification of steel substrates. In these
methods, the chromate conversion treatment is useful method to improve the corrosion resistance of steel. It is well known
that the dissolution from the base steel due to the scratched or defective parts on the chromate film can be suppressed by the
self-healing effect of chromate film without further treatment. As the development of a new chemical conversion coatings,
which shows self-healing effect, has been required for further improvement of the corrosion resistance of steel in recent years,
it is important to clarify the mechanisms related to self-healing effect of chromate film. Thus, the aim of the present study was
to investigate the time variation of film resistance of chromate film related to the self-healing effect on the steel surface by a
three-dimensional (3D) impedance spectroscopy 1,2) .
An electrochemical impedance spectroscopy (EIS) is useful method to investigate dissolution mechanisms of steel
because the time constant observed in the impedance spectrum can be discriminated. The parameters involving film resistance
can be estimated by the curve-fitting of the measured impedance spectrum using an equivalent circuit. In this method, a time
stability is required in the electrode condition, indicating no variation of electrode reaction rate during the impedance
measurement. As the electrode reactions related to the self-healing effect of chromate film on the steel do not satisfy the time
stability, the distortion of impedance spectrum is observed in the low frequency range on the Nyquist plane. In this case, it is
difficult to estimate the film resistance related to the self-healing effect of the chromate film formed on the steel surface by the
curve-fitting of the measured impedance spectrum using the equivalent circuit.
We applied the 3D impedance spectroscopy 3-5) for investigation of the self-healing effect of the chromate film
formed on steel surface. In the impedance measurement, the impedance spectra were measured successively, and the
impedance was plotted on the 3D diagram whose axes are real, imaginary and time. The plots of impedance are connected by
the spline under tension function at each frequency. Because the instantaneous impedance at an arbitrary time can be obtained
from 3D diagram, the parameters involving film resistance can be estimated by the curve-fitting of the instantaneous
impedance at an arbitrary time using an equivalent circuit. We employed the 3D impedance spectroscopy for the investigation
of the time variation of the film resistance related to the self-healing effect of chromate film formed on the steel surface 1,2). We
prepared the scratched electrodes of chromated steel and chromated galvanized steel for the 3D impedance measurement in
order to examine the self-hearing effect of the chromate film. As we could obtain the instantaneous impedance at arbitrary
time from 3D impedance plot, the film resistance of each scratched electrode could be estimated by the curve fitting of the
instantaneous impedance using the equivalent circuit. I will present the 3D impedance of different types of scratched
electrodes of chromated steel and chromated galvanized steel, and I will discuss the film growth rate of chromate film owing
to self-hearing effect based on the time variation of film resistance estimated from instantaneous impedance at arbitrary time.
References
1) Y. Hoshi, Y. Endo, I. Shitanda, M. Itagaki, Y. Suzuki and S. Yamaguchi: J. Surf. Finish. Soc. Jpn., 67, (2016)
494-498.
2) Y. Hoshi: J. Surf. Finish. Soc. Jpn., 72, (2021) 462-466.
3) Z. B. Stoynov and B. S. Savova – Stoynov: J. Electroanal. Chem. 183 (1985) 133-144.
4) M. Itagaki, N. Kobari, S. Yotsuda, K. Watanabe, S. Kinoshita, M. Ue: J. Power Sources 135 (2004) 55-261.
5) M. Itagaki, K. Honda, Y. Hoshi, I. Shitanda: J. Electroanal. Chem. 737 (2015) 78-84.

Roles of Interstitial Elements in Anodic Dissolution Resistance of Martensitic Steels
Mariko Kadowaki1, Arkapol Saengdeejing2, Izumi Muto3, Ying Chen2, Yu Sugawara3, and Nobuyoshi Hara3
1
2
Fracture and Reliability Research Institute, Tohoku University, Sendai, Miyagi 980-8579, Japan
3
Department of Materials Science, Tohoku University, Sendai, Miyagi 980-8579, Japan
*email: KADOWAKI.Mariko@nims.go.jp
Keywords: carbon steel, corrosion resistance, martensite, polarization measurements, first-principles calculations
1. Aim and Scope

Martensitic carbon steels are favored for use as structural materials in applications such as automobiles and other
vehicles because of their excellent mechanical properties. The presence of interstitial carbon strongly affects the movements of
dislocation and imparts high strength to the steels. In addition to its effect on the mechanical properties, interstitial carbon also
plays an important role in the corrosion resistance of steels. It has been widely reported that interstitial carbon enhances the
corrosion resistance of steels 1-3). However, the reason for the superior corrosion resistance provided by interstitial carbon is
still unclear. In this research, both electrochemical measurements and first-principles calculations were conducted to
investigate the effect of interstitial carbon on the corrosion resistance of martensitic carbon steels.

The specimen was AISI 1045 carbon steel (0.44%C, 0.20%S, 0.85%Mn, <0.01%P, <0.01%S, <0.01Ni, <0.01Cr,
0.035%Al, 0.003%N, 0.002%O, all in mass%). The specimens were heat-treated at 1123 K for 10 h in air (21 vol.% O2 and
79 vol.% N2) and subsequently water-quenched. During this heat-treatment, the specimen surfaces were decarburized by the
oxygen in the air. As a result, a low carbon martensite was generated in the surface region of the specimens, and a high carbon
martensite (0.44 mass% C) was formed in the specimen core. The electrochemical properties of the low and high carbon
martensitic structures were measured separately using the surface and core regions. Potentiodynamic anodic polarization of
the low and high carbon martensitic specimens was conducted using boric-borate buffer solution with 1 mM NaCl at pH 8.0.
In addition to the electrochemical measurement, the first-principles calculations based on density functional theory
(DFT) implemented in the Vienna Ab initio Simulation Package (VASP) were carried out. The projector augmented wave
(PAW) method was employed 4). The exchange and correlation were treated using the generalized gradient approximation
(GGA) of Perdew-Burke-Ernzerhof (PBE) 5). For the calculation, the supercells with bulk bct crystal structures were used. All
the supercells included one interstitial carbon in the octahedral site. The carbon concentration was varied from 0.40 at.% to
5.88 at.% by changing the size of supercells.
3. Results
In the potentiodynamic polarization curves of the low and high carbon martensitic specimens in 1mM NaCl
containing boric-borate buffer at pH 8.0, the region of active dissolution appeared on both specimens at about -0.5 V. The
active dissolution current of high carbon martensite was lower than that of low carbon martensite, indicating that active
dissolution was suppressed by interstitial carbon.
Next, to clarify the reason for the superior dissolution resistance obtained by the interstitial carbon, first-principles
calculations were conducted, and the effect of interstitial carbon on the electronic density of states (DOS) of iron was analyzed.
It has been widely known that the valence electrons at Fermi level are readily transferred among ions and metals during
electrochemical reactions. Therefore, the DOS at and near the Fermi level is important for determining the electrochemical
reactivity 6, 7 ). In other words, it is understood that a high DOS at and near the Fermi level increases the electrochemical
reactivity. Since the active dissolution of steels is the oxidation reaction of iron, the DOS at and near Fermi level is one of the
important parameters for determining the resistance against active dissolution. The calculation results clearly showed that the
DOS of the iron near and at the Fermi level decreased with the increases in the interstitial carbon content. That is, it is highly
likely that the electrochemical reactions such as the active dissolution are considered to be suppressed by interstitial carbon.

In addition to above calculations, the charge distribution around interstitial carbon was analyzed. It was confirmed
that regions with a high charge density between the iron and carbon atoms, and the valence electrons were transferred from
the iron atom to the carbon atom. Considering that the valence electrons near and at the Fermi level determine the nature of
the electrochemical reactions including dissolution reaction, this electronic interaction also appeared to be related with the high
dissolution resistance of martensite.
4. Conclusions
1) According to the polarization measurements, the interstitial carbon suppressed the dissolution reaction of
martensite.
2) First-principles calculations showed that the electronic density of states (DOS) of iron near the Fermi energy
decreased with increasing interstitial carbon.
3) The change in the electronic structure of iron appeared to be related with the superior dissolution resistance
provided by interstitial carbon.
Acknowledgement
This work was performed under the support of a Grant-in-Aid for JSPS Research Fellow (grant No. JP18J20518). The
authors acknowledge the Center for Computational Materials Science of the Institute for Materials Research, Tohoku University for
the support of the supercomputing facilities.
References
1) F. J. Martin, P. M. Natishan, E. J. Lemieux, T. M. Newbauer, R. J. Rayne, R. A. Bayles, H. Kahn, G. M. Michal, F. Ernst,
and A. H. Heuer: Metall. Mater. Trans. A 40A (2009) 1805.
2) A. Chiba, M. Koyama, E. Akiyama, and T. Nishimura: J. Electrochem. Soc. 165 (2018) C19.
3) M. Kadowaki, I. Muto, Y. Sugawara, T. Doi, K. Kawano, and N. Hara: J. Electrochem. Soc. 164 (2017) C962.
4) G. Kresse and J. Furthmüller: Phys. Rev. B, 54 (1996) 11169.
5) G. Kresse and D. Joubert: Phys. Rev. B, 59 (1999) 1758.
6) P. C. Searson, P. V. Nagarkar, and R. M. Latanision: Int. J. Hydrogen Energy 14 (1989) 131.
7) L. M. C. Pinto, P. Quaino, E. Santos, and W. Schmickler: ChemPhysChem 15 (2014) 132.

Corrosion resistant steel for bridges and life cycle cost
Fumio YUSE1*, Masahiro MATSUSHITA2
1 Materials Research Laboratory, Kobe Steel, LTD., Kobe, Hyogo 651-2271, Japan
2 Steel development section Kakogawa works, Kobe Steel, LTD., Kakogawa, Hyogo 675-0023, Japan
*email: yuse.fumio@kobelco.com
Keywords: bridge, corrosion, life cycle cost, coating, long-life steel sheet for coating
1. Introduction
In recent years, in the field of bridges, the recognition of maintenance, painting, and anticorrosion has been
increasing, and in addition to the reduction of initial construction cost, the reduction of maintenance costs and life cycle cost
(LCC) is required 1,2). In steel bridges, coating is carried out from the viewpoint of corrosion protection and appearance, but it
is necessary to repaint the coating because the coating film deteriorates over time and the corrosion protection performance
declines. Even in heavy anticorrosion coating systems, which have a longer coating life than general coating systems, the
period until the anticorrosion performance deteriorates is shorter than the service period of the bridge. Therefore, repainting
must be performed during the service period to maintain the anticorrosion performance. Therefore, prolonging the repainting
cycle is effective for LCC reduction.
In the examination of LCC, it is necessary to clarify the criteria for the degradation level of coating film and the
recoating time for the required performance. It is said that the repainting time will be decided by conducting a step-by-step
evaluation of each item of rust, peeling, discoloration and staining by inspection 3). Various factors are involved in the
deterioration of the coating film of actual steel bridges, and the deterioration progresses. It is said that local corrosion as well as
uniform corrosion occurring on the surface of the steel plate should be taken into consideration. Therefore, in many cases,
standards are set by each entity that conducts maintenance management. In addition, it is often difficult to continuously
observe the deterioration of coating film and subsequent corrosion evaluation of steel over a long period of time.
In this study, as a consideration of LCC, we report the results of corrosion resistance evaluation of long-term
exposure test for 15 years and examination of repainting life using ordinary steel and developed steel 4) (long-life steel sheet
for coating, which satisfies all the relevant JIS standards for conventional welded structural steel (JIS G 3106; SM) and has a
new function of inhibiting corrosion under the coating film added to the steel itself).
Coating is a corrosion prevention method that protects steel by blocking corrosion-promoting substances such as
oxygen, water and chloride ions from the coating film formed on the steel surface. As time passes, the coating film
deteriorates and its corrosion protection performance declines. In other words, the degree of deterioration, which is a corrosion
index, increases with the number of years passed. When the index reaches a certain level, repainting should be considered (Fig.
1). Rusting, peeling, and blistering are used as indicators of deterioration in the corrosion protection performance of the
coating film, and the area ratio of rusting, peeling, and blistering is used as an index.
In general, the corrosion of steel bridges tends to start from the scratches and corners of the coating, and it has been
reported in some cases that the initial defects such as scratches and partial lack of coating thickness are the starting point for
the corrosion of heavily corrosion-protected coating systems, rather than the deterioration from the coating surface. In this
study, blister width was used as a corrosion index of coated steel.
Small specimens of ordinary steel and developed steel were placed under the girder of a bridge in Kobe City,
Hyogo Prefecture, and exposure tests were conducted (Fig. 2). The small specimens (150 x 70 x 6 mm) were sealed on the
back and sides with tape and coated with the old C-4 coating system (75 μm inorganic zinc, 120 μm epoxy resin, and 55 μm
fluorocarbon resin for a total of 250 μm). After curing, artificial coating defects were imparted with a box cutter knife to
simulate the scratched areas where rust tends to spread. As a comparison, a bare (unpainted) specimen was also placed on the
same exposure stand.

The specimens were observed for appearance (cracking, peeling) and the blister width of the artificial coating
defect was measured. The specimens were cut and cross-sectional observation (video microscopy, SEM, EPMA analysis) was
conducted. In addition, X-ray diffraction measurements of the rust removed from the bare specimens were carried out to
identify and quantify the rust components.

Fig. 3 shows the measurement results of the blister width of the artificial coating film defect after the exposure test.
Because of the effect of the inorganic zinc layer, the progress of corrosion was slow, and the absolute value of blister width
was small, but developed steel was smaller than that of ordinary steel. From the cross-sectional observation result of the
artificial coating film defect part, it was confirmed that the inorganic zinc layer remained under the coating film, but
disappeared in the coating film defect part, and iron rust was observed. The corrosion depth of the steel material in the lower
part of the coating film was larger in the ordinary steel, and the corrosion progressed in the thickness direction.
The corrosion loss of bare (unpainted) developed steel specimens was measured, and the results of comparison
with those of ordinary steel are shown in Fig. 4. The corrosion rate of developed steel is smaller than that of ordinary steel year
by year, and the initial component design has been achieved. And, formed rust densification (beta-FeOOH) was also
confirmed 5,6). The same state is observed in the coating film defective part of the coating material, and the amount of
corrosion and the amount of generated rust are small, and as a result, it is presumed that the coating film blister is suppressed.
Fig. 5 shows the mechanism assumed to occur in improving the corrosion resistance of paint films on the
developed steel. This mechanism is expected to work to inhibit under-film corrosion even when corrosion originates in defects
in paint films.
In this study, if the blister width (1 mm) is set as the degradation standard, it can be assumed that the standard is
reached after 10 years for ordinary steel, while it is reached around 13 years for developed steel in Fig. 3. Assuming that the
repainting life is the number of years required to reach the degradation standard, the repainting life of ordinary steel is 10 years
and that of coated steel is 13 years, which means that the repainting life of coated steel is about 1.3 times longer than that of
ordinary steel.
Assuming that the service life of a steel bridge is 100 years and that the service life of the old C-4 coating system of
ordinary steel is 30 years, the repainting service life of developed steel is calculated to be 1.3 times longer (about 39 years),
and the number of repainting decreases from three to two. In other words, the developed steel can contribute to the reduction
of LCC of steel bridges (Fig. 1).
4. Conclusion
A 15-year exposure test was conducted on an actual bridge. The results show that the developed steel, a steel plate
for bridges with long-life coating, exhibits excellent resistance against coating corrosion compared with ordinary steel. The
results, including the results of rust analysis, indicate that the mechanism of inhibiting under-film corrosion is working as
expected. The repainting life of the developed steel is considered to be about 1.3 times longer than that of the ordinary steel at
present, so it is expected to enable re-painting cycles to be lengthened and reduce the life-cycle cost of steel bridges.
References
1) Japanese Society of Steel Construction: JSSC Technical Report, No.55(2002) pp.24-41.
2) T. Tamakoshi : Report of General Studies on Land and Infrastructure Management. Ministry of Land, Infrastructure,Transport and
Tourism. No.294,(2006) p.1-3.
3) Japanese Society of Steel Construction : Heavy Duty Coating (Gihodo-books Japan, 2012)pp.153-163.
4) F.Yuse, M Matsushita and M Izumi: KOBELCO TECHNOLOGY REVIEW NO. 34 (MAR. 2016) pp.6-11.
5) T. Ishikawa: Zairyo-to-Kankyo. Vol.52, No.3 (2003), p.140-154.
6) F.Yuse: Rust Rrevention & Control Japan, Vol.63, No.6 (2019) pp.22-29.

Fig. 1 Schematic diagram of relationship between repainting life and corrosion index (degree of corrosion) and life cycle cost image.
Fig. 2 Example of installation location Fig. 3 Relationship between exposure years and Fig. 4 Relationship between exposure
and exposure test conditions. blister width of ordinary steel and developed steel. years and thickness loss.
Fig. 5 Mechanism of inhibition of under film corrosion on the developed steel.

Fundamentals of Corrosion Engineering of Metallic Materials and Development of
Ultrahigh Corrosion Resistant Stainless Steels by Novel Laser Techniques
TSUTSUMI Yusuke,
email: TSUTSUMI.Yusuke@nims.go.jp
Keywords: stainless steel, zirconium, corrosion resistance, inclusions
1. Introduction
In the field of materials engineering, physical properties such as mechanical properties are considered as the most
important properties, however, chemical properties such as corrosion resistance are also critical properties that cannot be
ignored. In particular, Japan is island country where metallic materials are frequently used in coastal areas. Therefore, the
problems of failures and accidents caused by corrosion reaction of structural materials in our countries are more serious than
in other countries. The author and the researchers in our group have been studying the corrosion evaluation and the
development of techniques to improve the corrosion resistance of biomaterials and structural materials. In this presentation,
the efforts of these researches will be introduced.
2. Electrochemical surface treatment for removement of inclusions on metals

Zr possesses high corrosion resistance in both acid and alkali solutions owing to the passive film on its surface.
However, similar to stainless steels, it is susceptible to localized corrosion by chloride ions. When Zr is used as implant
materials, the concentration of chloride ions in a living body is always maintained at approximately 0.14 mol L-1 via
physiological homeostasis. The implanted Zr will necessarily be in contact with the chloride ions in the body environment,
and the use of inhibitors to prevent corrosion is inappropriate. Therefore, the biosafety of Zr can be evaluated by elucidating
the mechanism of the localized corrosion in chloride-ion-containing solutions. With the above background, the authors have
performed research on the development of surface treatment methods that enable the improvement of localized corrosion
resistance of Zr prior to research on stainless steels. Similar to stainless steel, it was considered that the selective elimination of
the corrosion-inducing inclusions will increase the localized corrosion resistance of Zr. Thus, novel electrochemical treatments
comprising anodic and cathodic polarization cycles were developed in the present study to eliminate the inclusions on the Zr
surface. The corrosion resistance of the Zr specimens, which were subjected to electrochemical treatments under various
conditions, was evaluated using anodic polarization tests in a simulated body fluid.
Figure 1 shows a schematic illustration of the concept of the electrochemical surface treatment that was developed
in this study. Surface on Zr and stainless steels contain numerous exposed inclusions. When the surface is anodically polarized
over a certain potential in chloride-containing solutions, the local dissolution of one of the most soluble inclusions is initiated.
This is accompanied by the dissolution of the surrounding matrix of the inclusion. When the applied potential is switched and
the specimen is cathodically polarized, the anodic reaction is electrochemically suppressed. This results in the inhibition of the
dissolution reaction and the repassivation of the surface. The progress of the forced dissolution reaction via anodic polarization
results in the expansion of the corrosion dip. When the dissolution dip expands to beyond a certain size, the inner inclusion is
Fig. 1 Schematic illustration of the electrochemical surface treatment performed in this study1)

completely dissolved; alternatively, the inclusion loses the mechanical support from the contacting matrix and is released into
the solution. This prevents the dissolution of the repassivated sites, even during the application of the anodic potential in
subsequent steps. The multiple anodic and cathodic polarization cycles decrease the number of inclusions that are responsible
for localized corrosion, and the repassivated dips remains on the specimen surface. Furthermore, the easily dissolved
inclusions are highly likely to be removed, and the inclusions that are most probable to induce the corrosion of the specimen
are removed preferentially. Therefore, the devised electrochemical surface treatment comprising anodic and cathodic
polarization cycles is expected to significantly improve the corrosion resistance of the treated materials.
Figure 2(a) shows the low-magnification OM
image of the electrochemically treated Zr surface. The
presence of numerous black dots along with an
interference-colored area around the dots was observed. Figure
2(b) shows the high-magnification LM image and
three-dimensional profile image of the area around one of the
black dots. The numerous dots represented a micron-scale dip
indicated a trace of the dissolved inclusion. The anodic
reaction rate was effectively controlled under the constant
current condition. The Zr ions that were produced from the
anodic reaction site diffused into the surrounding matrix.
Subsequently, corrosion products such as Zr oxide and
hydroxide were formed owing to the significant increase in the
pH that was assisted by the buffering ability of the treatment
electrolyte. The interference-colored areas around the dips
might have originated from the deposition of the corrosion
products.
These results indicate that the repeated cycles of
electrochemical anodic and cathodic voltages and currents can
selectively remove inclusions that induce localized corrosion
on Zr surfaces. This technique can also be applied to stainless
steels. One recent study has shown that only MnS inclusions
on austenitic stainless steel (Type 316L) surfaces can be
selectively dissolved and removed by adjusting the selection of
(a) Low magnification OM image, and (b) High
the treatment medium and the conditions of the voltage and
magnification laser micrograph and 3D depth
current cycles. Details will be presented in the day's
profile of the Zr surface after the electrochemical
presentation.
treatment.1)
3. Fabrication of inclusion-free matrix by additive-manufacturing techniques
Recently, laser powder bed fusion (LPBF) process which is a type of additive manufacturing (AM), has been
attracting attention as an advanced processing tool for fabrication of metallic materials especially in biomedical field. The
direct-forming process by AM with the applicability of intricate-structured materials is strong advantage for manufacturing
value-added and relatively small products such as medical implants or aerospace assemblies. Thus, corrosion resistance of
type 316L austenitic stainless steel fabricated by LPBF with various difference in the preferential orientation and the exposed
plane direction was investigated.
Gas-atomized 316L stainless steel powder (EOS GmbH, Germany) was used as the primary material for specimen
fabrication by LPBF in this study. The nominal composition of the powder was Fe-18Cr-14Ni-2.5Mo-0.03C, and the powder
particle size was < 53 μm. The LPBF process was performed in an argon atmosphere using a 3D printer (EOSM290, EOS
GmbH, Germany). The crystallographic texture of LPBF-processed materials can be controlled by adjusting the scanning
strategy and laser irradiation conditions. To examine the evolved texture and planes of interest of the specimens, the z-axis was
defined as the build direction, and the x- and y-axes were defined as the laser scanning directions. In this study, we fabricated

cubic 316L specimens with dimensions of 11 mm × 11 mm × 11 mm under different LPBF conditions. The xz- and yz-planes
in specimens B and C fabricated using the XY-scan strategy were considered equivalent; therefore, the corrosion tests for the
xz-plane were omitted. The specimens were cut mechanically to expose their yz-, xz-, and xy-planes. No post-processing was
performed on the LPBF specimens.
The mirror-finished surfaces of both the commercially available stainless sheet and LPBF-processed specimens
(plate-shaped and process condition A: the most strongly oriented cystalographic texture, respectively) were observed. The
optical and secondary electron micrographs of each specimen are shown in Fig. 3. The commercially available specimens
showed a large number of small particles, indicating the presence of exposed inclusions of various sizes. Meanwhile, in the
case of the LPBF-processed specimens, the exposed planes (yz, xy, and xz) hardly showed the presence of inclusions. Thus,
the precipitation of metal inclusions, which led to localized corrosion, could be effectively inhibited by the LPBF process.
Fig. 3 Surfaces of 316L stainless steels prepared from commercially available sheet and LPBF process observed via laser
microscopy (upper) and SEM (lower) 2)
4. Corrosion resistance evaluation

Anodic polarization tests (linear sweep voltammetry) were performed using a potentiostat (HABF-501G, Hokuto
Denko, Japan) connected to a function generator (HB-111, Hokuto Denko, Japan) with an analog cable. A saturated calomel
electrode (SCE) and platinum electrode were used as the reference and counter electrodes, respectively. The specimens were
fixed in a polytetrafluoroethylene holder with an O-ring. The exposed area contacting the electrolyte was 0.35 cm2 (6.7 mm in
diameter). After immersing the specimens in a simulated body fluid (physiological saline: 0.9 mass% NaCl aqueous solution,
aerated) at 37 °C, their open circuit potentials (OCPs) were recorded for 10 min. Then, a gradient anodic potential was applied
at a constant sweep rate of 1 mVs-1 from the initial potential of −50 mV from the OCP. The measurement was stopped when
the current density limit of 1 mAcm-2 was recorded. The tests for all five specimens were conducted under open-air conditions.
Figure 4 shows the polarization curves of the electrochemically treated Zr specimens and LPBF-processed type 316L stainless
steel specimens in physiological saline. The pitting potentials of all specimens that were specially treated or fabricated were
significantly higher than those of reference specimens. These experimental results indicate that localized corrosion of these
specimens is significantly inhibited, resulting in almost no risk of corrosion occurrence even in corrosive environments
containing chloride ions.

Fig. 4 Polarization curves of electrochemically-treated Zr (left) and LPBF processed type 316L stainless steel (right)
measured in physiological saline (0.9mass% NaCl aqueous solution at 310K, open-air condition) 1,2)
5. Conclusions
The present study demonstrated two-individual techniques for improvement of metallic materials: the
electrochemical treatments comprising anodic and cathodic polarization cycles for removement of inclusions, and LPBF
process for fabricating inclusion-free metallic structures. Both techniques are highly effective in inhibiting localized corrosion
in chloride ion environments. In other words, inclusions on the surface and inner matrix of the materials are key factor in the
occurrence of localized corrosion. If such inclusions can be selectively removed, the materials can reclaim their original and
intrinsic corrosion resistance. Authors believe that these techniques will be utilized in the establishment of a sustainable
societies in future.
References
1) Manaka T, Tsutsumi Y, Ashida M, Chen P, Katayama H, and Hanawa T: Mater. Trans.. 62 (2021) 788-796.
2) Tsutsumi Y, Ishimoto T, Oishi T, Manaka T, Chen P, Ashida M, Doi K, Katayama H, Hanawa T, and Nakano T: Additive
Manufacturing 45 (2021) 102066.

Corrosion Behavior of Steel Rebar in Concrete
Studied with Hyperbaric-oxygen Accelerated Corrosion Test
Kotaro Doi1,*, Sachiko Hiromoto1, Eiji Akiyama1 and Koichi Tsuchiya2
1
2
International Center for Young Scientists, National Institute for Materials Science, Tsukuba, Ibaraki 305-0047, Japan
*Email: DOI.Kotaro@nims.go.jp
Keywords: steel rebar, concrete, corrosion, mill scale, hyperbaric-oxygen accelerated corrosion test
1. Introduction
Concrete structures containing steel rebar are widely used for large-scale constructions such as buildings, bridges and
highways. Concrete structures often lose their long-term reliability by corrosion of steel rebar. Nowadays, many concrete
structures require repair or reconstruction because of their aging. Generally, in concrete, alkalinity of the environment is
helpful for reinforcing steels to form the passive films and to exhibit superior corrosion resistance. Therefore, it is difficult to
demonstrate corrosion of reinforcing steel in concrete in the laboratory in a short time. A new method for acceleration of
corrosion of reinforcing steel is necessary.
Recently, some researchers tried to accelerate the corrosion of steel rebar in concrete by enhancement of metal dissolution.
On the other hand, we developed a novel accelerated corrosion test method (Hyperbaric-oxygen Accelerated Corrosion Test,
HOACT)1). In the HOACT, the oxygen reduction reaction which is the rate-limiting process of steel rebar corrosion is
enhanced by preparing the pressurized oxygen gas, and the corrosion of steel rebar in concrete is accelerated.
In this presentation, the effect of oxygen gas pressure and Cl- concentration in mortar on the corrosion of iron in mortar
was examined. In addition, the role of mill scale on the corrosion of steel rebar in mortar and the mechanism of steel rust
formation in mortar was also examined.
2. Effect of oxygen gas pressure and Cl- concentration in mortar on the corrosion of iron in mortar2)
A pure iron (99.5 %) coupon embedded in mortar with cover thickness of 5 mm was used for HOACT. The mortar was
produced by mixing of ordinary Portland cement paste and fine aggregates with a weight ratio of water-cement to fine
aggregates of 0.6:1:3. In the mortar, NaCl solution was used as mixing water to induce breakdown of the passive film on the
sample. Cl- concentration of mixing NaCl solution was 0, 0.6, and 2.0 M. In the HOACT, the sample was exposed to a humid
pressurized O2 gas or ambient air at over RH 95% in the high-pressure container. The O2 gas pressure was 0.1, 0.4, 0.6, 1.1,
and 2.1 MPa. After 14-day HOACT, the sample was extracted from mortar, and surface of the sample was observed using the
optical microscope. The cross section of the samples was characterized using scanning electron microscope (SEM) by
detecting back scattered electron.
The sample was hardly corroded in ambient air without Cl- because the passive film protected the sample surface. The
sample with 0.6 M Cl- was corroded in 0.1 and 0.4 MPa pressurized O2 gas. In addition, the corrosion on the sample with 2.0
M Cl- was obviously accelerated in 0.1, 0.4 0.6, and 1.1 MPa pressurized O2 gas. The passive film breakdown and metal
dissolution were enhanced by Cl- and the oxygen reduction was enhanced by supplied pressurized O2 gas. However, corrosion
of the sample was little observed in case of containing 0.6 M Cl- over 0.4 MPa O2, and 2.0 M Cl- in 2.1 MPa O2 contrary to
expectation. The thickness of rusts of the sample containing Cl- was increased with an increase in oxygen pressure until it
reached to a peak value, then the thickness of rusts adversely decreased over the peak value of oxygen pressure. The peak
value of oxygen pressure increases with an increase in the amount of Cl-. With 2.0 M Cl-, the thickest rust was formed in 0.6
MPa O2 gas. Up to 0.6 MPa, the thickness of rusts increased in proportion to the oxygen pressure. This result indicates that the
HOACT has an adequate oxygen pressure to efficiently enhance the corrosion of sample in the case of relying on Cl- addition
to mortar to breakdown of passive film.

3. Role of mill scale on the corrosion steel rebar in mortar3)
Commercial steel rebars are produced by hot-rolling, and thick layers of iron oxides (mill scales) are formed on the steel
rebars. In this study, the role of the mill scale on the corrosion behavior of steel rebars in concrete was investigated by using
the HOACT and anodic and cathodic potentiodynamic polarization measurements. The sample was commercial steel rebar
with 19 mm diameter with or without mill scale. To remove the mill scale on the sample surface, electrolytic polishing was
carried out. The samples were embedded in mortar with 5.5 mm cover thickness. In order to enhance breakdown of passive
film on the steel rebar, 2.0 M NaCl solution was mixed to the mortar. Using these sample, HOACT was conducted. In the
HOACT, a pressured oxygen gas of 0.6 MPa was supplied to the samples in mortar. For comparison, corrosion of the samples
in mortar under ambient air was also discussed. After finishing the corrosion test under pressurized oxygen or ambient air, the
samples in mortar were embedded in resin, and steel rust formation between steel surface and mortar was observed using an
optical microscope and SEM. In addition, composition of the steel rust was analyzed using Raman spectroscopy
measurement. To investigate the effect of the mill scale on the corrosion resistance of the rebar, anodic and cathodic
polarization measurements of the steel rebars with and without mill scale were carried out in a simulated concrete pore
solution. Mercury-mercury oxide (Hg/HgO) electrode and Pt wire were used as reference and counter electrodes, respectively.
In the anodic polarization test, a saturated Ca(OH)2 solution with 0.23 M NaCl was used as an electrolyte at room temperature
to simulate the environment in mortar. The steel rebars were immersed in the electrolyte for 10 min until the open-circuit
potential (OCP) was stabilized, and then the potential of the steel rebars was swept with a sweep rate of 20 mV min-1 from
OCP until the current density reached 102 A m-2.
From the results of surface and cross section observation of mill scale, it was revealed that the mill scale of about 40 m
thickness was formed on the steel substrate, and the mill scale had initial defects in some places. In addition, there was a
crevice between the mill scale and the steel substrate. The corrosion of the rebar with mill scale was more significant than that
without mill scale. In the case of the sample with mill scale after 14-day HOACT, a rust layer initiated at the crevice between
the steel surface and mill scale, whereas no obvious corrosion was observed on the rebar without mill scale. From the results
of the HOACTs, it can be said that the corrosion resistance of steel rebars in the mortar is reduced by the presence of the mill
scale. The pitting potential of the rebar with mill scale obtained in the anodic polarization measurement was more noble than
that of the sample without mill scale. However, when the mill scale was scratched, the pitting potential was significantly
shifted to the less noble direction and it was below that of the rebar without mill scale. These results show that the mill scale
improves the corrosion resistance of the rebar in mortar, whereas the corrosion resistance of the steel rebar becomes even
worth than that of the rebar without mill scale when the mill scale contains defects. The mechanism of decreasing the
corrosion resistance of steel rebar with mill scale in concrete is presumably that the localized corrosion is enhanced in the
crevice between the mill scale and the steel rebar surface due to the intrusion of the solution containing Cl- and oxygen
through the initial defects of the mill scale.
Acknowledgement
This work was performed under the support of Cross-ministerial Strategic Innovation Promotion Program (SIP),
“Infrastructure maintenance, renovation and management” (Funding agency: JST) and Leading Initiative for Excellent Young
Researchers (Funding agency: JSPS).
References
1) K. Doi, S. Hiromoto and E. Akiyama: Materials Transactions, 59(6) (2018) 927-934.
2) K. Doi, S. Hiromoto, H. Katayama and E. Akiyama; Journal of the Electrochemical Society, 165(9), (2018) C582-C589.
3) K. Doi, S. Hiromoto, T. Shinohara, K. Tsuchiya, H. Katayama and E. Akiyama; Corrosion Science, 177 (2020) 108995.

Tensile Fracture of High Mn TWIP Steel
Kyung-Tae Park
Dept. of Mater. Sci. Engr., Hanbat National University, Daejeon, 34158, Republic of Korea
*email: ktpark@hanbat.ac.kr
Keywords: TWIP steel, Notch tensile tests, Plastic localization, Dimple fracture, Stress triaxiality
The two most appreciable fracture characteristics of Fe-Mn-C(-Al) twinning induced plasticity (TWIP) steel under
uniaxial tension are the near-absence of diffused necking and the fracture surface entirely consisting of fine dimples. These
characteristics are quite at odd in light that fracture of usual ductile austenitic steels such as austenitic stainless steel exhibits
considerable necking and relatively large dimples. TWIP steel and austenitic stainless steel possess relatively high stain
hardenability leading to remarkable combinations of elongation and tensile strength. The dominant mechanisms of strain
hardening and deformation of both steels are either similar or different depending on the stacking fault energy, i.e. transformation
induced plasticity (TRIP) or TWIP or planar glide. TWIP steel usually has the higher C content than austenitic stainless steel.
Accordingly, the unique fracture behavior of TWIP steel is thought to be closely related to mechanical twinning and its higher C
content. In the presentation, the fracture characteristics of TWIP steel under uniaxial tension reported in literature are reviewed
and discussed.
Macroscopic fracture
Macroscopic features of fracture of the smooth specimen of an Al-bearing TWIP steel (Fe-15Mn-0.65C-2Al) plate
under room temperature uniaxial tension (the nominal strain rate of 10-3 s-1) are shown in Fig. 1. The steel was annealed after cold
rolling and the grain size was ~25 m. A consecutive series of digital image correlation images showing effective strain
distribution at the moment of fracture (Fig. 1a) reveals (a) uniform deformation without PLC bands up to fracture, (b) near-
absence of diffused necking, (c) the highest effective strain at the center of the gage width at the fracture area, and (d) fracture
normal to the loading direction. Besides, the thickness-wise slant fracture is evident (Fig. 1b) and shallow surface cracks mostly
normal to the loading direction are observed near the fracture front (Fig. 1c). These features reveal a brittle nature of TWIP steel
macroscopically in spite of high strain hardenability and large uniform elongation.
Fig. 1 (a) Effective strain distribution at the moment of fracture, (b) SEM micrographs showing the thickness-wise slant fracture, (c) and the
front surface cracks of the Fe-15Mn-0.65C-2Al TWIP steel plate.
The brittle fracture features of TWIP steel (in particular without Al) are often explained by dynamic strain aging (DSA)
associated with C - dislocation interactions, i.e. Portevin - Le Chatelier (PLC) effect 1). DSA results in plastic localization in the
form of PLC band during deformation. In the stress-strain response, the serrated flow and negative strain rate sensitivity reflect
repetitive formation and propagation of PLC bands. The plastic localization is favored by plastic instability (Considére criterion),
strain rate softening (negative strain rate sensitivity) and thermal softening (due to adiabatic heating) 2,3), i.e. Eq. 1.
𝛿𝜀 𝛿𝜀 𝛿𝑇 0 (1)
Thermal softening is not significant compared to other contributions in the usual quasi-static tensile tests. The formation and

propagation of PLC bands enhance plastic localization. PLC band propagation occurs under near-constant stress (e.g. the plateau
portion in the type I serrated flow curve), providing a local plastic instability (the first term in Eq. 1) 1). The higher strain rate causes
the less waiting time of dislocations ahead of obstacles and weakens the C pinning effect, leading to negative strain rate sensitivity
(strain rate softening, the second term in Eq. 1). These two combined effects prompt plastic localization that causes the absence
of necking in Al-free TWIP steel. Al is known to alleviate aforementioned macroscopic brittleness by decreasing the C activity
and diffusivity 4). The absence of PLC bands in the uniformly deformed gage section and limited but detectable necking in the
Al-bearing steel in Fig. 1a are the effects of Al addition. The fracture appearance depends on the strain rate 3). While fracture
entirely occurs normal to the tensile direction under quasi-static conditions (e.g. Fig. 1a), the slant fracture along the macroscopic
slip lines, not only thickness-wise but width-wise, occurs with increasing the strain rate. The highest effective strain at the center
of the gage width at the fracture area indicates initiation of central cracks. Meanwhile, the surface cracks are reported to remain
confined to the surface and not to be a main cause of fracture 5,6). It has been suggested that the central cracks and surface cracks
are developed by different mechanisms as a result of bifurcation of plastic deformation in the two regions 4). The probability of
the surface cracking also decreases with increasing the Al content 4), implying its close relation with plastic localization such as
PLC bands.
Microscopic fracture
TWIP steel exhibits a typical dimple fracture microscopically. Dimples are usually fine (typically less than ~ 2 m) and
shallow except some large dimples associated with second phase particles (Fig. 2a) 7). It is indicative that fracture is primarily
attributed to void nucleation rather than growth. For the smooth specimen, entire fracture surface is covered with such fine dimples
almost without the shear lips at the edge of fracture surface. The intersections of mechanical twins and slip bands with grain
boundaries are known to be the primary void nucleation sites 8). As strain increases, the density of mechanical twin increases,
creating more potential void nucleation sites. Meanwhile the void growth rate increases with increasing the stress triaxiality 9).
However, void growth during tensile deformation of the smooth specimen of TWIP steel is suppressed because the stress
triaxiality remains almost constant (~0.33 for the smooth specimen) due to lack of necking 7,10). Accordingly voids remain fine
even after prolonged uniform elongation and the final fracture occurs by bridging or interlinkage of these fine voids. Void
interlinkage in ductile materials is often explained in terms of the void sheet mechanism 11). The void sheet is a planar feature
consisting of fine voids, usually oriented 45º with the tensile axis. The void sheet is formed by shear localization between primary
large voids and void nucleation inside shear localized region. It was reported that ~70% of fracture surface of the smooth specimen
of TWIP steel consists of void sheets 12).
Fig. 2 (a) A low magnification SEM micrograph showing the fracture surface of the smooth specimen of the Fe-15Mn-0.65C-2Al TWIP
steel plate consisting of fine dimples and few isolated large dimples, (b) SEM micrographs taken at the center and edge of the fracture
surfaces of the smooth and notched specimens of the same steel.
The void growth rate increases with increasing the stress triaxiality (𝜂 𝜎 /𝜎, 𝜎 : mean stress, 𝜎: effective stress),
resulting in a drastic decrease of the fracture strain for dimple fracture. In the case of the smooth specimen of TWIP steel, 
remains as ~0.33 up to fracture because of no necking, as aforementioned. The effects of  on dimple fracture of TWIP steel can

be explored by conducting the tensile tests with the specimens having the different notch geometry. Employing the Bridgman
analysis, for example, the notched specimens with R = 4a and 1.5a (R: notch radius, a: 1/2 of the notch width) in Fig. 2b have 
= 0.45 and 0.62 at the notch center respectively and  = 0.33 at the notch root regardless of the notch radius before deformation.
As expected, the fracture strain remarkably decreased with decreasing the notch radius: 62% for the smooth specimen, 12% for
the 4a specimen, and 7% for the 1.5a specimen. While fracture was initiated at the center of the gage width in the smooth specimen
as shown in Fig. 1a, macro-cracking first occurred at the notch root for all notched specimens (not shown here). The average
dimple size at the center of the fracture surface (the upper row of Fig. 2b) was little influenced by . This is primarily because 
at the center gradually decreases with deformation. In the present case, for the 1.5a specimen, the initial  of 0.62 decreased to
0.46 after fracture. The void growth was not significant under this condition. However, the dimples at the edge of the fracture
surface (the lower row of Fig. 2b) exhibited quite different appearances in spite of the similar  (i.e. ~0.33). The fracture surface
of the smooth specimen consisted of a mixture of unsheared dimples and sheared dimples. For the 4.5a specimen, dimples became
shallower and sheared more severely. All dimples at the edge of the 1.5a specimen was severely sheared and even the quasi-
cleavage facets were observed. It is of interest to note that, in spite of the comparable  (i.e. ~ 0.33), the dimple characteristic at
the center of the smooth specimen, i.e. uniform unsheared fine dimples, are quite different from those at the edge of the notched
specimens, i.e. severely shear dimples.  in the smooth specimen of TWIP steel is uniform along the gage width and its variation
is little during deformation while that in the notched specimen is inhomogeneous. This implies that dimple fracture characteristics
of TWIP steel are significantly influenced by distribution as well as its local value 13).
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Nano/microstructural engineering in lightweight high-entropy steel with multiple
characteristics
Hung-Wei (Homer) Yen1,*, Yi-Hsuan Sun1, Zen-Hao Lai1, Yi-Ting Lin1, Rui-Fan Tu2
1
Department of Materials Science and Engineering, National Taiwan University, Taipei, 10617, Taiwan
2
Iron and Steel R&D Department, China Steel Corporation, Chung Kang Road, Kaohsiung, 812401, Taiwan
*email: homeryen@ntu.edu.tw
Keywords: microstructure, lightweight steel, high-entropy steel, mechanical property
High-entropy steel, also named TRIPLEX or Fe-Al-Mn-C steel, has been defined to meet multiple engineering
requirements such as ultrahigh strength, excellent ductility and lower density. In the past 10 years, many studies focused on
alloy design with respect to density reduction, phase stability and mechanical behaviors in this grade of steel. Actually, there a
large space of nano/microstructural engineering to optimize the overall performance of high-entropy steels.
In this work, Fe-Al-Si-Mn-C-(Ni) alloys will be the newly-developed high-entropy lightweight steels meeting
multiple mechanical behaviors through various nano/microstructural engineering. When it is nearly austenitic steel, high
strength and supra ductility of over 70 % can be achieved under a slip-to-twinning plasticity1). When it is duplex steel with
austenite and D03 ordered phase, the steel own an ultrahigh ultimate strength of over 1300 MPa and excellent ductility of
about 45 % through an enhanced effect of geometrically necessary dislocations. When κ carbides are induced into the steels,
precipitation hardening brings about yield strength of 1500 MPa, ultimate tensile strength of over 1700 MPa and total
elongation of 15 % for this steel. Importantly, all these novel properties are achieved in steels with density lower than 7.0
g.cm-3, about 10% lighter than conventional steels. Therefore, this is a new high-entropy lightweight steel with multiple
characteristics in mechanical behaviors.
We will shortly discuss the behavior of hydrogen-induced delayed cracking (HIDC) in this new steel.
Hydrogen-induced plasticity seems observed when it is nearly austenitic steel2). Besides, excellent resistance to HIDC is also
obtained in 1300 MPa-grade duplex steel. In summary, high-entropy or compositionally complex concept, indeed, is able
drives new novelties for steels especially under effective nano/microstructural engineering.
Acknowledgement
This work was performed under the support of Grant Nos. 110-3116-F-002-002 and 109-2224-E-002-002.
References
1) Z.-H. Lai, Yi-Hsuan Sun, Yi-Ting Lin, Rui-Fan Tu, H.-W. Yen: Acta Materialia. 210 (2021) 116814
2) Z.-H. Lai, Yi-Ting Lin, Yi-Hsuan Sun, Rui-Fan Tu, H.-W. Yen: Scripta Materialia. 213 (2022) 114629

Study of microbanding in a Fe-30Mn-6.5Al-0.3C low-density steel
deformed at cryogenic temperatures:
Mechanisms and contribution to the mechanical behavior
Ivan Gutierrez-Urrutia, Akinobu Shibata, Kaneaki Tsuzaki

Research Center for Structural Materials, National Institute for Materials Science (NIMS)
Abstract:
Austenitic (face-centered cubic) Fe-Mn-Al-C low-density steels have been considered as structural
materials for cryogenic applications due to the attractive combination of mechanical properties such
as mechanical strength (yield strength of 0.5 – 1.0 GPa; ultimate tensile strength of 1.2 – 1.5 GPa),
tensile elongation (30 - 70%) and Charpy impact energy (40 - 140 J), which are comparable to that of
conventional stainless steels. Several studies have shown that the room-temperature deformation
behavior of austenitic Fe-Mn-Al-C low-density steels is characterized by the formation of microbands
(MBs) ascribed to deformation localization phenomena. These works have indicated that MB
formation results in a further plastic accommodation, and hence, enhances the ductility of these steels.
Due to the current interest in Fe-Mn-Al-C low-density steels as structural materials for cryogenic
applications, the investigation of MB formation at cryogenic temperatures can provide further insight
into the deformation behavior of these steels. The present study aims at studying the MB formation
mechanisms in austenitic Fe-Mn-Al-C low-density steels deformed at a cryogenic temperature. The
MB structure in an austenitic Fe-30Mn-6.5Al-0.3C (wt.%) low-density steel tensile deformed at -
196°C was investigated by combined electron channeling contrast imaging (ECCI) and electron
backscatter diffraction (EBSD). The interplay between the deformation structure and MB formation
was evaluated. Several microstructural aspects of microbanding such as the MB structure, MB
morphology, and MB alignment were quantitatively analyzed. From this analysis, several MB
formation mechanisms are proposed. Finally, the contribution of MBs to the mechanical behavior is
analyzed.

Manufacturing superior property medium Mn TRIP steel free of
Lüders bands by warm deformation + IA process
Mei Zhang, Yang Wang, Han Dong

School of materials science and engineering, Shanghai university
Abstract:
A novel process combination of thermal deformation and intercritical annealing (IA) is proposed to
optimize the mechanical properties and avoid Lüders bands of 7Mn steel. The test results show that
the prior austenite grain (PAG) size, carbides precipitation, dislocation density and stored deformation
energy before IA have great effects on the nucleation and growth of austenite during IA, and ultimately
influence the grain size, morphology, volume fraction and stability of retained austenite (RA) after IA.
The relatively high strain rate and low temperature deformation condition sample shows a mixture of
lamellar and equiaxed morphology structure after IA, and exhibits the best comprehensive mechanical
properties, with a product of ultimate tensile strength and total elongation (UTS×TE) value of
(53GPa∙%), owing to the 2-stage discontinuous transformation-induced plasticity (TRIP) effects.
Because the lamellar austenite is more stable than the equiaxed, block-like austenite dominates the
1st-stage plastic deformation, while the film-like dominates the 2nd-stage. It is further confirmed by
the interrupted tensile tests and nanoindentation investigation. This novel process is simple with low
industrial cost, which can provide a new guidance for development of lower cost fabricating
technology of medium Mn TRIP steel.

Mechanistic View on Electric Current Induced Kinetic Enhancement and Its Various
Examples in Steels
Heung Nam Han*
Department of Materials Science and Engineering & Research Institute of Advanced Materials, Seoul National University,
Seoul 08827, Republic of Korea
*email: hnhan@snu.ac.kr
Keywords: Electroplasticity, Electric current-induced kinetic enhancement, Microstructure reset
Electroplastic phenomenon has been demonstrated by that the elongation increases remarkably during deformation
under electric current without significant temperature rise due to Joule heating. Since the 1960s, the electroplasticity has been
actively investigated until recently 1,2); however, full explanation of electroplasticity mechanism has been lacking. In this
presentation, the origin of electroplasticity was elucidated based on numerical and experimental approaches 3). Ab-initio
calculations show that a charge imbalance near defects weakens drastically atomic bonding. The electroplastic behavior could
be well reproduced with microstructure-based FE simulations. In addition, the weakening of atomic bonding was confirmed
by measuring elastic modulus under electric current, which is inherently related to bond strength.
Fig. 1. Mechanism of electroplasticity 3)
As a fundamental approach of electroplasticity, we investigated the effect of electric current density on

recrystallization kinetics of ultra-low carbon steel through the microstructure characterization and mechanical property
analysis. A single pulse treatment (SPT) with different electric current densities and appropriate durations was utilized to
achieve a target peak annealing temperature. The experimental results show that the degree of recovery, recrystallization, and
grain growth tend to decrease with increasing the electric current density and then increase above a certain current density. The
athermal effect of electric current was examined by comparing the recrystallization fractions obtained in the SPT with those
measured in a conventional furnace heat treatment. The increase of the recrystallization fraction by the athermal effect was
calculated using Johnson-Mehl-Avrami-Kolmogorov (JMAK) equation adopting the additivity rule. The result of calculation
confirms that the athermal effect becomes prominent as the current density increases. The dependence of the athermal effect in
the SPT recrystallization on the current density was quantified by introducing effective activation energy and effective
temperature. We believe that the novel approach presented in this study can be extended to other electric current-induced
phenomena in metallic materials.

SPT 760ºC (Measured) SPT 760ºC (Calculated)
SPT 800ºC (Measured) SPT 800ºC (Calculated)
1.0
Recrystallization fraction
0.8
0.6
0.4
0.2
0.0
0 60 120 180 240
2
Electric current density (A/mm )
Fig. 2. Measured and calculated recrystallization fractions (left) and schematic diagram showing changes in thermal and
athermal effects as a function of electric current density (right) 4,5)
As one of the challenging applications of electroplasticity, in addition, we utilized sub-second electric pulsing,
which can enhance the kinetics of microstructural change to infinitely reset the damaged microstructure as a non-autonomous
self-healing method. The principle of microstructure resetting was explained based on three categories of resetting cores:
phase transformation, dislocation recovery, and recrystallization. Microstructure resetting assisted infinite reuse was
successfully realized using 301L and 316L stainless steels, which are applicable materials of the resetting core. This is a new
concept combining extreme simplicity, rapidness, and infinite repetition, which cannot be achieved by conventional methods.
In addition, various application examples such as electric current assisted trimming, joining and sintering will be introduced in
this presentation.
Fig. 3. Infinite reuse concept using microstructure resetting based on electric current-induced kinetic enhancement 6)

Acknowledgement
This work was performed under the support of the National Research Foundation of Korea (NRF) grants funded by the Ministry of
Science and ICT (MSIT) (No. 2019M3D1A1079215, 2020R1A5A6017701, and 2021R1A2C3005096).
References
1) C. Rudolf, R. Goswami, W. Kang, J. Thomas: Acta Materialia 209 (2021) 116776.
2) S. Zhao, R. Zhang, Y. Chong, X. Li, A. Abu-Odeh, E. Rothchild, D. C. Chrzan, M. Asta, J. W. Morris Jr., A. M. Minor: Nature
Materials 20 (2021) 468-472.
3) M. –J. Kim, S. Yoon, S. Park, H. –J. Jeong, J. –W. Park, K. Kim, J. Jo, T. Heo, S. –T. Hong, S. H. Cho, Y. –K. Kwon, I. –S. Choi,
M. Kim, H. N. Han: Applied Materials Today 21 (2020) 100874.
4) J. –W Park, H. –J. Jeong, S.-W. Jin, M. –J. Kim, K. Lee, J. J. Kim, S. –T. Hong, H. N. Han: Materials Characterization 133 (2017)
70-76.
5) K. Jeong, S.-W. Jin, S.-G. Kang, J.-W. Park, H.-J. Jeong, S.-T. Hong, S. H. Cho, M.-J. Kim, H. N. Han: Acta Materialia (2022)
under revision
6) H. –J. Jeong, M. –J. Kim, S. –J. Choi, J. –W. Park, H. Choi, V. T. Luu, S. –T. Hong, H. N. Han: Applied Materials Today 20
(2020) 100755.

Double Soaking of Medium Manganese Steels
Emmanuel De Moor1*, Alexandra G. Glover1,2, Josh J. Mueller, 1,2 David K. Matlock1 and John G. Speer1
1
Advanced Steel Processing and Products Research Center, Colorado School of Mines, Golden, Colorado 80401, USA
2
Los Alamos National Laboratory, Los Alamos, New Mexico, 87545, USA
*email: edemoor@mines.edu
Keywords: medium manganese steel, retained austenite, solute partitioning, martensite, yield point elongation
Medium manganese steels have received substantial attention from academia and the steel producing and using
communities. These steels are viable candidates for vehicle light weighting due to attractive properties combinations which
could enable downgauging of automobile components. Manganese alloying levels are usually between 5-15 wt pct, much
lower than fully austenitic steels such as stainless and high manganese twinning induced plasticity (TWIP) steels. Thermal
processing typically involves intercritical annealing and resulting microstructures are ultrafine grained ferrite/austenite
mixtures with potentially some martensite present.1) If a cold rolled material is used as starting material, the ferrite/austenite
grains tend to be equiaxed following heat treating. High elongation levels can be obtained as a resultant of substantial strain
hardening due to transformation induced plasticity (TRIP) when substantial austenite fractions are present with favorable
mechanical stability.
More recently, alternate thermal processing routes have been considered for medium manganese steels including
quenching and partitioning (Q&P), hot stamping, and double soaking (DS) amongst others.2,3,4,5,6) The DS heat treatment
will be considered in the present contribution and Figure 1 schematically shows the approach.
Figure 1 Schematic of double soaking heat treating. The primary soak is conducted in the intercritical range and the
secondary soak is conducted at a higher temperature. The two steps can be conducted discontinuously with intermediate
cooling to room temperature or continuously. Anticipated microstructural changes are indicated with  ferrite, p and s
primary and secondary austenite respectively and ’ martensite.4)
The primary soak consists of intercritical annealing to introduce austenite in the microstructure and to partition
solute manganese and carbon from ferrite into austenite. The secondary soak is conducted at a temperature in excess of the
first soaking temperature and aims at replacing the solute-lean ferrite present at the end of the primary soak with martensite
following final quenching to room temperature. This is achieved by transformation of the ferrite into austenite during the
(short duration) high temperature secondary soaking. The two steps can be separated by cooling to room temperature
(discontinuous) or can be done continuously.
DS has been applied discontinuously to a 0.14C-7.14Mn-0.23Si steel with an initial as-received microstructure of
ultrafine-grained ferrite and retained austenite (46 vol pct) produced by cold rolling followed by batch annealing in the

intercritical range which constituted the primary soaking step. The secondary soaking step was conducted over a
temperature range of 750 to 825 °C for times ranging from 10 to 120 s. The resulting retained austenite fractions are shown
in Figure 2. A decreasing austenite fraction is observed with time with substantial levels preserved at shorter annealing times
(e.g. over 20 vol pct remains for soaking times less than 60 s).
Figure 2 Retained austenite evolution as a function of secondary soaking hold time at the indicated temperatures.
As-received austenite volume percent in the cold rolled batch annealed condition is indicated by the dashed line. 4)
The character of microstructural evolution is further reflected in the transmission Kikuchi diffraction (TKD) phase
maps presented in Figure 3 which are overlaid with image quality maps.7) Green indicates ferrite/martensite whereas red
indicates austenite in the phase map. The as-received cold rolled and batch annealed (AR-BA) condition shown in Figure 3a
is a typical intercritically annealed medium manganese steel microstructure with equiaxed ultrafine ferrite and austenite grains.
The image quality is high in most grains which suggests a low dislocation density. The DS conditions shown in Figures 3b,
c, and d reflect microstructural evolution for secondary soaking at 750 °C, 775 °C, and 800 °C respectively at a fixed time of
30 s. In the DS-750 °C condition a number of ferrite grains with high image quality have been replaced by low image
quality ferrite constituents with traces of austenite. These areas are interpreted to have transformed during final quenching to
room temperature from the additional (secondary) austenite that likely formed during the secondary soak from solute lean
ferrite. A number of high image quality ferrite areas remain as well as equiaxed austenite grains. As the secondary soak
temperature increases, the ferritic areas with low image quality become predominant indicating increased martensite
formation while equiaxed grains of austenite remain in the microstructure.
Engineering stress/strain curves are shown in Figure 4a for a fixed secondary soaking time of 30 s at the indicated
temperatures. It is clear that the tensile behavior is greatly dependent on the employed secondary soaking temperature. At
the lower temperatures (< 725 oC) pronounced yield point elongations are observed followed by substantial strain hardening
and high tensile elongation similar to the tensile behavior of “conventional” intercritically annealed medium manganese steels.
With an increase in secondary soaking temperature, the stress-strain curve shapes systematically change to reduce or eliminate
the yield point elongation and transition the curve shapes to continuous yielding, higher yield strengths, and high strain
hardening rates leading to overall high ultimate tensile strengths and elongation levels (e.g. for T > 800 oC a UTS of
approximately 1700 MPa with 15 pct total elongation is obtained). The properties for the double-soaked steels exceed levels
observed for traditional intercritical annealing and hot-stamped low alloy steels. It is further noted that post-uniform
elongation is absent or limited for the higher temperature annealed samples which may also indicate that, although not
investigated here, local formability/hole expansion may be limited. The low post-uniform elongation may relate to the fresh
martensite introduced during final quenching and tempering/austempering following DS were thus investigated to reduce

martensite strength.5) Furthermore, these thermal signatures were investigated to more closely resemble the thermal
processing of industrial continuous annealing and/or hot dip galvanizing lines. Resulting engineering stress/strain curves for
the same material are shown in Figure 4b and conditions include the as-received batch annealed steel (BA), DS with
secondary soaking at 800 °C for 30 s, DS followed by tempering (DS-T) at 450 °C for 300 s, and DS followed by
austempering (DS-A) by holding at 450 °C for 300 s.
a) AR-BA
b) DS-750 °C c) DS-775 °C d) DS-800 °C

Figure 3 TKD phase maps overlaid with image quality maps for the a) as received batch annealed (AR-BA); and DS with
secondary soaking conducted for 30 s at b) 750 °C, c) 775 °C, and d) 800 °C.7)
a) b)
Figure 4 Engineering stress-strain curves developed using a 0.14C–7.17Mn–0.21Si cold rolled and batch annealed steel and
a) double soaking for 30 s using the indicated secondary soaking temperatures and b) double soaking at 800 °C/30 s followed
by austempering at 450 °C for 300 s (DS-A) or, tempering at 450 °C for 300 s and the as-received, batch annealed (BA) steel
as well as a DS sample. Secondary soaking was conducted at 800 °C for 30 s in all conditions.4,2,5)

The DS-A and DS-T conditions show an improvement in total and post-uniform elongation as compared to the DS
condition. Roundhouse yielding was observed for the DS-A condition but a yield point elongation returned in the DS-T
sample for the investigated tempering temperature/time combination. The strain hardening of the DS-A and DS samples
appear similar.
Since the as-received material in the above described studies was industrially batch annealed, the first soaking
parameters were already set. Judicious choice of the initial soaking will control austenite fractions and solute levels and can
lead to different responses during the second soaking step. For instance, a low temperature initial soaking leads to the
greatest amount of solute enrichment and may therefore yield greater final austenite levels. The presence of cementite
during initial soaking may also warrant further study as the latter high carbon phase may be dissolved during the second
soaking step and can influence the hardness of the martensite formed during final quenching.
In conclusion, double soaking offers an alternative opportunity to processing of medium manganese steels as high
strength and elongation levels beyond levels achievable with traditional intercritical annealing have been observed. The
higher strength levels likely result from the substitution of ferrite with martensite. Yield point elongation frequently observed
in medium manganese steels, can be reduced or eliminated by double soaking and substantial retained austenite levels remain
available to contribute to the steel’s strain hardening resulting in high elongation levels. Limited post-uniform elongation is
however observed. Overall, tensile properties are superior to typically observed for hot-stamped low alloy steels.
Acknowledgement
The authors gratefully acknowledge the support of the sponsors of the Advanced Steel Processing and Products Research
Center, an industry-university cooperative research center at the Colorado School of Mines.
References
1) R.L. Miller: Metall. Trans. 3 (1972) (905-912).
2) J.G. Speer, R. Rana, D.K. Matlock, A. Glover, G.A. Thomas, E. De Moor: Metals 9 (2019) 771 (1-9).
3) E. De Moor, J.G. Speer, D.K. Matlock: Proc. of the ICAS 2016 & HMnS 2016, Jeju, Korea, 5–10 September 2016
(182–185).
4) A. Glover, J.G. Speer, E. De Moor: Proc. of the Int. Symp. on New Developments in Advanced High-Strength Sheet Steels,
Keystone, CO, USA, 30 May–2 June 2017, AIST, Warrendale, PA, USA (2017) (189–197).
5) A. Glover, J.G. Speer, E. De Moor: Front. in Mater. 7 (2021) 622131 (1-11).
6) A. Glover, P.J. Gibbs, C. Liu, D.W. Brown, B. Clausen, J.G. Speer, E. De Moor: Metals 9 (2019) 761 (1-12).
7) A. Glover, PhD thesis, Colorado School of Mines, (2020).

Atomistic modeling and analysis of dislocation behaviors near grain boundary in iron
Masato Wakeda 1,*
1
*email: wakeda.masato@nims.go.jp
Keywords: Iron, dislocation, grain boundary, molecular dynamics
The interactions between dislocations and other lattice defects have large effects on the mechanical properties of
iron. For instance, the solute atom1,2), vacancy, precipitate, and other dislocations affect dislocation behaviors and macroscopic
yield strength. The grain boundary (GB) is one of the important lattice defects interacting with dislocations and inducing grain
boundary strengthening. The GB-dislocation interaction also affects the fracture of polycrystalline metals. Therefore, further
understating of GB-dislocation interaction should provide a necessary basis for the strengthening design of steel.
In this presentation, I introduce recent approaches of atomistic modeling and analysis of dislocation behaviors near
grain boundary in iron. The GB-dislocation interaction contains various stages, such as elastic interaction, absorption, pile-up,
transmission across GB, and nucleation from GB. In addition, the GB-dislocation interactions depend on GB structure,
dislocation type, temperature, alloy system (solute element), and stress state. In addition, the GB structure has various degrees
of freedom even in a single element system. For these reasons, the GB-dislocation interaction should have various physical
aspects and depend on various factors. We here focus on the dislocation transmission behaviors across GB in body-centered
cubic (bcc) iron and reveal the mechanism and dominating factors of the transmission behaviors. In experimental
nanoindentation, there are distinct differences in transmission behaviors depending on the GB types: 9-221 exhibits a higher
barrier effect for dislocation transmission across GB than  9-114 3). This is interesting because the two GBs exhibits a small
difference in GB energy. Using molecular static simulations, we investigated the origin of the GB-dislocation interaction in
terms of dislocation types, slip direction, and stress fields. In atomistic nanoindentation simulations of bicrystal models with
GB, the dislocations nucleate beneath the indenter; and the nucleated dislocations have slip directions, which agree well with
those predicted by the elastic stress fields before the dislocation nucleation. In addition, it is interesting that dislocations
approaching GB have different components between the two GB types. In the case of 9-114 GB, dislocations approaching
the GB mainly have an edge component. We confirmed that the edge dislocation makes large atomic displacement at GB,
which may enhance dislocation transmission across GB. This result suggests the important role of the dislocation component
on the transmission behaviors. The dislocation transmission behaviors across GB in bcc iron depend on misorientation angle
(GB structures) as well as the dislocation type. We investigated dislocation transmission behaviors at high angle GB and
small-angle GB in bcc iron using molecular dynamics simulations, which can consider temperature effects. In the case of
small-angle GB, the GB contains an array of dislocations or dislocation networks, and the GB-dislocation interaction has an
aspect of dislocation-dislocation interaction. In the atomistic simulations, the transmission behaviors change depending on the
dislocation types (i.e., edge or screw) and applied stress. In addition, dislocation transmission behaviors are different between
small-angle GB and large-angle GB. This atomistic knowledge should be fundamental for the strengthening design of iron
alloys based on the GB-dislocation interactions.
Acknowledgment
Some of the calculations for this study were performed using the Numerical Materials Simulator at the National Institute for
Materials Science. A part of this work was supported by JST, PRESTO Grant Number JPMJPR219A, Japan.
References
1) M. Wakeda, H. Kimizuka, S. Ogata, Journal of the Japan Institute of Metals and Materials 77 (2013) 409-414.
2) M. Wakeda, T. Tsuru, M. Kohyama, T. Ozaki, H. Sawada, M. Itakura, S. Ogata, Acta Mater. 131 (2017) 445-456.
3) M. Wakeda, Y.L. Chang, S. Ii, T. Ohmura, Int. J. Plast. 145 (2021) 103047.

In situ observation of small fatigue cracks in high-strength metals using synchrotron
radiation micro and nano computed tomography
Takashi Nakamura1, *
1
Division of Mechanical and Aerospace Engineering, Hokkaido University, Sapporo, Hokkaido 060-8628, Japan
*email: nakamut@eng.hokudai.ac.jp
Keywords: Gigacycle fatigue, Internal crack, Nondestructive inspection, Synchrotron radiation, Tomography, Steel, Titanium alloy
1. Introduction
Generally, the S–N curve of steel materials exhibits a horizontal line—i.e., a fatigue limit—at about 106–107 cycles.
However, it has been recognized that fatigue failure occurs in regions exceeding 107, even at stresses below the fatigue limit. This
phenomenon is called very high cycle fatigue (VHCF) or gigacycle fatigue, and it has been actively studied both in Japan and
abroad1 since the phenomenon was identified in the 1980s.2 VHCF in high-strength metals, such as high-strength steels and
titanium alloys, exhibits a peculiar phenomenon: fractures originate in the interior of the material. For example, nonmetallic
inclusions of several µm to several tens of µm in high-strength steels and crystal grains of several tens of µm in titanium alloys
are recognized as crack-initiation sites.3 However, it is difficult to detect such small cracks using conventional nondestructive
inspections, such as industrial X-ray computed tomography (CT) or ultrasonic CT. Due to the limitations of the observation
technique, the internal-fracture behaviors and their underlying mechanisms are not yet fully understood.
Third-generation synchrotron radiation facilities equipped with insertion devices, such as SPring-8, ESRF, and APS,
have recently attracted a great deal of attention. Thanks to its high spatial resolution and high-contrast imaging capability, X-ray
CT using high-brilliance synchrotron radiation, so-called SR-CT, has been applied to the field of material fractures.4 The author’s
group has been investigating the nondestructive detection of internal cracks in VHCF using SPring-8.5-7 In a series of studies, the
author’s group has used mainly projection CT (micro-CT) with a spatial resolution of approximately 1 µm. In recent years, the
group has applied phase-contrast imaging CT (nano-CT)8, 9 to observe small fatigue cracks and the surrounding microstructure
with a spatial resolution of approximately 200 nm or higher. The combination of micro-CT and nano-CT has the potential to
clarify the initiation and propagation processes of internal fatigue cracks. The present study introduces the recent SR-CT technique
optimized to detect small fatigue cracks based on an in situ fatigue-testing device available at SPring-8. Small fatigue cracks’
initiation and growth behaviors are discussed with reference to several images of cracks in titanium alloy and high-strength steel.
2. Material selection
The ultimate objective of the author’s group is to develop a universal method for evaluating internal fatigue fractures
in the VHCF regime.10 However, fatigue tests in the VHCF region and SR-CT experiments require considerable time, labor, cost,
etc., and it is impossible to obtain data for every kind of material. Therefore, we examined only three metals—(α+β) titanium
alloy, β titanium alloy, and precipitation-hardened martensite stainless steel—as representative materials in which internal
fractures are frequently observed. More specifically, we used (α+β) type Ti-6Al-4V, β type Ti-22V-4V, and SUS630 as
representatives of dual-phase titanium alloys, single-phase titanium alloys, and vitally important high-strength steel, respectively.
The imaging experiment was performed at BL20XU of SPring-8. This beamline provided the projection CT and the
phase-contrast imaging CT.8,9 In both cases, the synchrotron radiation from the undulator was monochromatized into
monochromatic X-rays and irradiated to the specimen. The projection CT utilized the absorption of X-rays as they passed through
the specimen, and the physical limit of the spatial resolution was 1 µm or higher, with a millimeter order of field of view. The
imaging CT used a Fresnel zone plate, and the phase shift of the X-ray traveling through the sample was converted to contrast
using a Zernike phase plate. Although the field of view was limited (approximately a few tens of micrometers) compared to
projection CT, the spatial resolution was extremely high (200 nm or higher).
An in situ piezo fatigue-testing device was developed to perform fatigue tests on the beamline.11 The capacities of the
tensile and compressive loads were 600 N and 3800 N, respectively. The entire system was set on a rotation stage of the beamline

during the imaging process. A digital servo controller (Shimadzu 4830) was used to generate an accurate load via PID feedback
control. An arbitrary loading waveform could be applied to the specimen with a frequency from DC to about 300 Hz depending
on the material and configuration of the specimen.
4. Obtained images of small fatigue cracks

This section presents several examples of the images of small fatigue cracks in (α+β) type titanium alloy and
precipitation-hardened martensite stainless steel. A previous study has provided some information about the small-crack behaviors
of β type titanium alloy.11
4.1 (α+β) type titanium alloy

The material used was (α+β) Ti-6Al-4V.5-7 The 20-mm-diameter × 1000-mm-round bars were subjected to a solution
treatment (1203 K × 3.6 ks → A.C.) and an aging treatment (978 K × 7.2 ks → A.C.). After heat treatment, the mechanical
properties were as follows: tensile strength: 943 MPa; 0.2% proof stress: 860 MPa; elongation: 17%; reduction of area: 40 %;
and Vickers hardness: 316 Hv. The microstructure was a dual-phase structure consisting of a primary α grain and an (α+β) grain
containing alternating lamellae of α and β phases. The average grain size of both grains was approximately 10 μm. The fatigue
specimen was lathe turned from the bar and had a straight section of 3 mm with a diameter of 0.7 mm. The specimen surface was
finished with #800 to #2,000 emery paper. An in situ fatigue test was conducted at σmax = 650 MPa under a stress ratio of R = 0.1
and at a frequency of 120 Hz. The fatigue life at this stress level was distributed around 2–4 × 107 cycles. The straight section of
the specimen (ϕ 0.7 × 3.0 mm) was repeatedly observed using micro-CT from 1.0 × 107 to 1.18 × 107 cycles. Several cracks were
magnified using nano-CT to clarify the details of their growth behaviors.
Field of view
(Imaging type-CT) Existed at
1.10×107
A
(α+β) α
(a) (b) Bending
Fig. 1. Internal fatigue crack detected by micro-CT. (a) N = 1.10 ×107 cycles. (b) N = 1.12 Fig. 2. Magnified view of the dashed
×107cycles. The loading direction is the vertical direction in the figures. square in Fig. 4 (b) via nano-CT.
Fig. 1 shows examples of the internal crack images at a virtual cross-section parallel to the loading direction. During
CT imaging, the tensile load equivalent to the maximum stress in the fatigue test (σmax = 650MPa) was applied. X-ray energy,
projection number, exposure time, voxel size, and field of view were 30.0 keV, 1800, 0.025 s, 0.5 µm, and 1 × 1 mm2, respectively.
Fig. 1 (a) was observed at 1.10 ×107 cycles and Fig. 4 (b) at 1.12 ×107 cycles. In both figures, the fatigue crack and the surrounding
microstructure were identified. The dark and bright parts corresponded to the α-grain and (α+β) grain, respectively. Crack growth,
which originated from the right-side crack tip in Fig. 1 (b), was observed from 1.10 ×107 to 1.12 ×107 cycles. This crack extension
likely occurred in the α-grain. Fig. 2 shows a magnified view of the white-dashed square in Fig. 1 (b) observed using nano-CT.
X-ray energy, projection number, exposure time, voxel size, and field of view were 30.0 keV, 1800, 0.5 s, 0.0387 µm, and about
63 × 63 µm2, respectively. The crack shape and surrounding microstructure were much more clearly visible than in the micro-CT
image. Very straight crack growth was confirmed to occur in the α-grain, as the dark part of Fig. 1 (b) suggested. The newly
generated crack reached and stopped at the adjacent grain boundary. Considering the linear and inclined crack extension, this part
corresponded to the faceted feature12 that was particularly evident on the fracture surface of the internal crack.
Including this crack, a total of 63 internal cracks were detected over the course of 1.18 × 107 cycles. Almost all the
initiation sites corresponded to the α-grain, and their features were very similar to those of the extended portion of the crack tip
shown in Fig. 2. The phenomenon of many internal cracks originating in one specimen has been reported in a previous study7;
however, the number of detected cracks was significantly increased in the present study, from 287 to 63. This increase resulted
from the improvement in image quality, including the effect of using a thinner specimen (ϕ 0.7).

In (α+β) Ti-6Al-4V, the faceted feature12 is an essential characteristic of the fracture surface around the fatigue-fracture
origin. In particular, in internal fractures, the aggregation of plural facets (multiple facets) is observed on fracture surfaces and is
considered pivotal in clarifying the mechanism of internal-crack growth. The presence of multiple facets may be caused by one
of two processes: (1) plural internal cracks originate from individual facets, independently propagate, and coalesce with each
other, or (2) multiple facets are formed sequentially during their propagation from a single origin. Although many initiation sites
were found in the specimen used in this study, there was no evidence that the cracks in question merged with each other. This
suggests that multiple facets are not formed by the coalescence of the microcracks that originate from plural facets but are rather
induced during crack propagation from a single origin, as shown in Fig. 2.
4.2 Precipitation-hardened martensite stainless steel

The material used was SUS 630. It was subjected to a solution treatment (1313 K × 1.8 ks → W.C.) and an aging
treatment (753 K × 3.6 ks → A.C.). This material was provided by NIMS and was originally prepared to create a fatigue data
sheet.13 The mechanical properties after heat treatment were as follows: tensile strength: 1370 MPa; 0.2% proof stress: 1230 MPa;
elongation: 16%; reduction of area: 61%; and Vickers hardness: 458 Hv. The fatigue specimen was lathe turned from the material
and then surface finished with #800 to #2000 emery paper to form a straight section of 5 mm with a diameter of 0.6 mm. A fatigue
test was conducted at σmax = 650MPa under a stress ratio of R = –1 with a frequency of 220 Hz using the piezo fatigue-testing
device.
SUS 630 has a higher density than titanium alloys; therefore, SR-CT requires higher energy to guarantee sufficient X-
ray transmittance. Even though a thinner, 0.6-mm-diameter specimen was used, the X-ray energy needed to be increased to 37.7
keV, the maximum value available at the current optical setting. Because nano-CT was unavailable for 37.7 keV in the present
study, only micro-CT was performed. Projection number, exposure time, voxel size, and field of view were 1800, 0.12 s, 0.537
µm, and 1 × 1 mm2, respectively. The first image was taken when the number of loading cycles reached 2.0 × 106. Then,
fortunately, a tiny surface crack that originated from a surface nonmetallic inclusion was detected; it can be seen in Fig. 3 (a), (b),
and (c).14 The size (√area 3)) of the surface inclusion projected to the plane perpendicular to the loading direction was 9.9 µm, as
shown in Fig. 3 (d). The length of the surface crack that originated from this inclusion was 5.3 µm.
Fig. 3. Fatigue crack originating from an inclusion observed using micro-CT. (a) Top view of the crack (plane perpendicular to
loading axis). (b) Magnified view of the crack in (a). (c) Side view of the same crack (plane parallel to the loading axis, which
corresponds to the vertical direction in the figure). (d) Magnified view of the inclusion and crack in (b).
When fatigue testing on the same specimen was repeated, the specimen fractured only after an additional cyclic load
of 0.19 × 106 cycles. After the fracture, the specimen was observed again using micro-CT, and the fractured surface was observed
using a scanning electron microscope. On the fracture surface, another 10.8-μm internal inclusion was observed. This inclusion
was slightly larger than the 9.9-μm surface inclusion (Fig. 3 (d)) that was responsible for the fracture. The specimen exhibited
other internal inclusions that were larger than the surface inclusion shown in Fig. 3; however, these inclusions did not exhibit any
crack initiations. Although further investigations are required, it is likely easier for cracks to originate from surface inclusions than
from internal inclusions. Importantly, this observation also indicated that the crack initiation and its propagation up to the very
short distance of 5.3 μm consumed more than 90% (2.0 × 106 cycles) of the total fatigue life (2.19 × 106 cycles). The crack

initiation with a few micrometers from the nonmetallic inclusion (Fig. 3 (d)) consumed most of the fatigue life. In our next study,
we will use SR-CT to detect internal fatigue cracks in SUS 630. However, it remains challenging to detect tiny internal fatigue
cracks with a size similar to the crack shown in Fig. 3 (d). Therefore, it is necessary to continuously improve and optimize the
SR-CT technique for the visualization of internal cracks in this material.
5. Summary
This paper presented a recently developed SR-CT technique: the use of micro-CT and nano-CT to nondestructively
observe small fatigue cracks in high-strength metals. Example images of cracks in (α+β) Ti-6Al-4V and SUS 630 were introduced
to discuss the initiation and growth behaviors related to VHCF phenomena. The main findings are summarized below.
1. A crack extension in the α grain from an internal crack tip was detected in (α+β) Ti-6Al-4V. Its straight and inclined growth
to the loading direction matches the α-facet characteristics usually observed on the internal-fracture surface. This result
suggests that the so-called multiple facets on fracture surfaces in the VHCF regime are not formed by the coalescence of
plural individual microcracks but rather induced by the crack’s propagation from a single origin.
2. A crack initiation with a length of approximately 5 µm was successfully detected at a surface inclusion with a size of about
10 µm. Although larger internal inclusions were found in the control volume of the specimen, no clear sign of crack initiation
was observed around them. Moreover, the initiation of this very small crack consumed more than 90% of the fatigue life;
therefore, taking extreme care not to overlook cracks and continuous improvement of image quality will be indispensable
to observing internal cracks in this material.
Acknowledgments
The author expresses sincere gratitude to Daido Steel Co., Ltd., for providing (α+β) Ti-6Al-4V and to Dr. Y. Furuya at NIMS for
providing SUS630 with beneficial suggestions. The author is grateful to Dr. F. Yoshinaka, Dr. H. Oguma at NIMS, and Dr. N.
Fujimura at Hokkaido University for fruitful discussion. The synchrotron radiation experiments were performed at the BL20XU,
SPring-8 (Proposal No. 2017B1421, 2018B1289, 2019B2042, 2020A0172, 2021A0172, 2021B0172) with the approval of the
Japan Synchrotron Radiation Research Institute (JASRI). The author expresses sincere appreciation to Dr. A. Takeuchi, Dr. M.
Uesugi, and Dr. K. Uesugi at JASRI for providing their ideas and suggestions for utilizing SR-CT. This study was funded by the
Japan Society for the Promotion of Science, Japan (grant numbers: Scientific Research [A, 18H03748, and 21H04529]). The
author is grateful to several graduate students—Mr. Y. Tomoda, Mr. S. Modi, Mr. H. Morishita, Mr. T. Yamazaki, and Mr. G.
Xue—for their support in fatigue tests and computed tomography.
References
1) Sakai T, Nakagawa A, Oguma N, Nakamura Y, Ueno A, Kikuchi S, Sakaida A. Int J Fatigue. 2016;93:339–351.
2) Naito T, Ueda H, Kikuchi M. Metall Trans. 1984;15A:1431–1436.
3) Murakami Y. Metal Fatigue: Effects of Small Defects and Nonmetallic Inclusions, Second Edition, Academic Press, Elsevier
Ltd. (2019).
4) Wu S, Xiao T, Withers PJ. Eng Fract Mech. 2017;182:127–156.
5) Nakamura T, Yoshinaka F, Nakayama S, Oguma H, Shiozawa D, Nakai Y, Uesugi K. Mech Eng Lett. 2016;2:16-00233-16–
00233.
6) Yoshinaka F, Nakamura T, Nakayama S, Shiozawa D, Nakai Y, Uesugi K. Int J Fatigue. 2016;93:397–405.
7) Yoshinaka F, Nakamura T, Takeuchi A, Uesugi M, Uesugi K. Fatigue Fract Eng Mater Struct. 2019;42:2093–2105.
8) Takeuchi A, Suzuki Y. Microscopy 2020;69:259–279.
9) Takeuchi A, Uesugi K, Uesugi M, Toda H, Hirayama K, Shimizu K, Matsuo K, Nakamura T. Rev Sci Instrum.
2021;92:023701.5
10) SPring-8 Users Office, Brief Description of Long-term Proposals Approved for 2020A, SPring-8/SACLA Information,
2020;25-2:154–159.
11) Xue G, Nakamura T, Fujimura N, Takahashi K, Oguma H, Takeuchi A, Uesugi M, Uesugi K. Eng Fract Mech.
2022;263:108308.
12) Liu X, Sun C, Hong Y. Int J Fatigue. 2016;92:434–41.
13) National Institute for Materials Science, Japan. NIMS Fatigue Data Sheet No. 118. 2014.
14) Modi S, Fujimura N, Takahashi K, Nakamura T, Takeuchi A, Uesugi M, Uesugi K. Final Brief Paper of the Eighth
International Conference on Very High Cycle Fatigue (VHCF8). 2022:2B12.

Various strength properties of low-alloy steels in high-pressure hydrogen gas
and their hydrogen compatibility
Hisao Matsunaga1,*
1
Department of Mechanical Engineering, Kyushu University, Fukuoka 819-0395 Japan
2
Research Center for Hydrogen Industrial Use and Storage (HYDROGENIUS), Kyushu University, Fukuoka 819-0395 Japan
*email: matsunaga.hisao.964@m.kyushu-u.ac.jp
Keywords: low-alloy steels, hydrogen gas, ductility, fatigue life, fatigue crack growth, fracture toughness
Quenched and tempered low-alloy steels having martensitic microstructure are promising materials, primarily in
the context of pressure vessels destined for the storage of hydrogen gas in hydrogen refueling stations 1). According to the
database established by the National Aeronautics and Space Administration (NASA) in the USA 2), low-alloy steels (e.g., AISI
4140) are classified as either “severely-” or “extremely-embrittled” materials with the occlusion of hydrogen. Thus, when
low-alloy steels are destined for use in hydrogen gas environment, the hydrogen-induced degradation of their mechanical
performance should be thoroughly taken into account in the strength-design.
For components used in high-pressure gas system, two different design methodologies have been developed: (i)
Design by Rule and (ii) Design by Analysis 3, 4). The former provides an infinite life design with a high safety factor, while a
low safety factor can be used as a premise for a finite life design in the latter. Even though the Design by Analysis involves
complex procedures such as leak-before-break (LBB), fatigue life and fatigue crack-growth (FCG) analyses 5, 6), it offers the
advantage of weight-saving and resultant better rationality. Therefore, a proactive application of Design by Analysis is more
desirable in any attempt to achieve superior economic efficiency of high-pressure hydrogen systems.
The strength properties of low-alloy steels in high-pressure hydrogen gas have been addressed by several
researchers over the past decade. Matsunaga et al. 7) carried out slow strain-rate tensile (SSRT) tests in 115-MPa-hydrogen gas
at ambient temperature using low-alloy steel, JIS-SCM435, with a tensile strength (TS) of ≈ 820 MPa. They reported that the
TS of the steel was not degraded in hydrogen gas, although its ductility loss was significant. Moreover, they conducted
tension-compression fatigue tests for the same material and demonstrated that, even in 115-MPa-hydrogen gas, the fatigue life
was not degraded in a relatively high-cycle regime (i.e., N > 105), while a remarkable degradation was noted in a
comparatively low-cycle regime (i.e., N = 104 ~ 105) 7). Subsequently, Ogawa et al. 8) also subjected the same material to
tension-compression fatigue tests in 115-MPa-hydrogen gas, using specimens with tiny semi-circular slits. The fatigue limit
was determined by the non-propagation condition of micro-cracks that initiated at notch-tips, for which the threshold stress
intensity factor range, ΔKth, was invariable, regardless of the presence or absence of hydrogen. Yamabe et al. 9) performed FCG
tests in 90-MPa-hydrogen gas, as well as cyclic pressurization tests between 0.6 and 45 MPa, using hydrogen vessels of
JIS-SCM435 with TSs of 830 ~ 950 MPa. According to their findings, the fatigue lives of the vessels could successfully be
predicted according to FCG-rate data, while the LBB condition was satisfied when the crack-fronts reached the outer surfaces
of the vessels. Furthermore, Ogawa et al. 10) investigated FCG behavior in JIS-SCM435 after single overloading in air and in
90-MPa-hydrogen gas. They discovered that substantial FCG retardation occurred even in hydrogen gas, the extent of which
was similar to that encountered in air. Considering the above-mentioned series of experimental facts, low-alloy steels with TSs
of less than or in the range of 900 MPa seem to be suitable for use in components exposed to high-pressure hydrogen gas. In
fact, such knowledge has partially been incorporated in standards 3) and technical guidelines 1) for the selection of materials
and the strength-design of hydrogen utilization systems.
The hydrogen sensitivity of low-alloy steels varies depending on their strength levels and microstructural
morphologies 2, 11, 12). In the aforementioned design methodologies, TS value is used in the definition of safety factor 3, 4). For
this reason, the hydrogen-induced TS degradation is not preferred in view of the hydrogen compatibility. It has been revealed
by a number of experiments that TS of material is degraded in high-pressure hydrogen gas when the TS exceeds 1000 MPa 2),
as shown in Fig. 1, in which low-alloy steels are no exception. Also, such a variation in susceptibility is particularly prominent
for FCG properties as elaborated by Matsuoka et al., who carried out FCG tests of low-alloy steels JIS-SCM435 and
JIS-SNCM439 with TSs of 820 ~ 1130 MPa at various test frequencies ranging from 0.001 to 1 Hz 11). Their key discoveries

are summarized as follows:
(1) When TS is less than 900 MPa, FCG is accelerated by a factor of 20 ~ 30 in a hydrogen gas environment, as compared to
an in-air condition. However, the acceleration rate is not affected by test frequency. Specifically, the acceleration is
“cycle-dependent”, for which the fatigue life (i.e., number of cycles to failure) is determinable by crack-growth analysis,
under the assumption of the presence of pre-cracks.
(2) In the case of TS greater than 900 MPa, the rate of hydrogen-induced crack acceleration monotonically intensifies with a
reduction in test frequency, as shown in Fig. 2. That is, the acceleration is “time-dependent”, for which the fatigue life is
unpredictable in terms of the number of pressurization cycles to failure. Thus, fatigue life design (i.e., Design by Analysis)
is not applicable.
Fig. 1 Relative tensile strength (RTS) as a function of TS in hydrogen gas at pressures of 69−115 MPa at ambient temperature.
10000
Relative fatigue crack growth rate, (da/dN H )/(da/dN Air)
90-115 MPa H2 at RT JIS-SCM435

R = 0.1 (K = 25 MPa m1/2 )
f = 0.001-1 Hz
JIS-SNCM439
1000 (K = 22-25 MPa m1/2 )
JIS-SM490B
(K = 30 MPa m1/2 )
100 JIS-S25C
(K = 25 MPa m1/2 )
JIS-S55C
(K = 25 MPa m1/2 )
10
Insusceptible to
test frequency Time-dependent
1
400 500 600 700 800 900 1000 1100 1200
Tensile strength, B (MPa)
Fig. 2 Relationship between relative fatigue crack-growth rate and tensile strength in low-alloy and carbon steels 2).

However, even after the remarkable progress of phenomenological understanding, the rationale behind the
strength-dependence of hydrogen sensitivity has not been well-established, despite its crucial importance not only for the
reliable use of components, but also for the development of novel materials with both superior strength and adequate
hydrogen compatibility.
In the presentation, a series of experimental results on various strength properties of low-alloy steels in
high-pressure hydrogen gas will be exhibited together with the microscopic processes of the hydrogen-induced degradation.
Based on them, hydrogen compatibility of low-alloy steels will be discussed and future challenge for research in the field of
hydrogen gas embrittlement will be proposed.
Acknowledgement
This work was partially supported by the New Energy and Industrial Technology Development Organization (NEDO),
Hydrogen Utilization Technology (FY2013∼FY2017).
References
1) JPEC-TD 0003, Technical document for safety use of pressure storage vessels made of low alloy steels used in hydrogen
refueling stations. Japan Petroleum Energy Center (2020).
2) NASA Safety Standard for Hydrogen and Hydrogen Systems: Guidelines for Hydrogen System Design, Materials
Selection, Operations, Storage and Transportation, NSS 1740.16-Rev. National Aeronautics and Space Administration
(2005).
3) KHK technical standard, KHKS0220. High Pressure Gas Safety Institute of Japan (2020).
4) J. Yamabe, H. Matsunaga, Y. Furuya, S. Hamada, H. Itoga, M. Yoshikawa, et al. Int. J. Hydrogen Energy 40 (2015)
pp.719-28.
5) Yamabe J, Itoga H, Awane T, Matsuo T, Matsunaga H, Matsuoka S. J. Press. Vessel Technol. Trans. ASME 138 (2016)
011401.
6) K. Ma, J. Zheng, Z. Hua, C. Gu, R. Zhang, Y. Liu. Int. J. Hydrogen Energy 45 (2020) 20132-41.
7) H. Matsunaga, M. Yoshikawa, R. Kondo, J. Yamabe, S. Matsuoka. Int. J. Hydrogen Energy 40 (2015) pp.5739-48.
8) Y. Ogawa, H, Matsunaga, J. Yamabe, M. Yoshikawa, S. Matsuoka. Int. J. Hydrogen Energy 43 (2018) pp.20133-42.
9) J. Yamabe, O. Takakuwa, H. Matsunaga, H. Itoga, S, Matsuoka. Int. J. Hydrogen Energy 42 (2017) pp.13289-99.
10) Y. Ogawa, K. Iwata, S. Okazaki, M. Nakamura, K. Matsubara, O. Takakuwa, et al. Mater. Lett. 308 (2022) 131115.
11) S. Matsuoka, H. Matsunaga, J. Yamabe, S. Hamada, T. Iijima. Trans. JSME 83 (2017) 17-00264.

Plastic deformation and dislocation motion at a fatigue crack tip of
a bi-modal Ti-6Al-4V alloy during dwell loading
Motomichi Koyama1,*, Yuma Aoki2, Masaki Tanaka3 and Kaneaki Tsuzaki1,2,4
1
Institute for Materials Research, Tohoku University, Katahira 2-1-1, Aoba-ku, Sendai, Miyagi 980-8577, Japan
2
Department of Mechanical Engineering, Kyushu University, Motooka 744, Nishi-ku, Fukuoka 819-0395, Japan
3
Department of Materials Science and Engineering, Kyushu University, Motooka 744, Nishi-ku, Fukuoka 819-0395, Japan
4
*email: motomichi.koyama.c5@tohoku.ac.jp
Keywords: titanium alloy, metal fatigue, fatigue crack growth, electron channeling contrast imaging, in situ observation
Ti-6Al-4V alloy shows characteristic fatigue crack propagation associated with the anisotropic plasticity evolution
at the crack tip1). In addition, the dwell effect, which is practically important to use Ti alloys, further enhances the complexity
of the fatigue crack propagation behavior. In this study, micro-mechanical and microstructural analyses were performed to
clarify the dwell fatigue behavior of a bi-modal Ti-6Al-4V alloy. Specifically, how dwell fatigue loading accelerates the crack
propagation was investigated. Dwell fatigue tests that contain a dwell process were conducted at room temperature for
understanding the effect of the dwell fatigue on two type of crack propagation modes: (1) crack propagation controlled by
crack tip dislocation emission (Mode I) and (2) crack propagation along a slip plane, associated with dislocation/damage
accumulation (Mode II). The fatigue tests were carried out under a load control including a 10-min displacement holding at
the peak force for only one cycle at several stress intensity factor ranges. To understand the relationship between crack tip
deformation and dislocation microstructure evolution during Mode I crack propagation, we applied digital image correlation
based strain mapping during the 10-min holding, secondary electron imaging to observe the fatigue striation, and electron
channeling contrast imaging of beneath the fracture surface. Furthermore, focusing on Mode II crack propagation, the
deformation behavior during the displacement holding was accurately observed through SE imaging under an in situ loading
test. As a factor controlling the dwell-induced acceleration of crack propagation, we visually clarified that the enhanced
dislocation emission at the crack tip by the thermally activated process is important. This creates the time dependency of the
plastic strain evolution. More specifically, the factors controlling the dwell-induced crack propagation acceleration were
concluded as follows.
(1) During Mode I fatigue crack propagation, spacing of the striations on the fracture surface was locally extended by the
displacement holding, indicating a significant acceleration of crack propagation. Moreover, the acceleration of crack
propagation remained during several cycles even after displacement holding, regardless of stress intensity factor range.
(2) The crack tip strain, which evolved along the loading axis, increased with time during the displacement holding. The
increase in striation spacing was proportional to the increase in strain at the crack tip. The dislocation structure near the
fracture surface observed through the electron channeling contrast imaging indicated that the number of dislocations
emitted from the crack tip was increased by displacement holding. The results conclude that the dwell process accelerates
crack propagation by assisting crack opening. The observed extra crack tip opening during the displacement holding
caused a delay of crack surface contact during the unloading process, resulting in the decrease in the plasticity-induced
crack closure effect.
(3) The in-situ SE imaging indicated that the displacement holding assisted shear deformation at the crack tip and caused a
delay of crack surface contact during the unloading process. This effect resulted in the increase in the effective stress
intensity factor range and the subsequent plasticity-related damage accumulation for Mode II crack propagation.
Acknowledgement
This work was performed under the support of JSPS KAKENHI (JP16H06365; 20H02457).
References
1) A. Maenosono, M. Koyama, Y. Tanaka, S. Ri, Q. Wang and H. Noguchi: Int. J. Fatigue 128 (2019) 105200.

Understanding the effect of microstructure on fatigue properties of weld heat affected zone
of low carbon steel based on microscopic fatigue crack initiation and growth behavior
Hideaki Nishikawa1,* and Yoshiyuki Furuya1
1
*email: NISHIKAWA.Hideaki@nims.go.jp
Keywords: low carbon steel, weld, heat affected zone, microstructure, fatigue, small fatigue crack
Fatigue crack of the welding initiate and grow at weld toe where has various microstructure according to heat history
of welding, called heat affected zone (HAZ). Hence, it is important to understand the effect of HAZ microstructure on fatigue
property for long term reliability of the welding. Especially, it is necessary to understand the small fatigue crack initiation and
growth behavior which is considered to be sensitive to microstructure.
Recently, we have been studied the effect of HAZ microstructure on fatigue properties by using the specimen with
HAZ microstructure which thermally simulated by heat treatment. In these study, we have investigated the effect of HAZ
microstructure on cyclic yielding behavior1), low-to-high cycle fatigue property2), giga-cycle fatigue property3) and microscopic
fatigue initiation and growth behavior4,5) by using newly developed our automatic microscope system6). From these research,
negative influence on fatigue life of coarse grain of HAZ were clarified. This paper briefly review these recent research from the
view point of microstructural small fatigue crack behavior.
In this study, more than 15 types of simulated HAZ microstructures were prepared by heat treatment which controlling
maximum temperature and cooling rate. Figure 1 shows example of microstructures images. Higher cooling rate generate
martensitic microstructure and lower cooling rate generate bainitic, pearlitic and ferritic microstructures. Coarse grain HAZ
(CGHAZ) microstructures were generated by higher maximum temperature and fine grain HAZ (FGHAZ) microstructures were
generated by lower maximum temperature. Average prior austenite grain size of prepared microstructures were 30 to 600 µm,
Vickers hardness were 150 to 400.
Macroscopic yielding property of these microstructure where comparable to other usual steels. Figure 2 shows
relationship between Vickers hardness, tensile strength and cyclic yielding stress of HAZ microstructures. Tensile strength was
proportional to Vickers hardness and cyclic yielding strength were proportional to tensile strength similar to ordinal steels
regardless of microstructural features. On the other hand, prior austenite grain size effects were revealed in low, high and giga
cycle fatigue properties as shown in Figure 3. As shown in Figure 3 a), fatigue life of CGHAZ microstructure group shows lower
fatigue life than FGHAZ group. In addition, internal origin giga cycle fracture occurred in CGHAZ microstructure in relatively
lower strength region. Hence, fatigue limit of CGHAZ were lower than FGHAZ microstructure as shown in Figure 3 b). In
addition, relationship between fatigue life and internal structure, such as martensite and bainite, was not clear.
Such macroscopic fatigue life difference between CG and FGHAZ microstructure were able to be understood by
microscopic fatigue crack initiation and growth behavior. Figure 4 shows examples of fatigue crack initiation behaviors.
According to crack and fracture surface orientation, fatigue cracks seems initiated along slip plane by shear stress regardless of
microstructure. In other words, fundamental fatigue crack initiation and growth mechanism of FG and CGHAZ were same. On
the other hand, early stage fatigue crack growth rate of each microstructures were different. Figure 5 shows fatigue crack growth
behavior of FG and CGHAZ microstructures. Regardless of microstructure, fatigue cracks initiated at very early stage of total
fatigue life as shown in Figure 5 a). However, early stage fatigue crack growth rate of CGHAZ were faster than that of FGHAZ
as shown in Figure 5 b). In this figure, average prior grain size were described by dotted line. Acceleration of early stage fatigue
crack growth of CGHAZ were mainly appeared in the region where the fatigue crack was smaller than prior austenite grain size.
In this region, fatigue crack were propagated along shear stress direction as shown in Figure 4 b).
On the other hand, tensile mode fatigue crack growth rate of HAZ microstructure were seems to follow the fracture
mechanics parameter6,7). Figure 6 shows an example of fatigue crack growth evaluation results of FGHAZ microstructure. Our
microscope observation system is applicable to direct measurement of fatigue crack opening point by using Digital Image
Correlation (DIC) technique6) as shown in Figure 6 a). Fatigue crack growth rates were well organized by using effective J integral
range as shown in Figure 6 b).

According to above results, fatigue life difference between CGHAZ group and FGHAZ group were mainly generated
by early stage shear mode crack growth acceleration of CGHAZ microstructure. It is considered that grain boundary has important
role on transition of fatigue crack growth mode of shear to tensile. In addition, shear mode crack growth rate seems potentially
faster than that of tensile mode growth rate in same crack length. It is able to conclude that coarse grain microstructure facilitate
to continue fast shear mode early stage fatigue crack growth process and decreases total fatigue life.
Figure 1 Examples of microstructure images of simulated HAZ4).
1500 1500
Tempered martensite
Carbon and Low alloy steel : Carbon steel, N
: Carbon steel, QT σyc =0.9 σB
Normalized Steel Tmax CR2
Carbon steel : Low alloy steel, QT
Cyclic yielding stress,σyc (MPa)
Steel Tmax CR2 B10-1.TXT : SUS304 B 1273 K 1 K/s

Tensile strength,σB (MPa)
B 1273 K 1 K/s B10-30.TXT : SUP7, 9A, 12 B 1273 K 30 K/s

B 1273 K 30 K/s B14-10.TXT : A7075-T5 B 1673 K 10 K/s
1000 B 1673 K 10 K/s 1000
C10-30.TXT : SUS630 H900 C 1273 K 30 K/s
C 1273 K 30 K/s D10-10.TXT : SUS630 H1075 D 1273 K 10 K/s
D 1273 K 10 K/s D10-30.TXT
D14-1.TXT D 1273 K 30 K/s
D 1273 K 30 K/s D 1673 K 1 K/s
D 1673 K 1 K/s D14-3.TXT
D14-30.TXT D 1673 K 3 K/s
D 1673 K 3 K/s E 1673 K 10 K/s
D 1673 K 30 K/s D210-10.TXT
D210-30.TXT F 1673 K 25 K/s
D2 1273 K 30 K/s σyc =0.6 σB G 1673K 1 K/s
500 D2 1273 K 10 K/s 500
D214-3.TXT
D214-30.TXT D2 1273 K 30 K/s
D2 1673 K 3 K/s E14-10.TXT D2 1273 K 10 K/s
D2 1673 K 30 K/s D2 1673 K 3 K/s
E 1673 K 10 K/s D2 1673 K 30 K/s
σB=3.14HV
0 0
0 100 200 300 400 0 500 1000 1500
Vickers hardness, HV Tensile strength, σB(MPa)
Figure 2 Relationship between Vickers hardness, tensile strength and cyclic yielding stress of HAZ microstructures2).
B10-1.TXT H900
B10-30.TXT H1075
B14-10.TXT SCM440, 180T
a) 0.05
b) 1400 C10-30.TXT
D10-30.TXT
S40C, 180T
Steel Tmax CR2 D14-1.TXT A7075-T5
Solid mark: Internal origin
Heat Treated Low Carbon Steel UniaxialD14-3.TXT
loading, R=-1 SCM440,
Open mark: Surface550T
origin
B 1273 K 1 K/s
Fatigue limit, σW (MPa)
(0.15C-1.5Mn, 0.07C-1.5Mn)
B 1273 K 30 K/s 1200 D210-10.TXT S40C, 550T
RT, R=-1
Strain amplitude εa (-)
B 1673 K 10 K/s D210-30.TXT

10
Fatigue strength at 1x10 cycles
D214-3.TXT
C 1273 K 30 K/s 1000 Simurated HAZ D214-30.TXT Fatigue strength at 10 10 cycles
0.01 D 1273 K 10 K/s (0.15C 1.5Mn 0.5Cr)
E14-10.TXT : SUP7, SCM440 and S40C
D 1273 K 30 K/s K214-20.TXT
A, PT = 1273 K,30 K/s
D 1673 K 1 K/s 800 K414-1.TXT
B, PT = 1273 K,10 K/s*
0.005 D 1673 K 3 K/s D10-10.TXT
C, PT = 1673 K,30 K/s
D 1673 K 30 K/s D, PT = 1673 K,3 K/s
E 1673 K 10 K/s
600
*Fatigue strength
F 1673 K 25 K/s at 10 7 cycles
G 1673 K 1 K/s 400 7
Fatigue strength at 10 cycles
D2 1273 K 30 K/s : 3 carbon steel, QT
0.001 D2 1273 K 10 K/s ,9 low alloy steel, QT
D2 1673 K 3 K/s 200 : 3 carbon steel, N
Dash mark: Strain controlled test D2 1673 K 30 K/s σW=0.53σB
0.0005 2 0
10 103 104 105 106 107 108 0 500 1000 1500 2000 2500
Number of cycles to failure, Nf (cycles) Tensile strength, σB (MPa)
Figure 3 a) low to high cycle fatigue life2) and b) giga cycle fatigue strength3) of HAZ microstructures. Open mark of a) and solid mark
of b) indicate the results of CGHAZ microstructure and the others indicate that of FGHAZ microstructures.

a) b)
Figure 4 Examples of microscopic fatigue crack initiation behavior and corresponds fracture surface morphologies for a) FGHAZ and
b) CGHAZ microstructure4). Arrows indicate initially detected crack tip position.
Figure 5 Small fatigue crack growth behaviors of FG and CGHAZ microstructures of a) fatigue crack growth curve and b) normalized
fatigue crack growth rate4). One of the typical CGHAZ data was highlighted in the figures.
a) b) c)
Figure 6 Fatigue crack growth evaluation of FGHAZ microstructure7). a) direct measurement of crack opening stress by using DIC
technique and small fatigue crack growth rate represented with b) stress intensity factor and c) effective J integral range calculated from
directly measured crack opening stress.

Acknowledgement
This work was supported by the Council for Science, Technology and Innovation (CSTI), the Cross-ministerial Strategic Innovation
Promotion Program (SIP), and “Structural Materials for Innovation” (Funding agency: JST).
References
1) H. Nishikawa and Y. Furuya: Mater. Trans., 60 (2019).
2) H. Nishikawa, Y. Furuya, S. Igi, S. Goto, F. Briffod, T. Shiraiwa, M. Enoki and T. Kasuya: Fatigue Fract. Eng. Mater. Struct., 43
(2020) , 1239.
3) H. Nishikawa and Y. Furuya: ISIJ Int., 59 (2019) , 1926.
4) H. Nishikawa, Y. Furuya, T. Kasuya and M. Enoki: Mater. Sci. Eng. A, 832 (2022) , 142363.
5) H. Nishikawa and Y. Furuya: Tetsu-To-Hagane/Journal Iron Steel Inst. Japan, 105 (2019) , 1179.
6) H. Nishikawa and Y. Furuya: ISIJ Int., 60 (2020) , 2090.
7) H. Nishikawa and Y. Furuya: Tetsu-To-Hagane/Journal Iron Steel Inst. Japan, 105 (2019).

Yielding mechanism in poly crystalline ferritic steel
Setsuo Takaki1,*
1
Neturen Co., Ltd., 7-4-10 Tamura, Hiratsuka-city, Kanagawa 254-0013, Japan
Emeritus Professor of Kyushu University
*email: takaki.setsuo.491@m.kyushu-u.ac.jp
Keywords: ferritic steel, yielding mechanism, Hall-Petch relation, Bailey-Hirsch relation, grain size, dislocation density
1. Introduction
In my presentation, three topics will be introduced on the yielding behavior of polycrystalline ferritic steel. First one
is the effect of purity of ferritic steels. Discontinuous yielding of ferritic steels has been believed due to Cottrell locking of
dislocations by interstitial elements such as C and N, because yield stress decreases with purifying1). However, authors et al.
have proved that Hall-Petch (HP) coefficient decreases with reducing the total amount of C and N below 50 ppm (0.005%)
and this results in the decrease of yield stress even at the same ferrite grain size2). The yielding based on grain refinement
strengthening is characterized by Step-type yielding that accompanies yield elongation.
Second topic relates the effect of temper rolling (about 1% of cold rolling). Temper rolling was developed to
suppress the stretcher strain in pressed thin-plate steels. By temper rolling, the step-type yielding has disappeared and yield
stress drops greatly3). The role of temper rolling has been explained in connection with the Cottrell locking until now, but it is
true that such a yield drop occurs in high purity poly crystalline iron4). This result suggests that the behavior of yield drop by
temper rolling is not due to the Cottrell locking but due to the change of yielding mechanism.
Third topic is the effect of grain size on the yielding behavior in cold worked ferritic steels. In annealed steels,
yielding occurs by dislocation emission from grain boundary (grain boundary dislocation yielding) but, in cold worked ferritic
steels, it occurs by the movement of dislocations in matrix (inner grain dislocation yielding)5). With decreasing grain size, the
dislocation density increases even at the same percentage of cold rolling and this leads to the increase of yield stress based on
the mechanism of inner grain dislocation yielding6,7).
2. Effect of carbon on the yielding behavior of poly crystalline ferritic steels

In ferritic steels containing carbon more than 0.005%, HP coefficient is constant at 0.6 GPa∙μm1/2 8,9) and yield
stress σy of poly crystalline ferrite is expressed by the following
equation as a function of grain size : d [μm]
σy[GPa] = 0.05 + 0.6×d[μm]-1/2 (1)
However, in the carbon concentration range below 0.005%, HP
coefficient decreases with decreasing carbon content2). Fig. 1
shows the effect of carbon on the yielding behavior of poly
crystalline ferrite5). Even in the same grain size, yield stress
decreases with decreasing solute carbon due to the decrease of
HP coefficient. It should be noted that yield stress depends on
carbon content as well as ferrite grain size in the carbon content
range; C<0.005%. Step yielding accompanies yield elongation
and the amount of yield elongation becomes larger with
decreasing grain size.
3. Effect of cold rolling on the yielding behavior of poly crystalline ferritic steels
Yielding of annealed ferric steels is characterized by the step-type yielding, as shown in Fig. 1. However, the step
yielding disappears by temper rolling and yield stress drops greatly. Fig. 2 shows the effect of prior cold rolling on the yield
stress4). It is interesting that yield drop appears in not only 0.04%C steel but also de-carburized steel (high purity iron). This
result indicates that the behavior of yield drop does not relate the existence of carbon. The difference of yield stress (0.07 GPa)
in annealed specimens can be explained by the change of HP coefficient at the grain size 40μm. In the deformation range
after the yield drop, yield stress is higher in 0.04%C steel than de-carburized steel. Since the data of dislocation density ρ
are reported in the original paper4), data of yield stress are re-plotted in Fig. 3 as a function of ρ. The data after yield drop

follows an identical line expressed by the following equation:
σy[GPa]=0.05+1.8×10-8√ρ (2)
This result proves that the yield stress of cold rolled specimens is basically determined by the mechanism of dislocation
strengthening. On the other hand, yield stress of annealed specimens is determined by the mechanism of grain refinement
strengthening as expressed by Eq. 1. The result of Fig. 3 indicates that yielding mechanism has been changed from grain
refinement strengthening to dislocation strengthening by charging about 1% of deformation. Since higher applied stress is
required for grain boundary dislocation yielding, the behavior of yield drop appears during the change of yielding mechanism.
4. Effect of grain size on the yield stress of cold worked ferritic steels
Grain size affects the yield stress of cold worked specimens as well as annealed specimens. Fig. 4 shows the effect
of grain size on yield stress and dislocation density in cold rolled specimens6,7). At a same percentage of deformation, yield
stress becomes higher with decreasing grain size although it also depends on the amount of deformation. This result makes us
imagine that some additional relationship exists between grain refinement strengthening and dislocation strengthening.
However, it should be noted that dislocation density is markedly changed depending on the grain size: At a same percentage
of deformation, dislocation density is higher in specimens with smaller grain size. Especially in the case of 1.3μm specimen,
dislocation density has been heightened to 1×1015/m2 by 10% cold rolling, that is same level as that in martensite10).
Regarding the effect of grain size on dislocation density, two mechanisms may be considered6,7). One is an increase of misfit
dislocations around grain boundary with increasing the total grain boundary area. The other one is a decrease in moving

distance of dislocations, that leads to an increase of dislocations to produce same amount of plastic strain. Anyway, yield stress
of cold worked specimens should be discussed in connection with their dislocation density. Fig. 5 summarizes the yield stress
σy of cold rolled specimens as a function of dislocation density6,7). The relationship given by Eq. 2 is also shown in the figure
by bold line. It is found that all data are around that line independent of grain size and the amount of deformation. The friction
stress σ0 of pure iron is about 0.05 GPa at room temperature but it is changeable depending on the chemical composition of
steels through the contribution of solid solution strengthening. Apart of error in Fig. 5 is due to the difference in the σ0 value
of steels.
The contribution of dislocation strengthening should be evaluated by the increment of strength Δσ (=σy -σ0).
Fig. 6 summarizes the values of Δσ for the specimens used in Fig. 3 and Fig. 511). The result in Fig. 6 proves that the yield
stress of cold worked specimens is governed by only dislocation density, although that is changeable depending on the
chemical composition and grain size of steels even at a same percentage of deformation.
5. Effect of the character and distribution of dislocations on

the mechanism of dislocation strengthening
Modified Williamson-Hall method12) in X-ray diffraction
analysis enables the evaluation of the character of dislocations as
well as dislocation density. Fig. 7 shows the change of dislocation
character (a) and yield stress (b) in a ferritic steel with cold rolling of
10% through 80% in thickness reduction13). Screw component S
means the fraction of screw component in all dislocations. In the
case all dislocations are of screw-type, S=1. It is found that
dislocations are of mixed dislocation (S≒0.5) at the early stage of
deformation but the fraction of edge dislocation becomes larger
with an increase of dislocation density. Such a behavior is
reasonable because the recovery of screw dislocations will be also
encouraged in heavily deformed specimens. Regarding the
dislocation strengthening, edge dislocation has about 1.4 times large
potential in comparison with screw dislocation, as shown in the
figure (b). Dispersion coefficient δ expresses the uniformity of
forest dislocations on a slip plane. If the dispersion of forest
dislocation is completely uniform, δ=1. Here, an assumption δ
=0.21 was applied so that theoretically calculated values (bold lines)
covers all experimental data. Broken line in the figure shows the
relationship obtained by Eq. 2. Yield stress is almost center between
two bold lines in the low dislocation density range but it shifts
toward the line of edge dislocation in higher dislocation density
range. This behavior just corresponds to the change of S-value in
the figure (a). This result indicates that the character of dislocations

gives a large effect on the behavior of dislocation strengthening as well as dislocation density. In addition, the distribution of
dislocations should also affect the dislocation strengthening but it is not so easy to control the distribution of dislocations. We
may need further discussion on the effect of dislocation distribution on the dislocation strengthening.
Summary
Fig. 8 shows the yielding mechanisms in poly crystalline metals11). In annealed metals, yielding is governed by the
mechanism of grain boundary dislocation yielding and yield stress follows Hall-Petch relation as a function of grain size d.
Hall-Petch coefficient ky is affected by the elements segregated at grain boundary. However, in metals containing dislocations
within matrix, yielding is governed by the mechanism of inner grain dislocation yielding and yield stress follows
Bailey-Hirsch relation as a function of dislocation density ρ. The character and distribution of dislocations should affect the
Bailey-Hirsch coefficient kd and the term of kd√ρ is affected by 1) deformation condition (temperature, strain rate,
deformation mode, etc.) 2) chemical composition and 3) microstructure (grain size, texture, precipitates, etc.). When annealed
steels have been cold worked, yielding mechanism changes from grain boundary dislocation yielding to inner grain
dislocation yielding. In the case the amount of deformation is small, yield drop appears due to the change of yielding
mechanism.
References
1) J.R.Low Jr. and M.Gensamer: Trans. AIME, 158 (1944), 207-249.
2) K.Takeda, N.Nakada, T.Tsuchiyama and S.Takaki: ISIJ Int., 48 (2008), pp.1122-1125.
3) A.J.K.Honeyman: Sheet Metal Industries, 34 (1957), 51-65.
4) A.J.Goldman: Trans. ASM, 57 (1964), 900-908.
5) S.Takaki: J. Japan Inst. Met. Mater., 83 (2019), pp.107-118.
6) Y.Tanaka, S.Takaki, T.Tsuchiyama and R.Uemori: TETSU-To-HAGANE, 104 (2018), 284-291.
7) Y.Tanaka, S.Takaki, T.Tsuchiyama and R.Uemori: ISIJ Int., 58 (2018),1927-1933.
8) W.B.Morrison: Trans. ASM, 59 (1966), 824-846.
9) M.Eto, S.Fukushima, T.Sasaki, Y.Haraguchi, K.Miyata, M.Wakita, T.Tomida, N.Imai, M.Yoshida and Y.Okada: ISIJ Int.,
48 (2008), 1142-1147.
10) D.Akama, T.Tsuchiyama and S.Takaki: ISIJ Int., 56 (2016), 1675-1680.
11) S.Takaki: Ferrum, 26 (2021), 423-426.
12) T.Ungár and A.Borbély: Appl. Phys. Letter, 69 (1996), 3173-3175.
13) S.Takaki: TETSU-To-HAGANE, 107 (2021), 780-783.

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ICAS 2022

The 7th International Conference on Advanced Steels

May 29 - June 1, 2022· in Tsukuba, Japan

The full program is available at the following website

The full program is available at the following website

Keywords: carbon, nitrogen, stainless steel, deformation behavior, hydrogen embrittlement

ICAS 2022 The 7th International Conference on Advanced Steels -1-

Table 1: Alloy compositions and stacking fault energy (SFE) values.

ICAS 2022 The 7th International Conference on Advanced Steels -2-

ICAS 2022 The 7th International Conference on Advanced Steels -3-

ICAS 2022 The 7th International Conference on Advanced Steels -4-

Tadashi Furuhara1,2, Yongjie Zhang1, Mitsutaka Sato1, and Goro Miyamoto1,3

Keywords: steel, phase transformation, precipitation, crystallography, interface, alloying element

ICAS 2022 The 7th International Conference on Advanced Steels -5-

ICAS 2022 The 7th International Conference on Advanced Steels -6-

ICAS 2022 The 7th International Conference on Advanced Steels -7-

2. Required properties of UHSSs for automobile application

ICAS 2022 The 7th International Conference on Advanced Steels -8-

difference and distribution of each composed phase such

3. Advanced analyzing technique of microstructure of UHSSs

(a) SEM image (b) C mapping

(c) C line profile 0.3

ICAS 2022 The 7th International Conference on Advanced Steels -10-

ICAS 2022 The 7th International Conference on Advanced Steels -11-

Keywords: Quenched & partitioned/nanostructured bainitic/medium-Mn steels, C/Mn partitioning.

Fig. 4: SEM micrographs of non-deformed and ausformed medium C steel specimens.

ICAS 2022 The 7th International Conference on Advanced Steels -16-

ICAS 2022 The 7th International Conference on Advanced Steels -17-

ICAS 2022 The 7th International Conference on Advanced Steels -18-

ICAS 2022 The 7th International Conference on Advanced Steels -19-

ICAS 2022 The 7th International Conference on Advanced Steels -20-

Keywords: recovery, recrystallization, three-dimensional analysis, Avrami exponent

2. Materials and Methods

3. Results and Discussion

ICAS 2022 The 7th International Conference on Advanced Steels -21-

ICAS 2022 The 7th International Conference on Advanced Steels -22-

Figure 1 EBSD analysis of HR (a), L-NA(b) and H-NA(c) bands

ICAS 2022 The 7th International Conference on Advanced Steels -23-

ICAS 2022 The 7th International Conference on Advanced Steels -24-

ICAS 2022 The 7th International Conference on Advanced Steels -25-

The effect of inclusion morphology on the RCF life

ICAS 2022 The 7th International Conference on Advanced Steels -26-

Percent failed (%)

inclusions, we carried out SEM observation on the surface of the

cracks were propagated to a direction perpendicular to the ball rolling

ICAS 2022 The 7th International Conference on Advanced Steels -27-

length of the perpendicular cracks increases with the

(b) N=1x105 cycles (c) N=1x106 cycles

filtered-back projection algorithm. (b) N =1 x 106 cycles

ICAS 2022 The 7th International Conference on Advanced Steels -28-

Fig. 7 Process of RCF crack propagation

ICAS 2022 The 7th International Conference on Advanced Steels -29-

Keywords: Steel, Microstructure, Mechanical properties, Nb-bearing steel

ICAS 2022 The 7th International Conference on Advanced Steels -30-

Fig. 1 Phase diagram of Fe-Nb containing 0.2 wt% C

Table 1 Mechanical properties of as-forged sample tested at various temperatures

ICAS 2022 The 7th International Conference on Advanced Steels -31-

ICAS 2022 The 7th International Conference on Advanced Steels -32-

ICAS 2022 The 7th International Conference on Advanced Steels -33-

Keywords: Solubility product, Grain growth, Pinning effect, Precipitate

Materials and method: A low-carbon micro-alloying steel with the composition of

ICAS 2022 The 7th International Conference on Advanced Steels -34-

where D is the grain diameter, 𝑀0 is the pre-exponential factor, 𝑄 is an activation energy, R