Calphad xxx (xxxx) xxx–xxx
Contents lists available at ScienceDirect
Calphad
journal homepage: www.elsevier.com/locate/calphad
Summary report of CALPHAD XLV – Awaji Island, Japan, 2016
Abstract
CALPHAD XLV Conference was held from May 29 to June 3, 2016 in
Awaji Island, Japan, with 76 oral presentations, 100 posters and 5
software demonstrations. 206 participants from 24 countries partici-
pated in this conference. The topics covered by the conference were in
nine categories:High-throghput technique and Materials Integration (I,
II), Ab initio calculations (I, II, III), Thermodynamic database and
software, Thermodynamic modeling and theory (I, II), Experiments and
application (I, II, III, IV), Diffusion and Kinetics (I, II) and
Thermodynamic assessments (I, II). In addition to these, two sessions
entitled Frontier in Materials Science are organized and Profs. Y.
Shibuta and A.P. Tsai introduced their leading-edge studies on large
scale computations of solidification and quasi crystals, respectively. As
a new attempt, short presentation sessions along with poster pre-
sentations were introduced. In this summary, authors, title and ab-
stracts of all presentations are reported.
Invited lectures
Solidification in GPU supercomputer: linkage between ato-
mistic and continuum scales
Yasushi SHIBUTA1, Munekazu OHNO2, Tomohiro TAKAKI3
1
Department of Materials Engineering, The University of Tokyo,
Tokyo, Japan
2
Division of Materials Science and Engineering, Hokkaido
University, Sapporo, Japan
3
Faculty of Mechanical Engineering, Kyoto Institute of Technology,
Kyoto, Japan
Thanks to the recent progress in high-performance computational
environments, the range of applications of computational metallurgy is
expanding rapidly [1]. Especially, with considerable benefit from the
high parallel efficiency of graphics processing units (GPUs), large-scale
simulations have ranged from the nucleation [2] and subsequent soli-
dification [3] in large-scale molecular dynamics simulation up to bil-
lionatom system to the competitive growth of millimeter-size dendrite
assemblages in a large-scale phasefield simulation [4]. In the pre-
sentation, cutting-edge simulations of solidification performed on GPU
supercomputer are introduced with a brief introduction to the current
state of computational studies on solidification.
References
[1] Y. Shibuta, T. Ohno and T. Takaki, JOM 67 (2015)1793.
[2] Y. Shibuta, K. Oguchi, T. Ohno and T. Takaki, Sci. Rep. 5 (2015)
13534.
[3] Y. Shibuta, S. Sakane, T. Takaki, M. Ohno, Acta Mater., 105
(2016) 328.
[4] Takaki, M. Ohno, Y. Shibuta, S. Sakane, T. Shimokawabe, T.
Aoki, J Cryst. Growth, 442 (2016) 14.
https://doi.org/10.1016/j.calphad.2017.09.001
0364-5916/ © 2017 Elsevier Ltd. All rights reserved.
Quasicrystals: A group of electron compounds
A.P. Tsai
Institute of Multidisciplinary Research for Advanced Materials,
Tohoku University Sendai 980-8577 Japan
Quasi-crystal (QC) is no longer a unique structure matter since it has
been confirmed as an equilibrium phase in more than one hundred
alloys. It is clear that stability of stable QCs can be understood within
the framework of Hume-Rothery rules. Even more interesting, it is
found that stable QCs are strict electron compounds, which only formed
for alloys with sharp valence electron concentration (e/a: electron-atom
ratio). Actually, most stable QCs were discovered on the basis of the e/a
criterion. With these stable QCs, structural analysis is allowed to study
on a single-grained sample. Icosahedral quasicrystal (IQC) and ap-
proximant phases compete for stability, where the phase formed de-
pends strongly on thermal history. In the talk, we will be mainly dealing
with the stability of IQCs and approximants which have been reported
recently, in terms of e/a and phase diagram, and discussing the con-
tribution of entropy due to structural flexibility.
Reference
1. A.P. Tsai, Chem. Soc. Rev. 42 (2013) 5352.
Oral presentations
O1
CALPHAD Databases Development for Integrated
Computational Materials Engineering
Wei-Wei Zhang1, Nicholas Hatcher1, James Saal1, Andrew Bobel2,
Jiadong Gong1, Jason Sebastian1, Gregory Olson1, 2
1
QuesTek Innovations LLC, 1820 Ridge Avenue, Evanston, IL USA
60201
2
Department of Materials Science and Engineering, Northwestern
University, Evanston, IL USA 60208
Integrated Computational Materials Engineering (ICME) methodol-
ogies and tools have been developed at QuesTek to design a series of
novel alloys with customized properties that meet performance re-
quirements in critical applications. CALPHAD thermodynamics has
provided a framework for ICME materials design with broad applic-
ability. High quality thermodynamic databases for multicomponent
systems enable accelerated materials design. Three case studies will be
demonstrated in this presentation:
1) A thermodynamic database has been developed in collaboration
with Thermo-Calc Software AB to understand thermo-chemical inter-
action between thermal barrier coatings (TBCs) and calciummagne-
sium-aluminum-silicon oxides (CMAS) and support the design of novel
TBCs that are resistant to attack by CMAS. Binary through quaternary
thermodynamic interactions have been incorporated into the database
and calibrated with high precision experiments from Prof. C. Levi’s
group at University of California, Santa Barbara. The results have been

used to evaluate the thermodynamic model and establish possible
pathways for novel CMAS-resistant TBC designs.
2) An understanding of the quaternary Q-phase precipitate will
enable the design of advanced cast aluminum alloys that maintaining
strength at elevated operating temperatures. Based on a thorough un-
derstanding of this Q phase by Local Electrode Atom Probe (LEAP) at
Northwestern University and in combination with experimental litera-
ture data, QuesTek has updated the thermodynamic description of the
Q phase in its proprietary databases to enable the design of novel cast
aluminum alloys for high-efficiency engines.
3) QuesTek has developed methods for applying high-throughput
DFT databases to explore the high entropy alloys (HEA) for industrial
gas turbine components. This tool has been integrated with the con-
struction and/or modification of a large CALPHAD thermodynamic
database. Potential compositions are experimentally verified by lab-
scale alloy synthesis and characterization.
O2
High-throughput CALPHAD modeling: A case study of Al-Ni
Richard Otis1, Zi-Kui Liu1
1 also predicated, and comprehensively compared with the experimental
Pennsylvania State University, 303 Forest Resources Laboratory,
University Park, PA 16802, USA,
e-mail: rao140@pasu.edu
High-troughput CALPHAD moelling is desirable for rapid develop-
ment and maintenance of multicomponent systems. As demonstrated
earlier [1], this requires that the relations between experimental mea-
surements, first-principles data and fitted model parameters be ex-
plicitly encoded in accessible databases so that they can be queried,
copied and analyzed indefinitely, especially for the purposes of quickly
updating complex CALPHAD model with new data.
Toward that end we preset a case study of the automated determi-
nation of modle parameters for phases in the Al-Ni system.
“Automated” means that the user need only to choose sublattice models
for all phases in the system while a computer program determines the
best parameter degrees of freedom and their optimal values. The au-
tomation approach is based on using first-principles data from density
functional theory, augmented by finite-temperature predictions from
phonon calculations and the Debye model, to make an initial guess for
model parameters. Crucially, special quasirandom structure data is also
included to provide initial guesses for the enthalpy of mixing.
From this initial guess we are able to compute an approximate phase
diagram that, in the case of Al-Ni, roughly predicts all of the known
phase equilibria including a metastable fcc ordering temperature within
50K of the previously assessed value. Finally we refine the model using
experimental thermochemical and phase equilibrium data. This is also
done automatically, using an iterative procedure that finds the most
sensitive parameters for the given dataset. In the future we intend for
this approach to be scaled up to include more components and more
sophisticated sublattice models.
Reference
[1] S. Shang, Y. Wang and Z. K.Liu, “ESPEI: Extendible, Self-opti-
mizing Phase Equilibrium Infrastructure for Magnesium Alloys,” S. R.
Agnew, N R. Neelameggham, E. A. Nyberg, W. H. Sillekens, Eds.,
Magnesium Technology 2010, Seattle, WA, Minerals, Metals and
Mateirlas Society/AIME, 184Thorn Hill Road, Warrendale, PA, 2010,
pp.617-622.
O3
An numerical inverse method for high-throughput determina-
tion of composition-dependent interdiffusion coefficients in
ternary and multicomponent alloys
Lijun Zhang*, Weimin Chen, Jing Zhong, Yong Du
2
Calphad xxx (xxxx) xxx–xxx
State Key Laboratory of Powder Metallurgy, Central South
University, Changsha, Hunan, 410083, P.R. China
*Corresponding author: xueyun168@gmail.com; lijun.zhang@
csu.edu.cn
High-throughput determination of reliable composition dependence
of interdiffusion coefficients is not only of theoretical interest but also
of practical importance, especially with the boost of the MGI and ICME
projects nowadays. For binary systems, the Boltzmann-Matanno
method and its variations with the aid of a single diffusion couple are
widely utilized to determine the compositiondependent inter-
diffusivities. However, the situation becomes much more complicated
in ternary systems, not to mention the multicomponent alloys.
The present report first demonstrates the careful development of the
numerical inverse method for high-throughput determination of com-
position-dependent interdiffusion coefficients in ternary and even
multicomponent alloys. After realizing via the house-made code, the
reliability of the proposed numerical inverse method is then validated
in a series of ternary and multicomponent diffusion couples by com-
paring with the limited diffusivities evaluated via the traditional
MatanoKirkaldy method. In addition, different diffusion properties are
data. Finally, the presently developed numerical inverse method in
combination with diffusion multiple techniques are utilized to perform
highthroughput determination of interdiffusivity matrices in several
commercial alloys, including Nibased superalloys, high entropy alloys
etc.
Acknowledgments
The financial support from the National Natural Science Foundation
of China (Grant Nos. 51474239 and 51301208), and the Hunan
Provincial Natural Science Foundation for Youth of China (Grant No.
2015JJ3146) is greatly acknowledged. Lijun Zhang acknowledges the
project supported by State Kay Laboratory of Powder Metallurgy
Foundation, Central South University, Changsha, China, as well as the
support from Shenghua Scholar Program of Central South University,
China.
References
[1] K. Cheng, et al. Scripta Mater., 76 (2014) 5-8.
[2] W. Chen, et al. Scripta Mater., 90-91 (2014) 53-56.
[3] H. Xu, et al. J. Alloys Compds. 644 (2015) 687-693.
[4] W. Chen, et al. Scripta Mater., under review (2016).
O4
High Throughput Screening of Cubic Perovskite Structure for
Ammonia Synthesis as a Free Carbon Energy Source
Kihyun Shin, Hyuck Mo Lee*
Department of Materials Science and Engineering, Korea Advanced
Institute of Science and Technology (KAIST), 291 Daehak-ro, Yuseong-
gu, Daejeon 34141, Republic of Korea
*e-mail: hmlee@kaist.ac.kr
The Haber–Bosch process is one of the most well known chemical
reactions involving a heterogeneous catalyst. Ammonia has a huge
possibility as a next generation clean energy source because ammonia is
carbon free molecule, and has high energy density. However, the in-
dustrial Haber–Bosch process is complex and requires high temperature
and pressure of its reactant N2 and H2 gases and considerable plant
infrastructure. According to the recent studies, several molecular cat-
alysts and naturally occurring nitrogenase enzymes were capable of N2
reduction under ambient conditions. No heterogeneous catalysts have
been discovered that can produce ammonia in significant yields, though
various transition metals and metal oxide catalysts were used to break
the limitation of present catalytic activity. In this study, we tried to
investigate the cubic perovskite structure (ABO3) as a new catalyst
system to mimic enzymes. We performed high throughput screening

over the entire periodic table by setting the basic criteria such as heat of
formation, N and H adsorption energy, and adsorption site. Then, we
suggest possible catalyst systems among the various cubic perovskite
structures by evaluating the catalytic activity of N2 reduction.
O5
Stability analysis of Nd(Fe,Ti)12 and Nd(Fe,Ti)12N compounds
as high performance permanent magnet materials
Ying Chen1, Arkapol Saengdeejing1, Masashi Matsuura2, Satoshi
Sugimoto2
1 Cluster Variation Method (CVM). Since in the CVM one needs to deal
Department of Nanomechanics, School of Engineering, Tohoku
University 6-6-01 Aramakiaoba, Aoba-ku, Sendai, 980-8579, Japan
2 tion of the cluster probabilities is required. Early on, the task of char-
Department of Materials Science, School of Engineering, Tohoku
University 6-6-02 Aramakiaoba, Aoba-ku, Sendai, 980-8579, Japan
Recently, a serise of the ThMn12-type coumpounds, NdFe12,
NdFe12N, were predicted theoretically as the promising high perfor-
mace permanent magnet materials with the high magnetization and
magnetocrystalline anisotropy energy compariable to the well known
Nd-Fe-B magnets[1-3]. However, these compounds are very difficult to
be sythesised in the experiments due to the thermodynamical instabilty.
The present study attampts to investigate the origin of the intability in
NdFe12 and NdFe12N, to discuss the effect of Ti-doping on the sta-
blization of the NdFe11Ti and NdFe11TiN alloys. Calculations of the
electronic structure are based on GGA-PAW, +U are used for Ti. The
Debye-Gruneisen approximation, as well as the phonon calculations are
performed to estinmate the finite temperature properties. The calcula-
tions revealed that (1) The vibration effect at finite temperature brings
the possibility of stabilization of the NdFe12 at 620K; (2) The analysis
and comparison of different features of the effective pair interactions in
NdFe12 and NdFe11Ti shows that introducing attractive pair interac-
tions due to Ti-doping is one of reasons of the stablization of NdFe11Ti;
(3) the mixing energy of NdFe12 and NdTi12 has been evaluated, the
system with the minimum mixing energy at the whole concentration
range is NdFe11Ti, which is consistent with the experimental results.
References
[1] T. Miyake, et al., J. Phys. Soc. Jpn. 83 (2014) 043702.
[2] Y. Harashima, et al., arXiv (2015): 1507.03777v1.
[3] Y. Hirayama, et al., Scripta Mater. 95 (2015), 70.
[4] R. Coehoorn, Phys. Rev. B 41 (1991), 11790.
O6
Prediction of impurity diffusion activation energy in metal by a
combination of data-mining and ab initio calculation
Kewu Bai, Yingzhi Zeng
Institute of High performance Computing, 1 Fusionopolis Way, #16-
16 Connexis, Singapore 138632
To understand and simulate alloy microstructure using thermo-
dynamic-kinetic method, the selfconsistent diffusion model parameters,
such as impurity diffusion activation energy are highly needed. The
advance of ab initio method enables a reasonable estimation of the
values, which however requires a lot of computation resources for the
huge number of materials systems. In this presentation, by a combi-
nation of data-mining and ab initio calculation, we are able to effi-
ciently predict and assess the impurity diffusion activation energy for
diffusion in FCC metals, as well as light-weight atom diffusion in BCC,
FCC, and HCP metals. On the basis of the developed model, we further
develop a linear approximation, which may shed light on the delicate
relationship between diffusion activation energy and properties of the
constituent components in diffusion couples.
Reference
[1] Yingzhi Zeng and Kewu Bai, Journal of Alloys and Compounds
624 (2015) 201–209.
3
Calphad xxx (xxxx) xxx–xxx
O7
Approximate Solutions to the Cluster Variation Free Energies
by the Variable Basis Cluster Expansion
J.M. Sanchez1 and T. Mohri2
1
Institute for Computational Engineering and Sciences and Texas
Materials Institute, The University of Texas at Austin, Austin, Texas,
U.S.A.
2
Institute for Materials Research, Tohuko University, Sendai, Japan
In this presentation we propose an efficient approach to obtain
series of approximate solutions to the free energy functional in the
with a large number of configurational variables, an efficient descrip-
acterizing the cluster probabilities was simplified by using a set of
correlations functions [1,2] that, in turn, were shown to form a com-
plete and orthogonal set of configurational variables in the finite con-
figurational space of the CVM. In particular, the completeness of the set
of correlations functions allowed expressing the energy of the system in
the form of a generalized Ising-like model, and the cluster probabilities
as a linear form in such correlations functions [1]. The approach was
subsequently formalized by Sanchez, Ducastelle and Gratias [3] and
extended to infinite system. When applied to the energy of formation, it
has become known as the Cluster Expansion (CE) method.
The CE method in the configurational basis introduced by Sanchez,
Ducastelle and Gratias [3], referred here as the SDG basis, has become
the method of choice to obtain effective cluster interactions from the
energies of a set of ordered compounds obtained from some im-
plementation of Kohn-Sham equations in Density Functional Theory. Of
necessity, the CE of the energy is always truncated at some maximum
cluster size, in which case the energy takes the form of a generalized
Ising-like model. Several methods have been developed to truncate the
CE in the SDG basis. However, it has been shown that in the presence of
no-local terms in the energy, which will typically depend non-linearly
in the overall concentration of the system, the CE in the SDG basis does
not converge [4]. This lack of convergence of the CE raises questions
about the implementation of the CE in the SDG basis. An approach that
properly addresses non-linear concentration dependences in the energy
of the system is to perform the CE in the Variable Basis introduced in
Ref. [4].
The CVM free energy functional offers a well-controlled case study
to investigate the truncation of the CE in the SDG basis versus the
truncation of the CE in the Variable Basis. Our main result is that the
truncation of the CE of the probabilities in the SDG basis leads to large
errors in the CVM free energy as we move away from the 50/50 con-
centration and, eventually, to negative values of the probability dis-
tributions. On the other hand, truncation of the CE in the Variable Basis
gives a sequence of free energies that converge uniformly towards the
full CVM free energy.
References
[1] Sanchez. J.M., and de Fontaine, D., Phys. Rev. B 17 (1978)
2928.
[2] Mohri, T., Sanchez, J.M., and De Fontaine, D., Acta. Metall.
Mater. 33, (1985) 1171.
[3] Sanchez, J.M., Ducastelle, F., and Gratias, D., Physica 128A,
(1984) 334.
[4] Sanchez, J.M., Phys. Rev. B 81, 224202 (2010) 224202.
O8
Describing the Laves phases using a cluster expansion de-
scription
J.-C. Crivello1,2, T. Mohri2, J.-M. Joubert1
1
ICMPE-CNRS, Thiais, France

2
IMR, Tohoku University, Sendai, Japan
Among the Topologically Close Packed phases (TCP), the Laves
phases AB2, such as the cubic C15, are of the utmost importance.
Because the precipitation of these phases should be avoided in high-
temperature metallic alloys, their prediction by thermodynamic mod-
elling is essential.
For decades, Laves phases have been modeled by using the so-called
sublattice model in the Compound Energy Formalism (CEF) [1,2]. If the
energy of all end-members is correctly given, this approach can express
the Gibbs energy of the phase for a multi-component system. In this
way, the homogeneity range of the TCP phase as the function of the
concentration could be estimated [3]. The only drawback of this
methodology is the empirical expression of the temperature depen-
dence. Without the use of temperature dependent interaction para-
meter, the entropy is only coming from the point correlation, as in the
frame of the Bragg-Williams approximation.
The present work focuses on the description of the C15 phases by
using the cluster expansion method. After the crystallographic analysis
of the structure, some approximations in the interaction are considered
and lead to the energy expression by a limited set of clusters up to the
tetrahedron. Both the Cluster Expansion Method (CEM) and the Special
Quasi-random Structure (SQS) have been used to describe the sub-
stitutional solid solution. For SQS, reasonable supercells have been
generated for several concentrations. Moreover, with a given set of
clusters, we discuss the potential application of the Cluster Variation
Method (CVM) to describe the entropy of the C15 phase.
By coupling one of these techniques (CEM or SQS) with the Density
Functional Theory (DFT), first-principles calculations have been per-
formed on the disordered Laves phases. The results such as the inter-
action parameters obtained for a selection of known systems (Mg-Cu,
…) have been compared to those from thermodynamic assessments
obtained in the frame of the Calphad modeling.
References
[1] B. Sundman, and J. Ågren, J. Phys. Chem. Solids, 42 (1981) 297-
301.
[2] J.-O. Andersson et al. Acta Metall., 34 (1986) 437-445.
[3] J.-M. Joubert and J.-C. Crivello, Applied Sciences, 2 (2012) 669-
681.
O9
Ab initio determination of lattice stabilities and comparison to
CALPHAD
F. Körmann1,2, B. Grabowski1, T. Hickel1, A.V. Ruban3, Y. Gong4,
R.C. Reed1,4, J. Neugebauer1
1
Max-Planck-Institut für Eisenforschung, Düsseldorf, Germany
2
Delft University of Technology, Delft, Netherlands
3
KTH Royal Institute of Technology, Stockholm, Sweden
4
University of Oxford, Oxford, UK
Lattice stabilities are one of the fundamental concepts upon which
CALPHAD is based. For elements where only one of the phases is stable
the lattice stability of the other phases cannot be directly measured.
Following the original ideas of Kaufman [1], Saunders et al. [2] have
used extrapolations of melting temperatures and entropies of fusion to
determine the lattice stabilities of all unary elements, building thereby
the basis of all current CALPHAD implementations. So far, it was im-
possible to provide independent atomistic simulations to verify the
universally used lattice stabilities.
Over the recent years we have developed a set of ab initio tools [3-6]
that allow to compute highly accurate Gibbs energies up to the melting
temperature including all relevant excitation mechanisms. Applying
these techniques, we have computed temperature dependent fcc and
hcp lattice stabilities of Al, Cu, and Ni. We show that for Cu and Ni the
ab initio lattice stabilities are qualitatively different from the CALPHAD
ones: CALPHAD predicts a destabilization of hcp, whereas the ab initio
4
Calphad xxx (xxxx) xxx–xxx
results show a clear stabilization of hcp with increasing temperature.
This finding has drastic consequences for the determination of stacking
fault energies which are closely related to the fcc and hcp lattice sta-
bilities and which are a central quantity in the deformation behavior of
materials. We discuss the possible origin of the discrepancy between
CALPHAD and ab initio in terms of the extrapolations used to determine
the CALPHAD lattice stabilities.
References
[1] L.Kaufman, in "Phase Stability in Metals and Alloys"(McGraw-Hill,
N-Y., 1967), p. 125.
[2] N. Saunders, A. P. Miodownik and A. T. Dinsdale,Calphad 12
(1988), 351.
[3] B. Grabowski, L. Ismer, T. Hickel and J. Neugebauer, Phys. Rev.
B 79 (2009) 134106.
[4] F. Körmann, A. Dick, B. Grabowski, T. Hickel and J.
Neugebauer, Phys. Rev. B 85 (2012) 125104.
[5] A. Glensk, B. Grabowski, T. Hickel and J. Neugebauer, Phys.
Rev. Lett. 114 (2015) 195901.
[6] A. I. Duff, T. Davey, D. Korbmacher, A. Glensk, B. Grabowski, J.
Neugebauer and M. W. Finnis, Phys. Rev. B 91 (2015), 214311.
O10
Thermodynamic assessment of the Fe-Nd-Dy-Cu-B system
H. Ohtani 1,3, Y. Horino1, J. Luo2, M. Saeki1, M. Enoki 1,3
1
IMRAM, Tohoku University, 2-1-1, Katahira, Aoba-ku, Sendai,
980-8577, Japan
2
Kyushu Institute of Technology, 1-1, Sensui-cho, Tobata-ku,
Kitakyushu, 804-0015, Japan
3
JST-CREST, 7, Gobancho, Chiyoda-ku, Tokyo, 102-0076, Japan
【Introduction】The permanent magnets based on Nd2Fe14B phase
are widely used for electric engineering fields. However, there is a
problem that the thermal demagnetization occurs at higher tempera-
ture. To prevent the demagnetization, a method of using fusible Nd-Cu
alloy was recently proposed.[1] Then in the present study, thermo-
dynamic assessment of the Fe-Nd-Dy-Cu-B system was attempted to
clarify the mechanism of this process.
【Procedures】The regular solution model was applied to liquid
phase and solid solutions. Intermediate compounds were described as
stoichiometric phases. All binary systems as well as the Fe-Nd-B, Fe-Dy-
B, Fe-Nd-Dy ternary systems were described by the results of the pre-
vious thermodynamic analysis. In the Fe-Nd-Cu system, the formation
enthalpy of δ (Fe13Nd6Cu) phase was evaluated using the first-princi-
ples calculation. The result was introduced to the optimization process
with some experimental phase boundary data. No information on the
phase equilibrium in the Fe-Dy-Cu and Fe-B-Cu systems is available,
and thus the genetic algorithm was applied for revealing existence of a
ternary phase in these systems. Based on these results, partition beha-
vior of elements between matrix and liquid phases during solidification
was investigated using the Scheil model simulation. Grain boundary
segregation during the heat treatment was also studied based on the
parallel tangent law.
【Results and Discussion】Figure 1 shows the calculated liquidus
projection of the Fe-Nd-Cu ternary system. It is characteristic that the
two-phase separation of the liquid phase exists between Fe-rich and
(Nd, Cu)-rich regions. The ternary eutectic reaction E1: Liquid ⇔ NdCu
+(Nd)+δ occurs in the Nd-rich region and the reaction temperature is
estimated about 790K. Figure 2 is the calculated content of each ele-
ment in grain boundaries varying with temperature when 0.1% of Cu is
added. According to the result, the Cu content increases with tem-
perature over around 780 K, while the Fe and Nd contents decreases in
grain boundaries. This behavior could be roughly explained from the
repulsive atomic interaction between Fe and Cu, as well as the attrac-
tive interaction between Cu and Nd in grain boundaries.
 Calphad xxx (xxxx) xxx–xxx

place a constraint on the excess parameters in an assessment of the

phase diagram, the consequences of which we discuss.
References
[1] Nazarov, R.; Hickel, T.; Neugebauer, J., Vacancy formation en-
ergies in fcc metals: Influence of exchange-correlation functionals and
correction schemes. Physical Review B 2012, 85 (14), 144118-1-7.
[2] Duff, A.I. et al. to be published

O12
First-Principles based Calculation of the Prototype Relaxor
Ferroelectric Phase Diagram
Authors names: Benjamin Burton, G. Dogan, D. Gopman and E.
Cockayne:
National Institute of Standatds and Technology, 100 Bureau Dr.
Gaithersburg, Maryland, 20899, USA
benjamin.burton@nist.gov
A first principles based model was formulated to study the relaxor
ferroelectric system Pb(Sc1/2Nb1/2)O3 (PSN) [1]. This model success-
fully reproduces ferroelectric (FE) - reaxor (RF) – Paraelectric (PE)
behavior as functions of temperature (T); pressure (P)[2]; near
neighbor (nn) Pb-O divacancy pairs (VPb-O)[3,4]; and diffuse X-ray and
neutron scattering[5]. Currently, we are analyzing the time evolution of
polar domains with the idea of identifying T* (where polar domain
growth slows significantly) and evaluating the relaxor/spin-glass ana-
logy; with emphasis on the prototype relaxor phase diagram.
References
[1] B.P. Burton et al. Phase Transitions, Vol. 79, Nos. 1–2,
January–February, 91–121 (2006),.
[2] S. Tinte et al. Phys. Rev. Lett. 97, 137601 (2006).
[3] R. E. Cockayne and B.P. Burton, Phys. Rev. B 69 144116 (2004).
[4] B.P. Burton et al. Phys. Rev. B 77, 144114 (2008).
[5] P. Ganesh, et al. Phys. Rev. B 81, 144102 (2010)

O13
First -principles calculation of the tetragonality of Fe -C and
Reference Fe -N systems
[1] H. Sepehri-Amin et al.: Scripta Mater, 63(2010), 1124-1127. Hideyuki Ohtsuka1, Van An Dinh2, Kaneaki Tsuzaki3, Koichi
Tsuchiyal, Ryoji Sahara1,
Truong Vinh Duy4, Tsukuru Ohwaki4, Hideaki Kitazawa1 and
O11
Terumi Nakamura1
Using DFT data to inform the assessment of the C-Zr phase 1
National Institute for Materials Science, 1-2-1 Sengen, Tsukuba,
diagram
Ibaraki, Japan.
Theresa Davey1, Andrew I. Duff1, Suzana G. Fries2, Michael W. Finnis1,3 2
1 Osaka University, Yamadaoka 2-1, Suita, Osaka, Japan.
Department of Materials, Imperial College London, Exhibition 3
Kyushu University, 744 Motooka, Nishi-ku, Fukuoka, Japan.
Road, SW7 2AZ London, UK 4
2 Nissan Arc, 1 Natsushima-cho, Yokosuka, Kanagawa, Japan.
ICAMS, Ruhr-Universität Bochum, Universitätsstraße 150, 44801
The effects of carbon and nitrogen content on the tetragonality and
Bochum, Germany
3 magnetic moment of the Fe -C or Fe -N systems have been evaluated using
Department of Physics, Imperial College London, Exhibition Road,
the first -principles calculation[1]. Three types of supercell, Fe54C1,
SW7 2AZ London, UK
Fe54C2, and Fe128C1 (which correspond to Fe -0.40C, Fe -0.79C, and Fe
Corresponding email: theresa.davey08@imperial.ac.uk
-0.17C mass%, respectively) are used for the calculation of Fe -C system.
One of the challenges of thermodynamic modelling has been in
The same supercells were also used for Fe -N system. The main results are
accurately representing the vacancies in ordered compounds, which are
as follows: (1) The total and mechanical energies of the Fe -C system with
often stable over a wide range in stoichiometry. Individual defect en-
carbon atoms at the octahedral sites are smaller than those of the system
ergies of formation are difficult to measure experimentally, and such
with carbon atoms at the tetragonal sites. The carbon atom at the octa-
data is not included explicitly in phase diagram assessments.
hedral site produces a relatively large expansion in one direction; (2) The
In recent years, it has become possible to use Density Functional
tetragonality of the Fe –C system obtained using the first –principles cal-
Theory (DFT) to calculate the formation energy of vacancies, or other
culation increases linearly with increasing carbon content and agrees well
point defects, with accuracy comparable to experiment [1]. In many
with experimental results. The average magnetic moment of the Fe atom
systems, no reliable experimental data is available. We show here how
increases with increasing carbon content; 3) The magnetic moment of the
such DFT data can be used to inform the assessment of a phase diagram,
Fe atom at the carbon atom nearest neighbor site is lower than that of pure
with reference to the carbon-zirconium system. This system has one
iron and increases with increased distance between the Fe and carbon
intermediate phase, ZrC1-y (rocksalt structure), which is stable over a
atoms. The projected density of states exhibits a hybridization with the
range of carbon content, with 0<y<0.12, depending on temperature.
main contributions being from Fe d and C p states, which leads to the
Using DFT calculations of the vacancy formation energy [2] we

5

abovementioned decrease in the magnetic moment of the Fe atom. (4) In
Fe54C2, the tetragonality and magnetic moment of the Fe atom change
with the distance between two carbon atoms, with the tetragonality being
0.981, 1.036, or 1.090. When the Fe- C -Fe pair, which consists of the first
carbon atom and its two nearest neighbor Fe atoms, is perpendicular to the
second pair, which consists of the second carbon atom and its two nearest
neighbor Fe atoms, the tetragonality is 0.981 and does not agree with the
experimental value. The mechanical energy is relatively large. On the other
hand, when the first pair is parallel to the second pair, the tetragonality is
1.036, which agrees well with experimental data. In this case, the me-
chanical energy is relatively small. When a straight C -Fe -C pair is formed,
the tetragonality is 1.090; (5) In a Fe54C2 supercell, the formation enthalpy
is relatively low when the calculated tetragonality is 1.036, and the ex-
istence probability under the assumption of a Boltzmann distribution is
high. In other cases, the formation enthalpy is relatively high and the ex-
istence probability is almost zero; (6) The average magnetic moment of an
Fe atom is proportional to volume, but it is not clearly related to the tet-
ragonality. It is believed that the increase in the magnetic moment of the Fe
atom by the addition of a carbon atom is primarily due to the magneto
-volume effect, and is not due to the tetragonality effect. (7) The repulsion
between nitrogen atoms at close distance is stronger than that between
carbon atoms.
Reference
[1] H.Ohtsuka, V.A. Dinh, T.Ohno, K.Tsuzaki, K.Tsuchiya, R.Sahara,
H.Kitazawa and T. Nakamura, ISIJ International, 55(2015), 2483-2491.
O14
Cluster Expansion Study of the Binary System in
Multicomponent Nd-Fe-B Permanent Magnet System
Arkapol Saengdeejing1, Ying Chen1, Masashi Matsuura2, Satoshi
Sugimoto2
1
Fracture and Reliability Research Institute, Graduate School of
Engineering, Tohoku University, Japan
2
Department of Materials Science, Graduate School of Engineering,
Tohoku University, Japan
In the Nd-Fe-B permanent magnet materials, several elements such
as C, B, Cu, Dy, etc. are added to the systems to improve the properties
of the magnet. Experimentally determining the phases in the multi-
component systems become difficult and costly. With the help of
CALPHAD-type thermodynamic model[1], it is possible to predict the
phases stability in such a complex multicomponent systems. However,
the accurate thermodynamic databases of the lower ordered systems
(binary, ternary, quarternary, etc.) are required in order to accurately
predict the phase diagram in those multicomponent systems. There are
very limited thermodynamic databases for the Nd-Fe-B ternary system
and even less for the higher ordered systems. First-principles calcula-
tions are proving to become more and more useful for providing some
of thermodynamic data where the experiments are in sufficient or im-
possible to carryout.
In this work, we performed first-principles calculations on several
binary solid solution phases shown in table 1 to obtain the mixing en-
thalpy data which will provide useful information for the construction
of thermodynamic databases, as well as reveal the essential features of
these binary systems from the electronic structures. First-principles that
based on density functional theory (DFT) are performed using Vienna
Ab-initio Simulation Package(VASP)[2]with projector augmented-wave
method(PAW)and generalized gradient approximation (GGA) that de-
scribe the exchange and correlation energies are used for the calcula-
tions. Cluster expansion which is used for calculate mixing enthalpy is
performed using Alloy Theoretic Automated Toolkit (ATAT)[3].
6
Calphad xxx (xxxx) xxx–xxx
References
[1] H. Lukas, S. G. Fries, B. Sundman, Computational
Thermodynamics (Cambridge University Press, Cambridge, 2007).
[2] G. Kresse, Phys. Rev. B 54, 11169 (1996).
[3] A. van de Walle, M. Asta, G. Ceder, CALPHAD: Comput. Coupling
of Phase Diagrams and Thermochem. 26, 539 (2002).
O15
An ab-initioprediction of the composition of κ carbidesin Fe-
Mn-Al-C steels
Poulumi Dey1, Roman Nazarov2, Biswanath Dutta1, Mengji Yao1,
Michael Herbig1, Martin Friák3, Tilmann Hickel1, Dierk Raabe1 and
Jörg Neugebauer1
1
Max-Planck-Institut für Eisenforschung GmbH, D-40237
Düsseldorf, Germany
2
Livermore National Laboratory, Livermore, CA 94550, USA
3
Institute of Physics of Materials, v.v.i., Academy of Sciences of the
Czech Republic, CZ-61662 Brno, Czech Republic
The quaternary Fe-Mn-Al-C alloys have generated enormous atten-
tion because of their interesting mechanical properties such as excep-
tional combination of high strength and ductility along with low den-
sity and high corrosion resistance. The improved mechanical properties
are to a large extent determined by the underlying microstructure
which comprises of an austenitic Fe-based matrix along with regularly
arranged nano-sized κ carbides (Fe,Mn)3AlC [1]. These finely dispersed
precipitates are coherently formed during annealing when the Al con-
tent is higher than 6 wt.% in these alloys. The prerequisite to the in-
vestigation of the thermodynamic stability of these precipitates is the
knowledge of their stoichiometry. Both are strongly influenced by the
interface to the matrix material. Further, the understanding of pre-
cipitation hardening in these alloys, demands detailed analysis of the
stoichiometry as an off-stoichiometric composition is expected to
modify the strengthening effects due to changethe anti-phase boundary
energy.
We, thus, perform a thorough investigation of the composition of
these precipitates with the aid of density functional theory (DFT) cal-
culations. Our ab-initio investigations predict a deviation from stoi-
chiometry for both Al and C in these κ carbides. The C off-stoichiometry
is an outcome of the compromise between the elastic and chemical
energies of the system. While the inherent elastic strain in the coherent
microstructure drives C away from κto the surrounding γ matrix, the
chemical energy gain bythe retention of C in the precipitate prevents
such a C outflow [2]. Furthermore, our study clearly shows that the off-
stoichiometry of C is coupled to the reduced Al content since the latter
can be explained by a combination of strain effect and Mn antisites in
the vicinity of C vacancies [3]. Our ab-initio based prediction has been
confirmed by experiments in which atom probe tomography (APT)
technique has been employed to measure the chemical composition of
these precipitates [3]. The underlying methodology can be extended to
other kinds of coexisting phases in which a coherent interface de-
termines thecomposition at thermodynamic equilibrium.
References
[1]I. Gutierrez-Urrutiaet al., Scripta Materialia, 68(2013)343.
[2] P. Deyet al., submitted to Physical Review B, (2016).
[3] M. Yao et al., Acta Materialia, 106 (2016) 229.

O16
Thermodynamic modelling of sigma phase using ab initio re-
sults
PAVLŮ Jana1,2, VREŠTÁL Jan1,2,3, ŠOB Mojmír1,3,2
1
CEITEC - Central European Institute of Technology, Masaryk
University, Kamenice 753/5, CZ-625 00 Brno, Czech Republic
2
Department of Chemistry, Faculty of Science, Masaryk University,
Kotlářská 2, CZ-611 37 Brno, Czech Republic
3
Institute of Physics of Materials, Academy of Sciences of the Czech
Republic, Žižkova 22, CZ-616 62 Brno, Czech Republic
Sigma phase is a structure which is frequently found in various
superaustenitic steels where it significantly influences mechanical
properties of alloys. For this reason many scientists have been working
to find its optimal thermodynamic description and to characterise
properly its behaviour [1-8]. Some of the models are based on the
qualified determination of parameters based on the assessment of ex-
perimental data [1-3]. Additionally, the knowledge gained from ex-
periments can be complemented by ab initio calculated data. These
data can help to give the physical meaning to the parameters used in
thermodynamic modelling [4-7] because the ab initio calculations
provide information on energies of formation of particular configura-
tions of studied phases with respect to occupation of sublattices, on
energy differences related to the change of magnetic ordering, and es-
timation of mechanical stability. As the power of computational tools is
increasing, it becomes possible to model sigma phase using a five-
sublattice model [6-7] which corresponds to the crystallography of
sigma phase. This presentation employs various available models, in-
troduces calculated phase diagrams and compares them with experi-
mental data for selected binary systems.
Acknowledgments
This research was supported by the Grant Agency of the Czech
Republic (Project No. 14-15576S) and by the project CEITEC 2020
(LQ1601) with financial support from the Ministry of Education, Youth
and Sports of the Czech Republic under the National Sustainability
Programme II. Financial support of the Academy of Sciences of the
Czech Republic (Project No. RVO:68081723) is also gratefully ac-
knowledged. The access to computing and storage facilities owned by
parties and projects contributing to the National Grid Infrastructure
MetaCentrum, provided under the program ‘Projects of Large
Infrastructure for Research, Development, and Innovations’
(LM2010005) is highly appreciated.
References
[1] J.-O. Anderson, B. Sundman, Calphad, 11 (1987) 83.
[2] J. Havrankova, J. Vrestal, J. Tomiska, Berichte der
Bunsengesellschaft für Physikalische Chemie 102 (1998) 1225.
[3] A.V. Davydov, U.R. Kattner, J. Phase Equilib., 24 (2003) 209.
[4] J. Houserova, J. Vrestal, M. Friak, M. Sob, Calphad, 26 (2002)
513.
[5] J. Houserova, J. Vrestal, M. Sob CALPHAD, 29 (2005) 133.
[6] S. Fries, B. Sundman, Phys. Rev. B, 66 (2002) 012203
[7] Z. Li, H. Mao, P. A. Korzhavyi, M. Selleby, Calphad, 52 (2016) 1.
[8] J.-M. Joubert, Progress in Materials Science, 53 (2008) 528.
O17
Phase Stability of Ni-Re and Ni-Ru Alloys:First-
principles Calculations and Calphad Modeling
G. Ghosh*, A. van de Walle**, M. Asta***
*Dept. of Materials Science and Engineering, Northwestern
University, 2200 Campus Drive, Evanston, IL 60208-‐3108, USA.
**Division of Engineering, Brown University, RI 02921, USA
***Dept. of Materials Science and Engineering, 384 Hearst Mining
Building, Berkeley, CA 64720-1760, USA
One of the advantages of first-principles methods is the ability to
7
Calphad xxx (xxxx) xxx–xxx
calculate thermodynamic properties of solids when they may be in-
accessible by conventional experimental methods. This is the focus of
this presentation. Both Re and Ru are used in modern Ni-base super-
alloys, to a greater or lesser extent. However, to date reliability of
thermodynamic parameters Ni-Re and Ni-Ru systems, even in com-
mercial databases, is uncertain due to lack of experimental data. This
makes Calphad modelling of these two important binary systems a
difficult task barring bruteforce approach to fit experimental phase
diagram data. Recently, we have undertaken a systematic and com-
prehensive study of phase stability of Ni-Re and Ni-Ru alloys to in-
corporate first-principles calculations and Calphad modelling.
Equilibrium phase diagrams of Ni-Re and Ni-Ru systems are topologi-
cally similar: the liquid phase at high temperatures, and two terminal
solid solutions (fcc in the Ni-side and hcp in Re/Ru side) at low/in-
termediate temperatures. There is no intermetallic phase, in either
system. However, partitioning of both Re and Ru are important in Ni-
base superalloys as they exert strong influence via misfit control (be-
tween γ and γ’), coarsening rate of γ’, solubility in γ, interfacial segre-
gation, and stability of topologically close packed phases (TCP). Several
TCP phases seem to be stabilized in multi-component Ni-base super-
alloys containing Re and Ru. We have carried out cluster expansion of
bcc, fcc and hcp defining thermodynamic properties of solid solutions
using ATAT package in conjunction with VASP. In addition, we have
performed a systematic study of phase stability of TCP phases (σ, µ,
Laves). These allow us Calphad modelling on a firm footing. Results will
be presented in detail.
Keywords: ATAT, cluster expansion, Calphad modeling, first-prin-
ciples calculations, solid solutions, Ni-base superalloys, TCP phases.
O18
Prediction of the site preference and properties of complex
alloy phases by combining thermodynamic model and abinitio
calculations
Bo Wu, Kangming Hu, Jinchang Huang, Zhenyi Wei, Qiong Peng,
Baisheng Sa, Zheyu Xie
Multiscale Computational Materials Facility, College of Materials
Science and Engineering, Fuzhou University, Fuzhou 350100, P.R.
China (E-mail:wubo@fzu.edu.cn)
The site preference of alloy elements on sublattice is of both fun-
damental and technical importance in materials science. For example,
the site preference gives hints to establish the sublattice model in
CALPHAD approach, as well as guide the alloying atom site arrange-
ment when carrying out ab initio calculations for physical and me-
chanical properties. In this contribution, based on the crystallographic
information of the corresponding prototype, we established the general
sublattice model to describe the site occupy behaviour, then the site
occupying fraction were solved by thermodynamics calculation with
the support of ab initio calculations. Thereafter, we distributed alloying
atoms randomly on the each sublattice in the applicable supercell based
on their site fractions (DRSS), thus the elastic or magnetic properties of
complex alloy phases were obtained using ab initiocalculations. We will
present our recently study on the fine microstructure and mechanical
properties of some selective alloy phases, including Ti2AlNb-based or-
thorhombic phase (O phase), multi-principal component alloy (so-
called high entropy alloys), and SmCo5-based magnetic materials. We
calculated the site occupying fraction and the corresponding properties,
and compared with other different approaches to deal with the solid
solution phase, i.e., special quasirandom structure (SQS) model and the
exact muffin-tin orbitals (EMTO) method in combination with the co-
herent potential approximation (CPA), as well as the available experi-
mental data. An applicable approach was established to predict the
fundamental microstructure and properties quantitatively for the alloy
phases with complex composition and complex structure.

O19
Phase boundary calculations for B2 ordered and disordered
phases in Fe-Si system by using CVM and Thermo-calc
N. Kiyokane1, T. Mohri2, Y. Chen3, T. Yamashita1, T. Iguchi4
1
Analysis and Characterization Research Department, JFE Steel
Corporation, 1 Kawasaki-cho, Chuo-ku, Chiba, Japan
2
Institute for Materials Research, Tohoku University, 2-1-1
Katahira, Aoba-ku, Sendai, Japan
3
School of Engineering, Tohoku University, 6-6-01 Aramakiaoba
Aoba-ku, Sendai, Japan
4
Numerical Simulation Research Department, JFE Steel
Corporation, 1-1, Minamiwatarida-cho, Kawasaki-ku, Kawasaki, Japan
Silicon is a very important element for steel materials due to its
significant effects on various properties. In Fe-Si system, the disordered
b.c.c. structure is present at low silicon contents and the B2 ordered
phase becomes stable as the silicon content increases. In the present
8
Calphad xxx (xxxx) xxx–xxx
study, we investigated the phase equilibria between these two phases
by Cluster Variation Method (CVM). The four-body atomic interaction
energies are obtained by combining first principles calculations [1]
with Cluster Expansion Method. CVM within tetrahedron approxima-
tion was employed with and without vibration effect [2]. The obtained
phase diagrams in Fig. 1(a) show an excessively high transformation
temperature compared with the experimental results. One reason for
overestimation of the transformation temperature stems from the fact
that the local atomic displacement is not considered. There is a differ-
ence of about 10 % between the atomic radii of iron and silicon in a
b.c.c. system, and this difference may have a large influence on phase
stability. Compared with the Bragg-Williams (BW) and CVM calcula-
tions, a reasonable phase boundary is obtained using Thermo-calc
software based on BW with SSOL4 as shown in Fig. 1(b). The SSOL4
databases of Fe-Si system may implicitly include this effect in these free
energy parameters.
References
[1] A. Saengdeejing et al., Comput. Mater. Sci., 70(2013), 100.
[2] T. Mohri et al., J. Phase Equilibria and Diffusion, 30(2009),
553.
O20
Thermodynamics of Critical Phenomenon and Its Prediction
Zi-Kui Liu, Yi Wang, and Shun Li Shang
Department of Materials Science and Engineering The Pennsylvania
State University, University Park, PA 16802, USA
A critical point is a dividing boundary dictating whether a system is
homogeneous or heterogeneous. In a system with two independent
potentials, a critical point is a zero-dimension point. When an addi-
tional independent potential is introduced, the prior critical point be-
comes a two-dimension critical line, which should end as a zero-di-
mension point in the three-dimensional space consisting of the three
potentials. This continues as more independent potentials are in-
troduced. The critical point is typically defined by the instability of a
homogeneous system when the second derivatives of the system energy
with respect to internal molar quantities reach zero. On the other hand,
when the critical point is approached from a heterogeneous system, this
definition is difficult to apply because the molar quantities are not

homogeneous in this heterogeneous system. Furthermore, each homo-
geneous subsystem in this heterogeneous system may not experience
the instability when the critical point is approached.
In the present work, we demonstrate that the critical point can be
considered as the statistic mixture of various stable and metastable
subsystems that we call microscopic states or simply microstates. We
show that the mixing entropy among microstates is responsible to the
formation of the statistically homogenous system consisting of one
stable microstate and many metastable microstates. The probabilities of
metastable microstates are dictated by the free energy differences be-
tween the stable and metastable microstates, which may be predicted
from first-principles calculations and modelled in the framework of the
CALPHAD method.
O21
Effective cluster interactions and intermetallics thermo-
dynamics: an historical perspective
Cláudio Geraldo Schön
Dept. of Metall. Mater. Eng., Escola Politécnica da Universidade de
Sao Paulo, Av. Prof. Mello Moraes, 2463 – CEP 05508-900 Sao Paulo,
Brazil.
The most successful statistical thermodynamics models in material
science rely on decomposing the internal energy of the system into
effective cluster interactions (ECIs), attributable to groups of inter-
acting atoms (the "clusters", like pairs, triangles, tetrahedra and so on).
This allows the application of several approaches to solve the complex
statistical mechanical problem of calculating the alloy entropy, hence
obtaining the system's Gibbs free energy. As a result, ordered inter-
metallics appear as a "natural" solution of these models, when inter-
actions of unlike atoms become predominant. This decomposition of the
internal energy into "cluster interactions" is so successful, that it is often
used in introductory materials thermodynamics classes around the
world as an example of "materials" application. The physical nature of
the ECIs, however, has been a subject of controversy in the specialized
literature. More recently, the advent of modern quantum mechanical
models for the calculation of electronic structure allowed the direct
determination of these parameters, with the obvious results that they
can be checked against experimental data on compound thermo-
dynamics and phase equilibria. The aim of the present work is to review
and clarify the context in which ECIs are used in the different formal-
isms introduced in the XXth century, in particular: 1) the early attempts
of using the Ising model to calculate phase diagrams of ordered alloys,
2) the formalism of Bieber and Gautier, with their "concentration de-
pendent" ECIs, 3) the cluster expansion method (CEM) and modern ab
initio phase diagram calculation, and 4) the position dependent cluster
interactions in the context of the Continuous Displacement - Cluster
Variation Method (CD-CVM). The perspectives for the future in the field
will be discussed.
O 22
First-Principles Study and Thermodynamic Modeling of Zn and
Au Impurities and vacancies in GaAs
Masoomeh Ghasemi1, Martin Stankovski2, Jonas Johansson1
1 portant free energy contributions, which have been calculated within
Solid State Physics, Lund University, Box 118 SE-22100 Lund,
Sweden
2 spectively. To get the chemical trends for phase transition tempera-
LU Open, Lund University, Box 117, SE-22100 Lund, Sweden
Controlled doping of semiconductor nanowires is of paramount
importance as they are potential building blocks of future electronic
and optoelectronic devices. The nanowires are commonly grown via a
Vapour-Liquid-Solid (VLS) mechanism [1] using foreign seed particles
(often Au particles). The electronic properties of nanowires can be
tuned via doping by foreign impurity atoms. However, unintentional
doping may also occur due to the incorporation of seed particle atoms
during growth as well sd formation of native defects in the nanowires.
The aim of the current project is to study the energetics and
9
Calphad xxx (xxxx) xxx–xxx
concentrations of native defects and foreign impurity atoms in the GaAs
nanowires [2-3]. In this work, the total energy of different point defects
in GaAs including the Zn dopant, Au seed particle and vacancies in
different charged states will be calculated via Density Functional
Theory (DFT). We are currently calculating the energetics of the defects
using DFT calculations and implementing the supercell method using
the Abinit code [4]. The interaction of the electrons with the ionic cores
is described using the Projector-Augmented Wave (PAW) method and
the Local Density Approximation (LDA) is used for the ex-
changecorrelation functional. Based on the relative stability of the de-
fects, we will set up a thermodynamic model for the GaAs compound
through the CALculation of PHAse Diagram (CALPHAD) method. The
thermodynamic model of the GaAs compound including Zn dopants, Au
impurities and vacancies can be expressed by a three-sublattice model
within the compound energy formalism (CEF) [5] as:
(Ga, VaGa, ZnGa)α(As, VaAs, AuAs)β(Va’,e-, h+)γ
where the first two sublattices, α and β, are the Ga and As sites,
respectively. The charge state of the ionised impurities and native de-
fects is represented by the third sublattice, γ. The model is chosen based
on the available experimental and first-principles data of the defects
and impurities in GaAs. As a result of the current study, the existing
thermodynamic model of the GaAs phase which does not take the im-
purity and native defect concentrations into account will be optimized.
This model can eventually be used for modelling the growth of Zn-
doped and Au-seeded GaAs nanowires.
References
[1] Wagner, R. S.; Ellis, W. C., Appl. Phys. Lett., 4 (1964), 89.
[2] Rogal, J., et al., Physica status solidi (b), 251 (2014), 97.
[3] Van de Walle, C. G., Applied Physics Reviews, 95, (2004), 3851.
[4] Gonze, X., et al., Comput. Computer Physics Communications,
180 (2009), 2582. [5] Hillert, M., Journal of Alloys and Compounds,
320 (2001), 161.
O 23
Phase diagrams in magnetic shape memory alloys: insights
obtained from ab initio thermodynamics
Biswanath Dutta, Tilmann Hickel, Jörg Neugebauer
Max-Planck-Institut für Eisenforschung GmbH, Düsseldorf, 40237,
Germany
Heusler alloys of the Ni-Mn-X (X=Ga, Al, In, Sn etc.) type have been
investigated in recent times with great interest due to their functional
properties (magnetic shape memory and magnetocaloric effect) [1].
These functional properties have their origin in the underlying ther-
moelastic martensitic transformation, which critically depends on the
composition. The observations of intermartensitic transformations have
further opened up the possibility of the presence of multiple martensitic
phases at the same composition. Therefore, any application of these
materials requires a detailed knowledge of the thermodynamic stability
of the invloved phases in the composition-temperature phase diagrams.
We have, therefore, developed an ab initio scheme based on density
functional theory (DFT) to derive all free energy contributions for the
relevant phases of the magnetic Heusler alloy Ni2+yMn1y+xGa1-x [2].
Here, vibrational as well as magnetic excitations form the most im-
quasiharmonic approximation and fixed-spinmoment approach, re-
tures, a polynomial interpolation of the free energies between different
compositions is employed.
An important outcome of this ab initio study is the prediction of
chemical trends for the martensitic transition temperature (TM), which
agree perfectly with available experimental data [3]. The stability of
modulations in the martensite has previously been discussed as an
adaptation effect to the interface to the austenite. Instead, our calcu-
lations have revealed that the modulated 5M phase is thermo-
dynamically stable as an individual phase. The intermartensitic

transformation (IM) happens between the modulated 5M and the non-
modulated L10 martensitic phases with the latter dominating the mar-
tensite in a rather large composition region. Another outcome of our
investigation is the remarkable similarity of the phase diagram of
Ni2+yMn1-yGa to that of Ni2Mn1+xGa1-x. This is a consequence of the
similar electronic properties of Ni-rich and Mn-rich alloys and indicates
that the number of valence electrons per atom e/a is a good descriptor
for martensitic as well as intermartensitic transition temperatures.
References
[1] T. Hickel et al., Adv. Eng. Mater., 14 (2012) 547.
[2] M. A. Uijttewaal et al., Phys. Rev. Lett., 102 (2009) 035702.
[3] B. Dutta et al., Phys. Rev. Lett., 116 (2016) 025503.
O 24
The third generation CALPHAD databases: Mo-Nb-Ta phase
diagram with the segmented model
Irina Roslyakova1, Lijun Zhang2, Setareh Zomorodpoosh1, Bo
Sundman3, Holger Dette4,
Ingo Steinbach1
1 reliable results for Al [6], Cu [8] and Ag [9], and even for magnetic
ICAMS, Ruhr-University Bochum, Germany
2 elements such as Cr [10]. The TU-TILD method, which provides even
State Key Laboratory of Powder Metallurgy, Central South
University, Changsha, P.R. China
3 thermodynamics of ZrC, an ultrahigh-temperature ceramic compound
CEA, Sacley, France
4 [7]. In the present work we use the TU-TILD method to model the
Faculty of the Mathematics, Ruhr-University Bochum, Germany
A novel thermodynamic modelling strategy of stable solid alloy
phases is proposed based on segmented regression approach [1]. The
model considers several physical effects [2] (e.g. electronic, vibrational
etc.) and is valid from 0K up to the melting temperature. The preceding
approach has been applied for several pure elements, Al, Cr, Ge, Ir, Mo,
Nb, Re, W, Fe, Ni and Ta. Results show good agreement with experi-
mental data at low and high temperatures.
Based on the fitted heat capacity function CP(T), other important
thermodynamic functions as Gibbs energy G(T), entropy S(T) and en-
thalpy H(T) have been established for the proposed segmented regres-
sion model [3]. The obtained temperature dependence for the Gibbs
energy function has been applied for the calculation of Mo-Nb-Ta
phase-diagram. Calculated phase diagrams have been compared with
the ternary Mo-Nb-Ta system published by Xiong et al.[4].
References
[1] Y. S.Toulouklin, Thermophysical properties of matter: The TPRC
Data, Volume 4: Specific Heat, Metallic Elements and Alloys, 1975.
[2] H. Lukas, S. Fries, B. Sundman, Computational Thermodynamics:
The Calphad Method, Cambridge University Press, 2007.
[3] I. Roslyakova, B. Sundman, H. Dette, Modeling of thermos-
physic properties for pure elements using segmented regression meth-
odology. CALPHAD XLIII, Changsha, China, 2014.
[4] Wei Xiong, Yong Du, Yong Liu, B.Y. Huang, H.H. Xu, H.L. Chen,
Zhu Pan, Thermodynamic assessment of the Mo-Nb-Ta system,
CALPHAD, 28 (2004), 133-140.
O25
Creating a new generation of Calphad databases: Challenges
and achievements
Sedigheh Bigdeli1, Sascha Maisel2, Dominique Korbmacher2, Blazej
Grabowski2, Huahai Mao1,3, Qing Chen3 and Malin Selleby1
1 100 44 Stockholm, Sweden
Materials Science and Engineering Department, KTH Royal
Institute of Technology, Stockholm, 100 44, Sweden
2 thermodynamic descriptions of the unary elements involved in these
Max-Planck-Institut für Eisenforschung GmbH, Max-Planck-Straße
1, 40237, Düsseldorf, Germany
3 phases in the systems are described within the framework of compound
Thermo-Calc Software AB, Norra Stationsgatan 9, SE-113 64
Stockholm, Sweden
In developing a new generation of Calphad databases, new models
[1] are used in which each term contributing to the Gibbs energy has a
10
Calphad xxx (xxxx) xxx–xxx
physical meaning. For example, harmonic vibrations of atoms are
modelled using the Einstein temperature, anharmonic vibrations,
electronic and magnetic contributions for solid phases each have spe-
cific terms and the two-state model [2] is used for the liquid phase.
These models have already been used to describe the thermodynamic
properties of unary Mn [3] and were then proven to work properly. To
continue the development, a new description for unary carbon is being
developed using the same models for diamond and liquid. For the more
complicated carbon allotrope, graphite, with different frequncies of
atomic viberations in different directions [4], a modified model using
two different Einstein temperatures is used.
To be able to develop new thermodynamic databases we are con-
fined to use existing computational tools but at the same time we want
to make the best possible use of atomistic methods [5]. These methods
have so far not been straightforward to use and have not been reliable
at finite temperatures. Recently, however, new methods have been
developed [6,7] for which the calculated thermodynamic properties at
finite temperatures are much more accurate, the calculations being time
efficient, and convenient. The UP-TILD method [6] was shown to give
better computational efficiency, has been shown to well describe the
thermodynamic properties of paramagnetic bcc Mn.
References
[1] Qing Chen and Bo Sundman, Journal of Phase Equilibria, 22 (6),
631(2001).
[2] W. Cahse, I. Ansara, A. Dinsdale, G. Grimvall, L, Höglund and H.
Yokokawa, Calphad, 19, 437 (1995).
[3] S. Bigdeli, H. Mao and M. Selleby, Physica Status Solidi (B), 252,
2199 (2015).
[4] J. Krumhansl, H. Brooks, The Journal of Chemical Physics, 21
(10), 1663 (1953).
[5] M. Palumbo, B. Burton, A. Costa e Silva, B. Fultz, G. Grabowski,
G. Grimvall, B. Hallstedt, O. Hellmann, B. Lindahl, P. E. A. Turchi and
W. Xiong, Phys. Status Solidi B, 251, 14 (2013).
[6] B. Grabowski, L. Ismer, T. Hickel and J. Neugebauer, Phys. Rev.
B 79 (13), 134106 (2009).
[7] A. I. Duff, T. Davey, D. Korbmacher, A. Glensk, B. Grabowski, J.
Neugebauer and M. W. Finnis, Phys. Rev. B 91 (21), 214311 (2015).
[8] A. Glensk, B. Grabowski, T. Hickel and J. Neugebauer, Phys.
Rev. X 4 (1), 011018 (2014).
[9] A. Glensk, B. Grabowski, T. Hickel and J. Neugebauer, Phys.
Rev. Lett. 114 (19), 195901 (2015).
[10] F. Körmann, B. Grabowski, P. Söderlind, M. Palumbo, S. G.
Fries, T. Hickel and J. Neugebauer, J. Phys.: Condens. Matter 25 (42),
425401 (2013).
O 26
Re-assessment of the Co-C and Cr-C systems for the third gen-
eration of thermodynamic databases
Zhou Li, Huahai Mao, Malin Selleby
Division of Computational Thermodynamics Department of
Materials Science and Engineering KTH Royal Institute of Technology,
The present work reassessed the Co-C and Cr-C systems. All of the
two systems were taken from the third generation database. Solution
energy formalism. The thermodynamic stabilities of Cr carbides in Cr-C
system were discussed. The optimizing parameters were assessed from
available phase equilibria and thermodynamic information. A new

description of two binaries is obtained and the calculated results are
compared with experimental phase diagram and thermochemical data.
O 27
Contour Diagrams and Their Applications
Fan Zhang, Shuanglin Chen, Weisheng Cao, Chuan Zhang, Jun Zhu
CompuTherm, LLC
437 S. Yellowstone Dr., Madison, WI, USA
A contour line is a curve along which a certain property is constant.
A contour map, which is a map illustrated with contour lines, is very
useful in visualizing property variation in a twodimensional or three-
dimensional space. Contour maps have found many applications in
meteorology, geology, environmental science, ecology, statistics, and
many engineering fields. Contour line/map is certainly not new to
people who work in the field of thermodynamics and phase diagrams.
One of the most commonly used contour maps (diagrams) is a liquidus
projection with isothermal lines.
A general algorithm has been implemented in Pandat software to
calculate two-dimensional property contour diagrams in multi-compo-
nent systems. In this presentation, we will present variety types of
contour diagrams, such as phase fraction, partial pressure, molar vo-
lume and driving force, and discuss their applications.
O 28
The Open Calphad software
Bo Sundman1, Ursula R Kattner2, Mauro Palumbo3 and Suzana G
Fries4
1
INSTN, CEA Saclay, France
2
NIST, USA
3
SISSA, Trieste Italy
4
ICAMS, SKTS, Ruhr University Bochum, Germany
The Open Calphad initiative can now provide a free, flexible and
powerful software for calculation of equilibria in multicomponent
materials for varying conditions. All basic parts of the system including
the source code and extensive documentation are now available at
http://www.opencalphad.org:
● a model package with multicomponent implementations of CEF
with ionic constituents, models for liquids with SRO and gases,
● a module for equilibrium calculations in parallel with flexible con-
ditions,
● methods for calculating various kinds of diagrams,
● a possibility to assess model parameters from experimental data,
● a software interface for thermodynamic and other materials data to
applications which can benefit from the parallelization.
OC can handle kinetic data (e.g mobilities) and other materials
properties that depend on T, P and the composition of each phase (e.g.
lattice parameters, elastic constants). There are still features that are
not fully implemented and tests, feedback and contributions from users
are welcome. For developers an updated version is available at the
opencalphad repository at http://www.github.org.
There are no databases provided with OC but OC welcomes the
development of a new unary database based on physical modeling and
high quality assessments of complex binary and ternary systems.
References
1. Bo Sundman, Ursula R Kattner, Mauro Palumbo and Suzana G
Fries, OpenCalphad - a free thermodynamic software, in Integrating
Materials and Manufacturing Innovation, {\bf 4}:1 (2015), open access
2. Bo Sundman, Xiao-Gang Lu and Hiroshi Ohtani, Comp Mat Sci,
{\bf 101} (2015) 127137
O29
Application of the nano-Calphad technique to metal-hydrogen
systems
11
Calphad xxx (xxxx) xxx–xxx
Jean-Marc Joubert, Yassine Oumellal, Claudia Zlotea
Chimie Métallurgique des Terres Rares, Institut de Chimie et des
Matériaux Paris-Est, CNRS, Université Paris-Est Créteil, 2-8 rue Henri
Dunant, 94320 Thiais Cedex, France
Metal–hydrogen systems are fascinating from both scientific and
technological point of view. In particular, the possible application as
hydrogen storage materials is responsible for intense research activities.
Following the recent general interest in nanomaterials, many works
have been devoted to the modification of the hydrogen absorption
properties when decreasing the particle size to the nanoscale [1].
Indeed, strong modifications of the thermodynamic properties have
been reported [2].
Following our investigation of metal–hydrogen systems by the
Calphad method [3-7], we have started the study of these systems using
the so-called nano-Calphad approach [8, 9].
This method has been applied to try to explain the facile synthesis of
single phase Pd–Rh alloys at the nanoscale in spite of a miscibility gap
and a complete thermodynamic description of this system including the
size effect has been obtained. Then, we applied this technique to me-
tal–hydrogen systems such as the prototypic Pd–H system.
References
[1] R. Griessen, N. Strohfeldt and H. Giessen, Nature Materials, 16
November 2015 (2015) 1-7.
[2] C. Zlotea and M. Latroche, Colloids and Surfaces A, 439 (2013)
117-130.
[3] A. Mascaro, C. Toffolon-Masclet and J.-M. Joubert, Calphad:
Comput. Coupling Phase Diagrams Thermochem., 41 (2013) 50-59.
[4] N. Bourgeois, J.-C. Crivello, A. Saengdeejing, Y. Chen, P.
Cenedese and J.-M. Joubert, J. Phys. Chem. C, 119 (2015) 24546-24557.
[5] J.-M. Joubert and S. Thiébaut, Acta Mater., 59 (2011) 1680-
1691.
[6] J.-M. Joubert, Int. J. Hydrogen Energy, 35 (2010) 2104-2111.
[7] J.-M. Joubert and S. Thiébaut, J. Nucl. Mater., 395 (2009) 79-88.
[8] S. Bajaj, M. G. Haverty, R. Arroyave, W. A. Goddard III FRSC and
S. Shankar, Nanoscale, 7 (2015) 9868-9877.
[9] J. Lee and K. J. Sim, Calphad: Comput. Coupling Phase Diagrams
Thermochem., 44 (2014) 129-132.
O31
Phase diagrams of Ni–H and Pd–H systems using ab-initio based
Cluster Variation Method and Monte-Carlo simulation
Natacha Bourgeois1, Pierre Cenedese1, Jean-Claude Crivello1,
Arkapol Saengdeejing2, Ying Chen2, Jean-Marc Joubert1
1
Institut de Chimie et des Matériaux Paris-Est, CNRS, Université de
Paris-Est Créteil, UMR 7182, 2-8 rue Henri Dunant, F-94320 Thiais,
France
2
Fracture and Reliability Research Institute, School of Engineering,
Tohoku University, 6-6-04, Aramaki Aza Aoba Aoba-ku, Sendai, Miyagi
980-8579, Japan
Under favourable temperature and pressure conditions, metals have
the capacity to absorb hydrogen reversibly. Either ordered hydrides or
disordered interstitial solid solutions may be formed. It is important to
be able to predict the hydride formation because of their central role in
hydrogen storage and many structural material embrittlement issues.
This work focused on the stability of hydrogen interstitial solid so-
lutions using an ab-initio based approach: on the basis of Density
Functional Theory (DFT) calculations, the hydrogen-vacancy interac-
tion energies on the interstitial lattice can be estimated using the
Cluster Expansion Method (CEM) [1] and used as input data in the
Cluster Variation Method (CVM) [2]. This approach allows us to com-
pute phase diagrams as well as the enthalpy and entropy of mixing
which can be injected into a more global CALPHAD assessment.
Besides, the CEM results also supplied a Monte-Carlo simulation [3],
allowing us to predict the atoms positions at the equilibrium.
The interstitial solid solution of hydrogen in the face centered cubic

host lattices of palladium and nickel were studied. We already used the
results of the CEM in the CALPHAD modelling of the Ni–H system [4],
in order to assess the interaction parameters. The present study goes
further by computing the phase diagrams of Ni–H and Pd–H systems
and investigated the mechanisms leading to the formation of the mis-
cibility gap observed in both systems.
References
[1] J. Connolly, A. Williams, Phys. Rev. B, 27 (1983) 5169–5172
[2] R. Kikuchi, Phys. Rev., 81 (1951) 988–1003
[3] K. Binder, Statics and Dynamics of Alloy Phase Transformations,
Springer US, Boston, 1994, 467–493
[4] N. Bourgeois, J. C. Crivello, A. Saengdeejing, Y. Chen, P.
Cenedese, J. M. Joubert, J. Phys. Chem. C, 119 (2015) 24546–24557
O32
On the chemical potentials of components in nano-phases
George Kaptay
Bay Zoltan Nonprofit Ltd for Applied Research, BAY-ENG, Miskolc,
3519 Hungary
University of Miskolc, Department of Nanotechnology, Miskolc
3525 Hungary
The chemical potentials of components in nano-phases determine
the equilibrium of nanomaterials. In this paper the difference between
the equilibrium of a nano-phase and the equilibrium of an analogous
macro-phase under same constraints is called a “nano-effect” for
brevity. Historically the first attempt to describe equilibrium of nano-
materials was due to Kelvin (1871), claiming that the nano-effect is due
to the increased curvature of the nanophase. This approach forms the
basis of the Kelvin paradigm, still widely used in chemistry, biology and
materials science (but not in physics). The Kelvin paradigm is the basis
of the Kelvin equation, the Gibbs-Thomson equation and the Ostwald-
Freundlich equation for the vapor pressure, melting point and solubility
of spherical (or quasi-spherical) nano-phases, respectively. The Kelvin
paradigm is also successful in the interpretation of more complex
phenomena, such as capillary condensation. However, the Kelvin
paradigm predicts no nanoeffect for not curved nano-phases, such as
crystals and thin films, contradicting experimental facts. Moreover, it
wrongly predicts that a cubic (or a thin-film shaped) nano-droplet is
more stable than a spherical nano-droplet of the same volume. In ad-
dition to its positive features, these and other shortcomings of the
Kelvin paradigm are discussed. A new paradigm is worked out in this
paper, claiming that the nano-effect is due to the increased specific
surface area of the nano-phase. Chemical potentials of components in
multi-component free standing nano-phases are derived within this new
paradigm. These equations are extended for multicomponent and multi-
phase nano-systems for the first time. The new paradigm leads to si-
milar results compared to the Kelvin paradigm in all situations when
the Kelvin paradigm was successful (such as capillary condensation).
Moreover, the new paradigm is able to provide meaningful solutions
also for problems, not tractable by the Kelvin equation, such as the case
of crystals and thin films having no curvature.
Previous papers on the subject:
G.Kaptay: J. Nanosci. Nanotechnol. 10 (2010) 8164–8170.
G.Kaptay: J Mater Sci 47 (2012) 8320-8335. G.Kaptay: Int. J.
Pharmaceutics 430 (2012) 253-257.
G.Kaptay: J. Nanosci. Nanotechnol. 12 (2012) 2625-2633.
A.Yakymovych, G.Kaptay, A.Roshanghias, H.Falndorfer, H.Ipser: J.
Phys. Chem. C 120 (2016) 1881-90.
O33
The Graph Method Explained
John E. Morral
The Ohio State University Department Of Materials Science and
Engineering Columbus Ohio, 43210, USA
When determining experimental phase diagrams of unknown
12
Calphad xxx (xxxx) xxx–xxx
systems, it is helpful to predict where invariant equilibria might occur
and make samples there first. Invariant equilibria are cornerstones of
isothermal sections, for a single sample can define the phases and
compositions of an entire multiphase region. If the unknown system
contains n components, an obvious method is to make a CALPHAD style
prediction using assessed thermodynamic databases of the surrounding
n1 component subsystems. Another option is the Graph Method. It can
offer more possibilities for invariant equilibria, because it is not
bounded by minimizing an estimated free energy.
The Graph method [1,2] has its foundation in Graph Theory. The
method’s purpose is to predict invariant equilibrium in an unknown
system. The method starts by drawing a graph that contains a point for
each known phase in the subsystems. If phases are known to be in
equilibrium in the subsystems, then a line is drawn between them. Thus
triangles on the graph indicate 3-phase equilibria and tetrahedrons 4-
phase equilibria.
The figure on the right is a graph of the quaternary system Ni-ReNb-
Cr [3]. The phases and 3- phase equilibria shown here were all found in
the ternary subsystems. The problem is to deduce the possible invariant
equilibria that could be in the system by investigating which tetra-
hedrons could be on this graph. Reference [3] and the presentation
explain the solution to this problem.
In addition to graphical methods there are matrix methods to solve
problems of invariant reaction prediction that involve more phases and
require more computational power [4]. The connection of matrix
methods to the graph method will be mentioned briefly.
References
1. V.A. Borisov, E.M. Slyusarenko, S.F. Dunaev, Babk Vestnik
Moskovskogo Universiteta Seriya Khimiya, 36 (1995) 564.
2. E.M. Slyusarenko, V.A. Borisov, M.V. Sofin, E.Yu. Kerimov, A.E.
Chastukhin, Determination of phase equilibria in the system Ni-V-Cr-
Mo-Re at 1425 K by using the graph method, J. of Alloys and
Compounds. 284 (1999) 171 – 189.
3. E. Kerimov, S. Nikolaev, E. Slyusarebko, Phase Equilibria in the
Quaternary Ni-Re-Nb-Cr System at 1375 K Determined Using the Graph
Method,J. Phase Equilib Diff.36(2), (2016).
4. V.I. Lutsyk and V.P. Vorob’eva, Matrix solution for Polyhedration
of Na-K-Ca-Cl-N-O, Na-K-Mo-W-F-O and Na-Ba-B-F-O Systems, IOP
Conf. Series, Mater.Sci.Engr.18 (2011) 22205
O 34
A value for empty bcc in the Calphad approach
N. Dupin
Calcul Thermodynamique, 3 rue de l'avenir 63670 Orcet FRANCE
When modelling the non-stoichiometry of B2 inter-metallic com-
pounds, the introduction of vacancies is needed in order to account for
the triple defects present for some of them, like Al-Ni. These compounds
showing in some systems a second order transitions with bcc solutions,
like in Al-Fe, the two phases should be modelled with a single Gibbs
energy equation when aiming at multicomponent descriptions. This
implies the definition of a fully empty end-member for the bcc phase.
Since 2006, the author has been using the expression 30.T for this
model parameter during the constitution of different multicomponent

databases. This expression has now been used by different assessors and
was recently recommended by Dinsdale et al. [1] but the approach
followed for its derivation has never been reported. It is based on some
ab initio results as will explained in this contribution. Its uncertainty as
well as the possibility to use this value for other phases will also be
discussed.
Reference
[1] A. Dinsdale, A. Khvan and A. Watson, Materials Science and
Technology, 30 (2014) 1715-18
O 35
Composition Dependence Modeling of the Molar Volume
Ursula R. Kattner1, Eric A. Lass1
1 model formalism was simply extended to the multi-component alumi-
Materials Science and Engineering Division, National Institute of
Standards and Technology, Gaithersburg, MD, USA
The CALPHAD method was originally used to model the thermo-
chemical properties and phase diagrams of alloy systems. Since its in-
ception, however, it has been expanded to describe diffusion mobilities
for the simulation of diffusional processes. Molar volume and com-
pressibility have been described for a few systems, with much of the
focus on temperature and pressure dependence. Hallstedt [1] examined
in 2007 the composition dependence of the molar volume in a number
of binary Al, Li, Mg and Si systems and derived its value for the me-
tastable structures of these elements. Although molar volume is a
property that is needed for the simulation of numerous materials pro-
cesses, it has been included only in a handful of proprietary CALPHAD
databases. Analyses of the composition dependence of the molar vo-
lume for a number of binary systems, including their intermetallic
compounds, and trends within the same periodic group, will be pre-
sented.
Reference
[1]B. Hallstedt, Calphad, 31 (2007) 292-302.
O 36
Trial for Viscosity Modelling of Al2O3-Na2O-K2O-SiO2 System
including Charge Compensation Effect based on Revised Quasi-
chemical Viscosity Model
Masanori SUZUKI 1 and Evgueni JAK 2
1 ments have shown quite a good correlation [4]. Very different me-
Formally in PYROSEARCH, The University of Queensland,
Australia; now Graduate School of Engineering, Osaka University,
Japan.
2 self-diffusivity in fcc Ti has been calculated by using ab initio methods
PYROSEARCH, The University of Queensland, Australia.
Slag viscosity is one of key properties essential for various me-
tallurgical and industrial processes such as glass productions and power
generation. Development of a reliable and general viscosity model has
been the focus of the present research, so that the viscosities of complex
slag systems could be predicted over a wide range of compositions and
temperatures. The unique viscosity change caused by the charge com-
pensation effect in aluminosilicate slag systems is one of complexities in
slag viscosities as composition dependence. It is believed that alumi-
nium cations charge-compensated by some basic cations (Na+, K+,
Ca2+ etc) make strong covalent bonds with surrounding oxygen anions
in tetrahedral coordination in molten slag, which leads to increase of
slag viscosity. In particular, significant viscosity increases are re-
presented when alkaline cations work as charge compensators in
molten aluminosilicate slags. The authors recently revised the quasi-
chemical viscosity (QCV) model that has been developed to predict
viscosities of molten slags in the multi-component oxide systems within
experimental uncertainties over a wide range of temperature and
compositions. [1] In the QCV model, the Eyring equation is used to
express liquid viscosity as a function of temperature and composition.
The QCV model relates the vaporisation and activation energies in the
slag viscosity expression to the slag internal structure through the
concentrations of various Si0.5O, Men+2/nO and Me1/nSi0.25O viscous flow
n+
structural units, which are calculated by a quasi-chemical
13
Calphad xxx (xxxx) xxx–xxx
thermodynamic model. The revised QCV model improved its mathe-
matical formalism, where some of slag viscosity features including
charge compensation effect in the Al2O3-containing systems have been
systematically evaluated. [2, 3] As a result, a number of shortcomings
in the previous model have been resolved. The present study attempts
to extend the revised QCV model to incorporate the Al2O3-Na2O-K2O-
SiO2 quaternary system, where the charge compensation effect is ex-
pressed by the NaAlO2 and KAlO2 associates in the latest quasi-chemical
thermodynamic model. A new mathematical formalism including these
associates are proposed to describe the charge compensation effect on
the activation energy of viscous flow as a function of composition. The
predicted viscosities successfully reproduced complex viscosity features
in the above quaternary system and its subsystems, and the present
nosilicate slag systems.
References
[1] A. Kondratiev and E. Jak, “A Quasi-chemical Viscosity Model for
Fully Liquid Slags in the Al2O3-CaO-‘FeO‘-SiO2 system”, Metall. Mater.
Trans., 36B (2005), 623.
[2] M. Suzuki and E. Jak, “Quasi-chemical Viscosity Model for Fully
Liquid Slag in the Al2O3-CaOMgO-SiO2 System - Part I: Revision of the
Model”, Metall. Mater. Trans., 44B (2013), 1435.
[3] M. Suzuki and E. Jak, “Quasi-chemical Viscosity Model for Fully
Liquid Slag in the Al2O3-CaOMgO-SiO2 System - Part II: Evaluation of
Slag Viscosities”, Metall. Mater. Trans., 44B (2013), 1451.
O 37
What is the melting point of fcc Ti?
Ying Tang1, Qing Chen1, Henry Wu2, Dane Morgan2
1
Thermo-Calc Software AB, Norra Stationsgatan 93, SE - 113 64
Stockholm, Sweden
2
Department of Materials Science and Engineering, University of
Wisconsin-Madison, 1509 University Avenue, Madison, WI 53706, USA
The melting points adopted by first and second generation pure
element databases [1-2] are more than 500 K apart for fcc Ti. A concern
about this large difference has been raised in constructing an atomic
mobility database for Ni-based superalloys [3]. As we know, the
available melting points and self-diffusion activation energies of ele-
tastable melting points thus suggest very different activation energies
for the selfdiffusion in the metastable structure. In this presentation, the
[5]. The melting point of fcc Ti was estimated on the basis of the cal-
culated activation energy. The estimated value has been further tested
against various other thermodynamic and kinetic considerations. Based
on the new information, the atomic mobilities in fcc Ni-Ti alloys were
reassessed. A new Gibbs energy description of fcc Ti was also proposed
following the third generation database approach [6-7] and using a
Debye temperature value based on ab initio calculations [8].
References
[1] L. Kaufman, PKP thermodynamic database, www.thermocalc.se,
1990.
[2] A. Dinsdale, Calphad, 15(1991)314-425.
[3] C. Campbell, W.J. Boettinger, and U. R. Kattner, Acta Materialia,
50(2002)775-92.
[4] J. Askill, Tracer Diffusion Data for Metals, Alloys, and Simple
Oxides, IFI/Plenum, New York, 1970, 19-26.
[5] T. Angsten, T. Mayeshiba, H. Wu, and D. Morgan, New Journal of
Physics 16(2014)015018.
[6] M. W. Chase, et al., Calphad, 19(1995)437-447.
[7] Q. Chen and B. Sundman, J. Phase Equilibria, 22(2001)631-644.
[8] Q. Chen and B. Sundman, Acta Materialia, 49(2001)947–961.
O38
An atomistic approach to clarify the role of yttrium in

activation of <c+a> slip in magnesium
Ki-Hyun Kim1, Jong Bae Jeon1,2, Nack Joon Kim3 and Byeong-Joo
Lee1
1
Department of Material Science and Engineering, Pohang
University of Science and Technology (POSTECH), Pohang 790-784,
Republic of Korea
2
Energy Components and Materials R&BD Group, Korea Institute of
Industrial Technology (KITECH), Busan 618-230, Republic of Korea
3
Graduate Institute of Ferrous Technology, Pohang University of
Science and Technology (POSTECH), Pohang 790-784, Republic of
Korea
The effect of Y addition on the slip behavior of an edge dislocation
on basal, prismatic and second-order pyramidal slip planes of Mg has
been investigated using a molecular dynamics simulation [1-3]. It is
found that Y increases the critical resolved shear stress of basal slip
more than that of non-basal slip and eventually reduces the difference
in the CRSS between different slip systems. Generally low solid-solution
effect of Y compared to other elements which is not reported to improve
the ductility of Mg (Al, for example) and the reduction of the anisotropy
in CRSS between different slip systems is proposed as the reason for the
experimentally reported [4] activation of <c + a> slip in Mg-Y alloys.
References
[1] K.-H. Kim et al., Scripta Mater. 108 (2015) 104.
[2] K.-H. Kim et al., CALPHAD 48 (2015) 27.
[3] Y.-M. Kim et al., CALPHAD 33 (2009) 650.
[4] S. Sandlobes et al., Acta Mater. 59 (2011) 429.
O39
Evaluation of the Young’s modulus of the Bio-implant β Ti al-
loys based on single-crystal elastic constants modeling
L. B.Liu1,2, X.Wang1, J.S.Liang1, L.G.Zhang1,2
1 thus determined and operational guidelines are established to avoid it.
School of Material Science and Engineering, Central South
University, Changsha, Hunan410083, China
2
Education MinistryKey Laboratory of Non−ferrous Materials
Science andEngineering, Changsha 410083, China
CALPHAD-type model was used to describe single-crystal elastic
constants of bcc solution phase in ternary Ti-Nb-Zr, Zr-Nb-Mo system.
The model parameters were evaluated based on available experimental
and first-principle calculations data. The composition-elastic properties
of full composition were predicted and are in agreement with experi-
mental data. It is shown thatβ phase can be divided into two regions by
a critical dynamical stability compositions line. For both Ti-Nb-Zr
ternary system, the corresponding valence electron number per atom
and polycrystalline Young’s modulus on the critical compositions are
about 4.04～4.08 and 29～33 GPa. Orientation dependencies of single-
crystal Young’s modulus have shown strong elastic anisotropy in Ti-rich
14
Calphad xxx (xxxx) xxx–xxx
concentrations. Compositions with Young’s modulus along <100>
direction match that of bone were found and can be approximately
written as (Ti,Zr)(1-x)Nbx (x=14～24 at.%) and Zr-(0～17 at%)Nb-(0～
5 at%)Mo .The current results present an effective strategy to design
biomedical alloys using computational modeling.
O41
Evaluation of possible nozzle clogging by spinel inclusions in
the continuous casting of silicon-manganese deoxidized steels
T. Botelho1, G. Medeiros2, M. Scal3, A. Costa e Silva1
1
EEIMVR-UFF Volta Redonda, Rio de Janeiro, RJ, Brazil
2
GERDAU COSIGUA, Rio de Janeiro, RJ Brazil
3
COPPE-UFRJ, Rio de Janeiro, RJ, Brazil
In open continuous casting practice for long steel products, even
using some steel shrouding, the occurrence of strong reoxidation cannot
be avoided, thus Al deoxidation is forbidden and the natural choice is
deoxidation with Si - Mn with residual Al sometimes assisted by CaSi
injection, aiming at low melting deoxidation products of general for-
mula of CaO (MnO). SiO2. Al2O3. However, in some cases, when the
ladle slag is tailored to improve desulfurization and deoxidation, ther-
modynamic conditions may lead to the incorporation of Al and Mg to
the steel by the reduction of slag oxides during ladle furnace refining. If
sufficient Al and/or Mg are incorporated to the steel, MgO.Al2O3 non-
metallic inclusions may form when some reoxidation of the steel takes
place during casting. The decrease of temperature associated with the
transfer to the caster and the processing in this equipment further
contributes to the precipitation of these solid inclusions. The result is
that unexpected clogging can occur. In the present work, we use com-
putational thermodynamics to evaluate the conditions that may lead to
the pickup of Mg and Al, quantify this pickup and evaluate the effect of
reoxidation and cooling on the formation of spinel inclusions. The
conditions that may lead to continuous casting clogging by spinel are
O 42
Chemical and thermal influences on the thermodynamic sta-
bility of the vanadium richoxidesystem
Jinichiro Nakano1,2, Marc Duchesne3, James Bennett1, Anna
Nakano1, Robin Hughes3, In-Ho Jung4
1
National Energy Technology Laboratory -U.S. Department of
Energy, 1450 Queen Avenue, Albany, OR 97321 USA
2
AECOM, P.O. Box 1959, Albany, OR 97321 USA
3
Natural Resources Canada, CanmetENERGY, 1 Haanel Drive,
Ottawa, ON K1A 1M1 Canada
4
Department of Mining and Materials Engineering, McGill
University, 3610 University Street, Montreal, QC H3A 0C5, Canada
Entrained flow gasifiers use both coal and petcoke as carbon

feedstock, with increasing use of petcoke as a major carbon source.
Little is known about the chemical and physical properties of slags with
petcoke additions, a carbon source high in vanadium impurities. To
understand phase equilibria of petcoke-derived slags, a range of Al2O3-
CaO-FeO-SiO2-V2O3 pure oxide mixtures representing simplified ver-
sions of U.S. and Canadian coal/petcoke carbon feedstock mixtures was
studied. This research is part of a larger program studying coal/petcoke
slag properties/behaviour [1]. In this study, the phase equilibria of
synthetic slags synthesized under controlled temperature, oxygen par-
tial pressure, and chemistry was investigated, with the research focus
on pseudo-binary vanadium oxidesystems. Equilibrium phase diagrams
of the systemsstudied areproposed.
Reference
[1]J. Nakano et al., Fuel, 161 (2015)364-375
O43
Influence of thallium oxide on formation of mullite phase
Oleg Chizhko
Association of German Engineers, Foreign Department, Post-Box 88,
369000 Cherkessk, Russia, Oleg.Chizhko@alumni.uni-karlsruhe.de
The application of this research is anti-corrosion coatings. We in-
troduce the content of alumosilicate compounds, which are stable
against the gaseous products of combustion processes for municipal
solid waste.
The ionic liquid model of Al2O3-SiO2-Tl2O3 system is constructed
with help of main constituents of the complex oxide phases. They are
the AlO+ oxy-cations and AlO3-3 oxy-anions of aluminum, the Tl+3
thallium cations and SiO4-4 silica-ion. These species build two sub-lat-
tices of Tl2SiAl6O14, which is the substitutional composite of Al6Si2O13.
The two cells for the positive and negative ionic unities interact in
correspondence with their electrical charge. Thus, we produce the long
range order without vacancies, which characterize the mullite. The two
and three phase fields are calculated with help of MeRS-dates software.
There is an operational system for databases of thermodynamic prop-
erties of complex oxide substances and for their melting points. It is also
the program facility and we evaluate the chemical potentials of all
possible reactions for material conglomerates. The stoichiometric
coefficients of the transformation processes are the quantities of phases
at an equilibrium. The thermal dependences of excess energies are
15
Calphad xxx (xxxx) xxx–xxx
interpolated in correspondence with experimental results for measuring
of heat capacities. In the modified crystal cell, the intensification of
oxygen bond is proved with Redlich-Kister’s power series for a molar
composition. The evident variation of elementary content of the stable
aggregations are visualized in a form of single areas and two phase
fields. We introduce coupling of metallic and covalent bonds as a
combination of electro-chemical interactions and use thermal treatment
with aim of growing of mono-crystalline grains, in which the heat
conductivity of oxide components is decreased because of addition of
Tl2O3.
O 44
Application of Thermodynamic Database for High Temperature
Steelmaking Process Simulations
In-Ho Jungand Marie-Aline Van Ende
Department of Mining and Materials Engineering McGill University,
Montreal, Canada
The main purposes of steelmaking process are refining, alloying,
and homogenizaiton of chemistry and temperature of molten steel. In
order to acheive these goals, many different unit processes are carried
out in proper sequnce at the temperatures between 1500 to 1700 ˚C.
During such processes, complex chmeical reactions between molten
steel, molten slag (liquid oxide solution), refractories (solid oxides),
non-metallic inclusions (solid or liquid oxide or oxysulfides) and gas
phases are involved. Therefore, the controlling of such chemical reac-
tions is key technology to produce best quality of liquid steel.
In order to understand complex chemical reactions, CALPHAD type
thermodynamic databases have been widely used in steelmaking pro-
cesses. Recently, the present authors have demonstrated successful
connection between thermdoynamic databases and kinetic mass trans-
fers of species in the reaction interface to predict the chemistry and
temperature changes of molten steel and all asociated phases using so-
called the Effective Equilibrium Reaction Zone Model (EERZ). In the
EERZ model as shown in Fig. 1, the mass transfer of the species at the
reaction interface is translated to effective reaction volume at interface
which is varied by strring energy in system. In the present study, the
concept of EERZ model will be introduced and several case examples for
the steelmaking process simulationswill be presented.

References
1) M.-A. Van Ende, Y.-M. Kim, M.-K. Cho, J.H. Choi and I.-H. Jung:
Metall. Mater. Trans. B, 2011, vol. 42, pp. 477-489.
2) M.-A. Van Ende and I.-H. Jung: CAMP-ISIJ, 2015, vol.28, pp. 527-
530.
3) M.-A. Van Endeand I.-H. Jung: ISIJ Inter. 2014, vol. 54, pp. 489-
495.
4) M.-A. Van Ende and I.-H. Jung: ISIJ Inter. 2014, vol. 54, pp. 489-
495.
5) M.-A. Van Ende and I.-H. Jung: “A Kinetic Ladle Furnace Process
Simulation Model: Effective Equilibrium Reaction Zone Model using
FactSage Macro processing”, Metall. Mater. Trans B, submitted, 2016.
O45
Cubic phase distribution in ultrafine WC–10Co–0.5Cr–xTa ce-
mented carbideand its effect on mechanical properties
Na Li1, Weibin Zhang1, Yingbiao Peng1,2, andYong Du1,*
1 rated, shedding light on a new mechanism of hillock formation and new
State Key Lab of Powder Metallurgy, Central South University,
Changsha, Hunan 410083, China
2
School of Metallurgical Engineering, Hunan University of
Technology, Zhuzhou 412007, PR China
*E-mail：yong-du@csu.edu.cn
The (Ta, W)C cubic phase distribution plays a key role in the mi-
crostructure and mechanical properties of ultrafine WC–Co–Cr3C2–TaC
cemented carbides. By integration of thermodynamic calculations and
key experiments, the influence of the cubic phase distribution in ul-
trafine WC–10Co–0.5Cr–xTacemented carbides was systematically in-
vestigated. A series of ultrafine grained cemented carbides were de-
signed and fabricated through ball-milling and vacuum sintering at
1410°C for1 h. The microstructure was investigated using scanning
electron microscopy (SEM). The electron backscattered diffraction
(EBSD) was used to measure the orientation and size of cubic phase
segregation. The results indicate that the cubic phase in the micro-
structure distributes more heterogeneously in the range of 0.2 to 0.7 wt.
% Ta addition, but finally the isolated cubic phase is homogeneously
distributed with a Ta contentfrom 0.7 to 1 wt%. Combining the ther-
modynamic calculation with the experiment, the mechanism for the
microstructure evolution has been revealed. Finite element method
(FEM) was applied to analyze the stress distribution based on the
images of the real microstructure obtained from EBSD. The stress dis-
tribution inside the material is highly non-homogeneous and the re-
gions of stress concentration are located at the cubic phase segregation.
Thus, the mechanical properties of alloys substantially depend on the
cubic phase distribution in the microstructure. A synergetic correlation
between the transverse rupture strength (TRS) and Rockwell hardness
was observed by mechanical tests, which is in accord with the FEM
analysis. The homogeneity of cubic phase can be designed and con-
trolled effectively via the present approach.
Acknowledgements
The financial support from National Natural Science Foundation of
China (Grant No.51371199) and Ministry of Industry and Information
Technology of China (Grant No. 2015ZX04005008) is greatly ac-
knowledged.
O 46
Silver nano-volcanic eruption: A CALPHAD un-puzzling
Shih-kang Lin1, Shijo Nagao2, Emi Yokoi2, Chulmin Oh2, Hao
Zhang2, Yu-chen Liu1, Shih-guei Lin1, Katsuaki Suganuma2
16
Calphad xxx (xxxx) xxx–xxx
1
Department of Materials Science and Engineering, National Cheng
Kung University, Taiwan
2
Institute of Scientific and Industrial Research, Osaka University,
Japan
Silver (Ag) is one of the seven metals of antiquity and an important
engineering material in the electronic, medical, and chemical industries
because of its unique noble and catalytic properties. Ag thin films are
extensively used in modern electronics primarily because of their oxi-
dation-resistance. Here we report a novel phenomenon of Ag nano-
volcanic eruption that is caused by interactions between Ag and oxygen
(O). It involves grain boundary liquation, the ejection of transient Ag-O
fluids through grain boundaries, and the decomposition of Ag-O fluids
into O2 gas and suspended Ag and Ag2O clusters. Subsequent coating
with re-deposited Ag-O and the de-alloying of O yield a conformal
amorphous Ag coating. Patterned Ag hillock arrays and direct Ag-to-Ag
bonding can be formed by the homogenous crystallization of amor-
phous coatings. The Ag “nano-volcanic eruption” mechanism is elabo-
applications of amorphous Ag coatings.
O47
Phase Equilibria of the Al-Cu-Fe system with the quasicrystal-
line phase
Sinn-wen Chen1, Po-han Lin1, Wojciech Gierlotka2
1
Department of Chemical Engineering, National Tsing Hua
University No. 101, Sec. 1, Kuang-fuh Road, Hsinchu 30013, Taiwan
2
Department of Materials Science and Engineering, National Dong
Hwa University No. 1, Sec. 2, Da-hsueh Road, Shoufeng, Hualien
97401, Taiwan
Quasicrystals have attracted intensive research interests due to their
unique structures and properties. Numerous investigations have been
carried out especially on the icosahedral phase of the Al-Cu-Fe ternary
system. The composition of the famous Al-Cu-Fe icosahedral phase is
Al63Cu25Fe12 with about 0.6 to 2.5at.% compositional solubility range
at different temperatures. Phase diagrams contain fundamental phase
equilibria information, and are important references for manufacturing
processes. This study determines the phase diagrams of the Al-Cu-Fe
system with the icosahedral phase. Al-Cu-Fe ternary alloys with com-
positions near the icosahedral phase were prepared and equilibrated at
680 ˚C and 850 ˚C for about 30 days. The icosahedral phase are in
equilibrium with ω-Al7Cu2Fe, β-Al(Cu,Fe) and λ-Al13Fe4 phases at 680
˚C, and are in equilibrium with liquid, β-Al(Cu,Fe) and λ-Al13Fe4 at
850˚C. Its compositions vary from Al-25.1at.%Cu12.4at.%Fe to Al-
22.7at.%Cu-12.8at.%Fe at 680˚C, and from Al-22.7at.%Cu-14.2at.%Fe
to Al22.7at.%Cu-13.6at.%Fe at 850 ˚C, respectively. There is no dom-
inating model for thermodynamic description of the icosahedral phases,
although line compound model and compound energy model have been
used. It has been reported that the Al-Cu-Fe icosahedral phase is a
mixture of Mackay and Bridgman clusters, where both types are re-
presented by two slightly different groups: M, M’, and B, B’, respectively
[Ref. 1]. To make thermodynamic modelling simpler, the average
composition of each cluster (M, M’, B, B’) has been calculated based on
stoichiometry and frequency of presence. Assuming that the Al-Cu-Fe
icosahedral phase is a random mixing of these four average clusters, the
Gibbs energies of each species as well as the Gibbs energies of inter-
actions are calculated based on phase equilibrium data. A good de-
scription agreement between experimental information and modelling
of the icosahedral phase has been found.

Reference
1: W. Steurer, S. Deloudi, Crystollagraphy of Quasicrystals:
Concepte, Methods and Structures, Springer Series in Materials Science,
Springer 2009.
O49
Unifying the CALPHAD sublattice model and the phase-field
model with finite interface dissipation
Matthias Stratmann1, Oleg Shchyglo1, Lijun Zhang2, Ingo
Steinbach1
1 modynamic description, being a pre-requisite of predictions on its time-
Interdisciplinary Centre for Advanced Materials Simulation
(ICAMS), Ruhr-Universität Bochum, D-44780 Bochum, Germany
2 sive literature survey has shown that many of the sub-systems con-
State Key Laboratory of Powder Metallurgy, Central South
University, 410083 Changsha, PR China
Modern multi-phase field models [1-4] rely on thermodynamic and
kinetic properties stored in CALPHAD databases. The data has to be
retrieved via internal or external minimization if phases are modelled
with sublattices and additional degrees of freedom. Recently, an ex-
tension to the phase-field model with finite interface dissipation [3-4]
has been developed, which models sublattice occupancy not only in a
single phase [5], but also between thermodynamic phases overlapping
in the diffuse interface. The additional measures will be presented to
cope with this situation under the constraint to conserve the total
composition, which is calculated from the phasesite-fractions.
Nevertheless, with given phase-site-fractions, temperature and pres-
sure, the thermodynamic and kinetic properties and its derivatives can
be calculated not only analytically, but also by said external modules
like OpenCalphad and Thermo-Calc to ease simulation setups. Further
implications for long- and short-range diffusion rigorously on each
sublattice according to [6] will be discussed. Finally case studies using
internal and external sublattice minimization will be presented to elu-
cidate the effectiveness of the approach.
References
[1] J. Tiaden, B. Nestler, H. J. Diepers, and I. Steinbach, Phys. D
Nonlinear Phenom., 115 (1998) 73–86
[2] S. G. Kim, W. T. Kim, and T. Suzuki, Phys. Rev. E, 60 (1999)
7186–7197
[3] I. Steinbach, L. Zhang, and M. Plapp, Acta Mater., 60 (2012)
2689–2701
[4] L. Zhang and I. Steinbach, Acta Mater., 60 (2012) 2702–2710
[5] L. Zhang, M. Stratmann, Y. Du, B. Sundman, and I. Steinbach,
Acta Mater., 88 (2015) 156–169
[6] J. Ågren, Solid State Commun., 42 (1982) 421-430
O50
Thermodynamic and kinetic modeling of Laves phase con-
taining systems for the development of high Cr ferritic steels
Aurélie Jacob1,2, Michal Talik1, Jennifer Lopez1, Bernd Kuhn1,
Erwin Povoden-Karadeniz2, Piotr Warczok2, Ernst Kozeschnik2
17
Calphad xxx (xxxx) xxx–xxx
1
Forschungszentrum Jülich, IEK-2, 52425 Jülich, Germany
2
TU Wien, Institute of Materials Science and Technology,
Getreidemarkt 9, E308, 1060 Vienna, Austria
Prediction of materials properties by employing computational
thermodynamics assists optimisation and acceleration of materials
processing and extension of service life. Prediction of the micro-
structure evolution is based on thermodynamic and kinetic multi-
component databases coupled with kinetic models of phase transfor-
mations [1]. In high-Cr ferritic stainless steel, precipitation of Laves
phase is important for high creep strength [2,3]. However, its ther-
and temperature dependent evolution, is not complete: a comprehen-
taining Laves phase have not yet been described via the Calphad
method, and thus existing databases cannot be used for simulations of
Crofer 22H stainless ferritic steel [3,4]. In this study, thermodynamic
optimizations of (Cr,Fe,Si)2(Nb,W) Laves phase containing systems
were performed [4,5]. Published modelling results were inserted in
multicomponent steel database ME-Fe [6], leading to a strong im-
provement of the predicted phase stability in Crofer 22H. The extended
thermodynamic database was then used for prediction of precipitation
kinetics of model alloys during different technological heat treatments,
and the results were compared with experimental data.
References
[1] E. Kozeschnik et al., Mater. Sci. Eng. A. 385 (2004) 157–165.
[2] J. Quadakkers et al., Crofer 22H, Patent number: PCT/DE2007/
000166, WO2007093148–A1; DE102006007598-A1 (2006).
[3] B. Kuhn et al., Material Science Engineering A. 594 (2014)
372–380.
[4] C. Schmetterer et al., Journal of Phase Equilibria Diffusion 35
(2014) 434–444.
[5] A. Jacob et al., Calphad, 50 (2015) 92–104.
[6] http://matcalc.tuwien.ac.at/
O 51
Thermodynamic calculation of γ nanoparticles formation in the
γ precipitates of Ni-Al alloy system
F.Forghani1, M. Nili-Ahmadabadi1,2, R. Abbaschian3
1
School of Metallurgy and Materials Engineering, College of
Engineering, University of Tehran, P.O. Box 14395-731, Tehran, Iran
2
Center of Excellence for High Performance Materials, University of
Tehran, P.O. Box 14395-731, Tehran, Iran
3
Department of Mechanical Engineering, University of California
Riverside, Riverside, CA 92507, USA
Cast nickel based superalloys are common candidates for high
temperature service conditions. The high temperature strength of these
superalloys is due mainly to the evolution of γ/γ microstructure.
Recently, a remarkable γ/γ microstructure has been characterized by
means of atom probe tomography as well as transmission electron

microscopy that make great interest among metallurgist [1]. The mi-
crostructure is a kind of hierarchical microstructure, in which the or-
dered (L12) γ precipitates form inside the disordered γ matrix and, in
turn, the γ phase particles form inside the γ precipitates. It was found
that the presence of γ nanoparticle inside γ precipitates affects coar-
sening kinetics and increases alloy hardness [1,2]. It is also hoped that
the γ particles will have a beneficial effect on the thermo-mechanical
properties and in particular on the morphological change of γ pre-
cipitates during creep deformation. In this study, the Ni-Al alloy system
(as a nickel based superalloy model) has been thermodynamically as-
sessed using CALPHAD method. The Gibbs free energy of γ and γ phases
for the Ni rich region of the binary system has been calculated em-
ploying two sublattice model. The results are in consistent favorably
with literature as well as experiments [3-6]. In particular, the model has
been used to interpret the phase separation phenomena in the γ pre-
cipitates of Ni-18Al (at.%) samples after double aging treatment. The
free energy changes during γ particles formation inside γ precipitates
has been calculated using the developed thermodynamic model.
Moreover, the possibility of spinodal decomposition or classical nu-
cleation mechanisms in the different range of composition and tem-
perature for the mentioned phase separation phenomena has been in-
vestigated from thermodynamic point of view.
References
[1] F. Vogel, N. Wanderka, Z. Balogh, M. Ibrahim, P. Stender, G.
Schmitz, and J. Banhart, Nat. Commun., vol. 4 (2013), Article number:
2955.
[2] M. Doi, D. Miki, T. Moritani, T. Kozakai, in Superalloys, 2004,
pp. 109–114.
[3] I. Ansara, B. Sundman, P. Willemin, Acta Metall., vol. 36 (1988),
pp. 977.
[4] I. Ansara, N. Dupin, H.L. Lukas, B. Sundman, J. Alloys Compd.,
vol. 247 (1997), pp. 20.
[5] W. Huang, Y.A. Chang, Intermetallics, vol. 6 (1998), pp. 487.
[6] N. Dupin, Thesis, Institut Nationale Polytechnique de Grenoble,
France, 1995.
O 52
Modeling of homogenization, dissolution and precipitation
phenomena in AM50 alloy and experimental validation
Manas Paliwal, In-Ho Jung
Department of Mining and Materials Engineering McGill University,
Montreal, Canada
Common commercial Mg alloys such as AZ (Al, Zn) and AM (Al, Mn)
are typically used in autmotive sector as both as-cast and wrought
products. Solution treatment (homogenization) after casting is an
18
Calphad xxx (xxxx) xxx–xxx
important step in wrought alloy production. The purpose of homo-
genization is to dissolve the secondary phases and eliminating micro-
segregation to the fullest extent so that an optimum microstructure is
achieved before rolling or extrusion processes.
In the present study a AM50 alloy is solution treated at 623 and 673
K for 1, 2 and 8 h respectively. As seen in Fig. 1 the microstructure
exhbhits the simultaneous dissolution of Mg17Al12 phase, homo-
genization of solute elements (removal of microsegregation) and pre-
cipitation of AlxMny phase. The solute distribution in the homogenized
microstrucure is characterized by EPMA and the precipitate size evo-
lution is investigated through TEM. In order to explain the experimental
results a multiscale model is developed which accounts for simulta-
neous homogenizaion, dissolution and precipitation phenomena. The
homogenization and dissolution models are based on 1D flux balance
approach with appropriate thermodynamic inputs from FactSage [1]
whereas the precipitation model is based on modified KWN theory [2].
References
[1]. C.W. Bale, E. Bélisle, P. Chartrand, S.A. Decterov, G. Eriksson,
K. Hack, I.-H. Jung, Y-B. Kang, J. Melançon, A.D. Pelton, C. Robelin and
S. Petersen, CALPHAD 31 (2009) 295-311.
[2]. R. Kampmann and R. Wagner R, Materials Science and
Technology vol. 5, VCH–Weinheim, Germany, 1991.
O 53
Determination of diffusion parameters of the intermetallic
compounds in Sn/Cu and Sn-xAg-yCu/Cu diffusion joints
Y. Yuan1,2, D. Li2, N. Moelans1,
1
KU Leuven, Department of Materials Engineering, Leuven,
Belgium
2
Karlsruhe Institute of Technology (KIT), Institute for Applied
Materials (IAM-AWP), Eggenstein-Leopoldshafen, Germany
The interfacial reactions between Sn (or Sn-rich solders), and
common metal substrates, such as Cu, are important for the perfor-
mance and reliability of the solder joints and have attracted a lot of
attention. However the reported diffusion parameters of related inter-
metallic compounds (IMCs) are still scattered and low temperature data
(below 150 ˚C) are rare. In this work, the growth behavior and diffusion
parameters of the IMCs formed in Sn/Cu and Sn-xAg-yCu/Cu diffusion
couples were investigated over the temperature range of 130 ˚C – 200
˚C. Considering the wavy type of the diffusion layers and the narrow
homogeneity range of the IMCs (Cu3Sn and Cu6Sn5), the integrated
interdiffusion coefficients were calculated using the Wagner’s method
based on the measured thicknesses of the IMC layers [1,2,3]. The ac-
tivation energies for diffusion through the IMCs were then evaluated
from the obtained integrated diffusion coefficients.

A pseudo-binary method is proposed and applied to Sn-xAg-yCu/Cu
ternary diffusion couples to obtain the integrated interdiffusion coeffi-
cients and activation energies for diffusion through the intermetallics
with limited solubility in one of the 3 elements. The activation energies
for diffusion derived with this method show only the properties of the
investigated phase, excluding the effects from adjacent phases.
A transient growth regime for Cu3Sn at the initial stage in cold-
bonded Sn/Cu and Sn-xAgyCu/Cu diffusion couples is observed. A
methodology is therefore proposed to determine the diffusion coeffi-
cients excluding effects from the transient initial growth stage by con-
sidering two diffusion times where the growths of both IMCs are in the
diffusion controlled stage.
The growth of Cu3Sn in Sn-xAg-yCu/Cu diffusion couples was found
to be a little slower than that in binary Sn/Cu diffusion couples. The
growth rate of the Cu6Sn5 phase in ternary Sn-xAg-yCu/Cu diffusion
couples is close to that in Sn/Cu diffusion couples. The Cu addition in
the Sn-based end-member is expected to favor the growth of Cu6Sn5
providing instantly available Cu atoms for the formation of Cu6Sn5. The
Ag addition is suggested to slightly decrease the thermodynamic ac-
tivity of Cu and Sn and further decrease the diffusion of Cu and Sn.
These interpretations were confirmed by a study of the diffusion be-
havior in Sn3.5%Ag /Cu and Sn-1.0%Cu /Cu diffusion couples. The
calculated activation energy for interdiffusion of Cu and Sn in the
Cu3Sn and Cu6Sn5 phases in Sn-xAg-yCu/Cu diffusion couples are quite
close to those obtained for binary Cu/Sn couples.
References
[1] Y. Yuan, Y. Guan, D. Li, N. Moelans, 661 (2016) 282-293.
[2] Y. Yuan, D. Li, N. Moelans, 69 (2016) 2015-2017.
[3] Y. Yuan, Y. Guan, D. Li, N. Moelans, Investigation of the diffu-
sion behavior in Sn-xAgyCu/Cu solid state diffusion couples, Submitted,
under review.
O54
Thermodynamics, Kinetics, and Molar Volumes of Martensitic
Transformation in Titanium Alloys
Jia-Yi Yan1, G.B. Olson2
1
Department of Materials Science and Engineering, KTH Royal
Institute of Technology, Brinellvägen 23, 10044 Stockholm, Sweden
2
Department of Materials Science and Engineering, Northwestern
University, 2220 Campus Drive, Evanston, IL 60208, USA
Modeling martensitic transformation in titanium alloys is funda-
mental to designing titanium alloys with transformation-induced plas-
ticity and toughening effect, shape memory, and superelasticity. For the
β-α’/α” martensitic transformation, we have improved the thermo-
dynamic descriptions at low temperatures using martensite start and
reversion temperatures, which is more accurate than extrapolating the
assessments based on phase equilibria at high temperatures. The
anomalous βstabilizing effect of Al, Sn, and Zr in Ti-V/Nb-base alloys
are correctly modeled for the first time. Using the improved thermo-
dynamic descriptions, the critical driving force for martensitic nuclea-
tion in titanium alloys is modeled based on solution-hardening inter-
facial friction. The competition between martensite and athermal ω
phase can be understood based on their transformation thermodynamic
and kinetic factors.
We have also built a database for the room-temperature molar vo-
lumes of β, α’, and α” phases. For martensite, α’ and α” phases are
modeled separately, and the actual martensitic structure is predicted as
the denser one. The molar-volume database serves designing a high
transformation dilatation, which enhances transformation toughening.
O55
Experimental visualization of ion diffusion paths in ceramic
ion conductors
Masatomo Yashima, Kotaro Fujii, Masahiro Shiraiwa, Yuichi Esaki,
Keisuke Hibino, Eiki Niwa
19
Calphad xxx (xxxx) xxx–xxx
Department of Chemistry, Tokyo Institute of Technology, Tokyo,
Japan
Email: yashima.m.aa@m.titech.ac.jp, web site: http://www.cms.ti-
tech.ac.jp/~yashima/index-e.php
Our group has developed new high-temperature neutron and high-
resolution synchrotron diffraction techniques to study the precise crystal
structures, nuclear and electron density in inorganic materials up to 1900
K. Bond valence method is useful to examine the ion diffusion paths.
These techniques enabled precise structure analysis leading to diffusion
path and structural disorder in ionic conductors. Here we present the
diffusion path of oxide ions in Bi2O3, Bi1.4Yb0.6O3, (La0.8Sr0.2)
(Ga0.8Mg0.15Co0.05)O3-δ, CeO2, Ce0.93Y0.07O1.96, PrBaCo2O5+δ (Fig. 1a)
[1], (Pr0.9La0.1)2(Ni0.74Cu0.21Ga0.05)O4+δ (Fig. 1b) [2,3],
Pr2(Ni0.75Cu0.25)0.95Ga0.05)O4+δ [4], and La0.64(Ti0.92Nb0.08)O3 at high
temperatures. A novel material NdBaInO4 has been synthesized by solid-
state reactions and its crystal structure has been determined by syn-
chrotron X-ray and neutron powder diffraction and ab initio electronic
calculations [5]. The bond valence sums (BVS) map of NdBaInO4 at 1000
˚C strongly suggests two-dimensional network of oxide-ion diffusional
pathways in the Nd2O3 unit (Fig. 1c). We have discovered the novel
material NdBaInO4 belonging to a new perovskite-related structure fa-
mily, and its crystal structure has been determined. NdBaInO4 exhibits
oxide-ion conduction. It was found that the Sr substitution at the Nd site
improves the oxide-ion conductivity of NdBaInO4 [6]. The present finding
might open a new window in chemistry, physics and materials science.
References
[1] Y.-C. Chen, M. Yashima, J. Peña-Martínez and J. A. Kilner,
Chem. Mater. 25, 2638 (2013).
[2] M. Yashima, M. Enoki, T. Wakita, R. Ali, Y. Matsushita, F. Izumi,
T. Ishihara, J. Am. Chem. Soc. 130, 2762 (2008).
[3] M. Yashima, N. Sirikanda, T. Ishihara, J. Am. Chem. Soc. 132,
2385 (2010).
[4] M. Yashima, H. Yamada, S. Nuansaeng, T. Ishihara, Chem. Mater.
24, 4100 (2012).
[5] K. Fujii, Y. Esaki, K. Omoto, M. Yashima, A. Hoshikawa, T.
Ishigaki and H. R. Hester, Chem. Mater. 26, 2488 (2014).
[6] K. Fujii, M. Shiraiwa, Y. Esaki, M. Yashima, S. J. Kim and S. Lee,
J. Mater. Chem. A 3, 11985 (2015).
O56
Microstructure Prediction for TMW-4M3 during Heat
Treatment
Takaaki Hara1, Shinichi Kobayashi1, Tomonori Ueno1, Katsunari
Oikawa2
1
Metallurgical Research Laboratory, Hitachi metals, Ltd., 1240-2,
Hashimacho, Yasugi, Shimane, 692-8601, Japan
2
Department of Metallurgy Graduate School of Engineering,
Tohoku University, Aoba-6-6-02, Aramaki, Aobaku, Sendai, 980-8579,
Japan
The alloy TMW-4M3 has been developed as a novel cast and
wrought alloy based on a concept of combining Ni-base and Co-base

superalloys[1]. This alloy contains higher amounts of Co and Ti than
Alloy 720Li as listed in Table 1. For practical applications, it is very
important to control the size and distribution of γ’phase as an intended
microstructure. However, precipitation behavior of this type of alloy
greatly depends on heat treatment conditions[2]. In this study, we
made a modification to the thermodynamic database in order to re-
produce the γ/γ’ phase boundary in the range of high Co composition.
By using it, both the nucleation rate calculation based on classical nu-
cleation theory and the microstructure evolution prediction based on
the phase field method were applied to the precipitation of in-
tragranular γ’ particles during the heat treatment process. The experi-
mental and simulated microstructures of four different heat treatment
conditions are shown in Figure 1. The simulated size of the secondary γ’
phase agrees well with experimental results.
References
[1] Y. Gu et al., Superalloys (2012), 903.
[2] D. U. Furrer et al., Scr. Mater., 40, 11 (1999), 1215. “TMW” is a
trademark of National Institute for Materials Science registered in
Japan.
O 57
Thermodynamics and thermal behavior of lithium batteries
Maren Lepple, Damian Cupid, Hans Jürgen Seifert
Institute for Applied Materials (IAM-AWP), Karlsruhe Institute of
Technology, Karlsruhe, Germany
Thermodynamics and phase diagrams of advanced materials used
for lithium battery design are directly linked to electrochemical per-
formances, heat generation and safety behavior during electrochemical
cell operation. However, such thermodynamic data are largely missing
even for the most important cathode materials e.g. Li(Ni,Mn,Co)O2
(NMC), LiFePO4 (LFP), LiMn2O4 (LMO) and their derivates. The situa-
tion is similar for anode materials based on Li4Ti5O12 (LTO), tin alloys
and conversion-type compounds (e.g. Cu-based), respectively.
Therefore, the priority program SPP1473 (WeNDeLIB), funded by the
German Research Foundation (DFG), aims at investigating thermo-
dynamic properties and phase diagrams and link them to electro-
chemical and thermal cell behavior. The fundamental research includes
heterogeneous phase equilibria, heat capacities, enthalpies, chemical
potentials as well as entropy measurements on full electrochemical
cells. CALPHAD-type thermodynamic models and descriptions of
ternary and multicomponent systems are then used to calculate
20
Calphad xxx (xxxx) xxx–xxx
reversible open circuit voltages of electrochemical (half) cells. Also full
coulometric titration curves are calculated and compared with experi-
mental information. The thermodynamic datasets and additional ther-
mophysical data can then be used for an advanced application-oriented
electrochemical-thermal modeling. The ultimate aim is the simulation
of thermal behavior, heat generation and physico-chemical conditions
for thermal runaway of lithium batteries.
O58
Two-step thermochemical solar-to-fuel efficiency CALPHAD
computation for strontium and chromium doped lanthanum
manganite perovskite oxides
Alexander H. Bork1, Erwin Povoden-Karadeniz2, Jennifer L.M.
Rupp1
1
Electrochemical Materials, Department of Materials, ETH Zurich,
Switzerland
2
Christian Doppler Laboratory for Early Stages of Precipitation,
Vienna University of Technology, Austria
A key to ensuring a sustainable energy future is to develop tech-
nologies producing sustainable fuels and reducing greenhouse gas
emissions. Two-step thermochemical fuel production is an energy
conversion technology utilizing solar thermal energy to heat a solid
which catalyses conversion of water and carbon dioxide into syngas, a
renewable fuel that can replace fossil fuels and mitigate CO2 emissions
[1].
Practical implementation of the technology is predicated on the
discovery of materials with a high thermochemical solar-to-fuel con-
version efficiency. Perovskites have attracted much attention recently
due to impressive fuel productivity [2, 3]. A high fuel productivity
shows the potential and viability of a material, but it does not imply
that it is the material with highest efficiency [4]. Literature on solar
thermochemical efficiency of perovskites is scarce and none of the ex-
isting studies determine the input data, such as heat capacity and
oxygen nonstoichiometry, in the entire technological relevant tem-
perature range of 1000-1800K. One can expect discrepancies in the
oxygen nonstoichiometry and heat capacity when the data is extra-
polated over a wide temperature range, which result in less reliable
estimates of the actual efficiency.
Here, we use CALPHAD data libraries on heat capacity and oxygen
nonstoichiometry of the compositions La1-xSrxMn1-yCryO3-δ in the entire
relevant temperature range of 1073-1873K for the solar-to-fuel appli-
cation. Thermochemical equilibrium models of fuel productivity are

accompanied by validations with experimental results in literature.
Further, we make predictions on the most efficient material in the
composition space La1-xSrxMn1-yCryO3-δ for different conditions e.g.
water partial pressure and operation temperature. The models reveal
that the optimum material is highly dependent on the solar reactor
operating conditions. Due to the wide possibilities of doping in per-
ovskites, there is a great need for mapping their thermodynamic
properties in the temperature range of 1000-1800K. The necessary key
experiments for CALPHAD modelling extended to further promising
perovskite candidates with high potential for this appealing renewable
energy technology are discussed.
References
[1] Chueh, W.C., et al., Science, 330 (2010), 1797-1801.
[2] McDaniel, A.H., et al., Energy & Environmental Science, 6,
(2013), 2424-2428
[3] Bork, A., et al., Journal of Materials Chemistry A, 3, (2015),
15546-15557.
[4] Scheffe, J.R., et al., Energy & Fuels, 27, (2013), 4250-4257.
O59
Thermodynamics aided design of nanostructures for gas sensor
and solar cells
Ping Wu1, Sang Sub Kim2, Chuen-Shii Chou3
1 been carried out following the CALPHAD technique in present work.
Singapore Univ Technol & Design, Singapore 138682, Singapore
2 Ternary parameters for individual phases were evaluated using in-situ
Inha Univ, Div Engn & Mat Sci, Inchon 402751, South Korea
3 X-ray diffraction (XRD) and Differential scanning calorimetry (DSC)
Natl Pingtung Univ Sci & Technol, Res Ctr Solar Photoelect
Applicat, Pingtung 912, Taiwan
A gas sensor measured its changes in electrical property upon ex-
posure to the testing gas molecules, and a solar cells device converted
solar photon energy into electricity. Although they share some com-
ment operation principles like electron/carrier transport [7] and che-
misorption [8-9], as well as nanostructure features like p-n junction [3]
and metal/compound surface decoration [2], no attempt is reported to
establish comment design guidelines for both applications.
Thermodynamic calculations, however, have been used in the devel-
opment of chemoresistive gas sensors [1-3, 7] and dye sensitized solar
cells [4-6]. In this presentation, the author will try to outline the
computational design procedures which may be used to speed up the
current trial and error approach in the design of gas sensor and solar
cells. A wide range of thermodynamic calculations will be applied, from
solution chemistry [1, 9], DFT [4, 7, 9] to correlation models [5].
Critical challenges and trends in the relevant research fields will also be
reviewed.
References
[1] Kim, Sang Sub; Sun, Gun-Joo; et al., RSC ADVANCES, 4 (2014)
1159-1162.
[2] Sun, Gun-Joo); Choi, Choi, Sun-Woo; et al., J MATER CHEM C, 1
(2013) 5454-5462.
[3] Kim, Sang Sub; Van Khai, Tran; et al., CHEM MATER 27 (2015)
4222-4228.
[4] Chou, Chuen-Shii; Su, Feng-Cheng; et al., ADV POWDER
TECHY, 25 (2015) 1285-1291.
[5] Chou, Chuen-Shii; Huang, Yan-Hao; et al., APP ENERGY 118
(2014) 12-21.
[6] Chou, Chuen-Shii; Chen, Chung-Yung; et al., ADV POWDER
TECH 26(2014) 1555-1562.
[7] Sobhan, Mushtaq; Xu, Qiang; et al., NANOTECHNOLOGY 26
(2015) 175501.
[8] Sobhan, Mushtaq; Xu, Qiang; et al., EPL 111 (2015) 18005.
[9] Shu, Guo Gang; Xu, Qiang; Wu, Ping, ACS APP MATER & INTER
7 (2015) 7576-7583.
O60
Experimental investigation and thermodynamic calculation of
the phase equilibria for thermal energy storage orientationally
21
Calphad xxx (xxxx) xxx–xxx
disordered organic molecular crystals: Ternary system
Pentaglycerinetris(hydroxymethyl)aminomethane-2-amino-2-me-
thyl-1,3-propanediol (PGTRIS-AMPL)
Dhanesh Chandra
University of Nevada Reno, Reno, Nevada, USA
Thermal energy storage materials are gaining importance in en-
vironmental and ecological systems. Reversible heat absorption and
release during solid state phase transitions over range of temperatures
can be achieved during phase changes in organic crystals. Among the
solid–solid heat storage materials, the most promising heat storage
materials are organic polyalcohol globular tetrahedral molecular crys-
tals such as (CH3)C(CH2OH)3 for PG, (NH2)C(CH2OH)3 for TRIS, and
(CH3)(NH2)C(CH2OH)2 for AMPL, which store a large amount of
thermal energy in their solid state high temperature phases with or-
ientationally disorder crystal structure. In this study, we obtained the
Gibbs energies of pure PG and pure TRIS derived utilizing the available
experimental data including temperature-dependency of heat capacity,
enthalpy, and transitions temperatures, as well as obtained optimized
binary phase diagrams of TRIS-PG and AMPL-PG by CALPHAD calcu-
lations. Compared with binary system, ternary solid solutions allowed a
wider selection of materials with different phase transition tempera-
ture, heat content, and compositions for thermal energy storage appli-
cations. A thermodynamic analysis of the PG-TRIS-AMPL system has
data, when considering the ternary phase equilibria. The phase
boundaries of the PG-TRISAMPL ternary system with 12 groups of
various compositions were determined experimentally by DSC and
XRD. Thermodynamic calculations of the PG-TRIS-AMPL system pro-
vide significant thermodynamic data for thermal energy storage sys-
tems. Ternary isotherms of PG-TIRS-AMPL at various temperatures and
pseudo-binary isopleths at different compositional combination were
presented in this work.
O61
Removing phosphorus from molten silicon: a thermodynamic
evaluation of distillation
Ioana NUTA1,2, Simon FAVRE1,2, Guy CHICHIGNOUD1,2, Kader
ZAÏDAT1, Christian CHATILLON1,2
1
Univ. Grenoble Alpes SIMAP F-38000 Grenoble, France
2
CNRS, SIMAP F-38000 Grenoble, France
Within the framework of purification of molten silicon for solar
cells, phosphorus is one of few impurities that remains problematic. The
present purpose is to develop a new method that leads to a final
phosphorus concentration around 0.5 wppm. We have first focused on
the main thermodynamic parameters that control the process: relevant
thermodynamic parameters are taken from literature, such as activities,
partial pressures and interaction coefficients. According to our results
[1], distillation of phosphorus under vacuum occurs at high tempera-
tures. Yet, the residual oxygen present in the vacuum is a hindrance to
the distillation, since it evaporates in the form of silicon oxides.
Reference
[1] Favre, S., et al., ECS Journal of Solid State Science and
Technology, 2016. 5(3): p. P129P137.
O62
Consideration for Solubility Limit of P-and N-type Doping
Elements in Thermoelectric Material β-FeSi2 based on Phase
Diagrams
Yoshisato Kimura1,2, Hiroaki Otani2,3, YawWang Chai1,2
1
Tokyo Institute of Technology, School of Materials and Chemical
Technology, Dept. of Materials Science and Engineering, 4259-J3-
19Nagatsuta-cho, Midori-ku, Yokohama 226-8502, Japan.
2
(by March 31, 2016)Tokyo Institute of
Technology,Interdisciplinary Graduate School of Materials and Science,

Dept. of Materials Science and Engineering.
3
Graduate Student now withKawasaki Heavy Industries, Ltd., Japan.
Thermoelectric power generation without the emission of green-
house gas could be an appealing approach for preserving global en-
vironment and conserving energy. The β-FeSi2 is an ecofriendly ther-
moelectric material which can be used at high temperatures around
1073 K. The intrinsic semiconductor β-FeSi2 can be controlled as both
p- and n-type by doping elements, which is advantageous for the pre-
paration of thermoelectric modules which consist of p- and n-type
thermocouples. The objective of the present work is to establish phase
diagrams of the Fe-Si-X ternary systems where X is doping elements,
since thermoelectric materials must be designed through the electrical
propertiesoptimization due to dopant concentration and microstructure
control.The phase equilibrium information plays important roles. Not
only the excellent thermoelectric properties but also the durability and
reliability are required for the development of thermoelectric materials.
The β-FeSi2 phase is formed by the peritoctoid reaction between α-
Fe2Si5 and ε-FeSi, as well as the eutectoid decomposition of α into β and
Si phases. The formation of β-FeSi2 usually requires long term heat
treatment depending on initial microstructure. We have aimed to fabri-
cate not only βFeSi2 single phase alloys but also composite alloys con-
sisting of β-FeSi2 matrix with the dispersion of SiO2 particles including
complex oxides[1]. To optimise electrical properties of composite alloys
having multi-phase microstructure, the partitioning of doping elements
between the β-FeSi2 matrix and coexisiting phases becomes a very im-
portant factor to be controlled. Note that the fabrication process of
composite alloys involves the eutectoid decomposition of α into β and Si
in which the dopant is partitionedand concentratedinβ phasebecause the
solubility in Si is almost zero.
Isotherms were evaluated at 1073 K, for the phase equilibrium in-
formation regarding β phase, and at 1373 K, regarding α phase, for the
Fe-Si-X ternary systems where X is Al and Mn as p-type dopants, Co as
an n-type dopant. The reaction scheme was considered to validate these
isotherms for the case of X=Mn. The solubilityof p-type Al was found to
be restricted small, less than 1 at%, in both α and β phases. Excess
doping of Al beyond the solubility limit results in unintended multi-
phase microstructure formation by impurity phases, which causes the
reduction of thermoelectric performance. The solubility of p-type Mn is
larger than about 10 at% in both α and β phases. The proper compo-
sitional range of Mn for composite alloys is roughly from 1.5 to 3 at%.
In the case of n-type Co, the solubility in α phase, about 12 at%, is
larger than in β phase, about 9 at%. Thermoelectric properties of
composite type β-FeSi2 alloys with doping Mn and Co were evaluated in
the temperature range from 300 K to 1073 K by the measurements of
Seebeck coefficient, electrical resistivity, and thermal conductivity.
Reference
[1]Y. Kimura, K. Takeno, A. Mori, Y.W.Chai,J. Jpn.Inst.
Met.,79(2015), 613-620(in Japanese).
O63
High Temperature Experimental Contribution to the
Thermodynamic Modeling of Corium Pools
S. Gossé1, A. Quaini1, C. Guéneau1, T. Alpettaz1, E. Lizon A Lugrin1,
N. Dupin2, S. Poissonnet3, P. Bonnaillie3
1
CEA Saclay ,DEN, DPC, SCCME, LM2T, 91191 Gif-sur-Yvette
Cedex, France
2
Calcul Thermodynamique, 63670 Orcet, France
3
CEA Saclay, DEN, DMN, SRMP, 91191 Gif-sur-Yvette Cedex, France
During a severe accident in a Pressurized or Boiling Water nuclear
reactor, extreme temperatures may be reached (T>2500 K). Under
these conditions, the oxide fuel (UO2) may react with the Zircaloy
cladding and with the steel vessel, forming a mixture of solid-liquid
phases called in-vessel corium. In the worst scenario, this very high
temperature mixture may pierce the vessel and spread on the concrete
underneath the reactor to form an ex-vessel corium. New high tem-
perature thermodynamic data are needed to better predict the high
22
Calphad xxx (xxxx) xxx–xxx
temperature behaviour of the corium+concrete system.
To approach these very high temperature interactions between the fuel,
the structural materials and the concrete, the LM2T at CEA Saclay Centre
uses an approach combining the thermodynamic modeling of a chemical
system representative of a simplified prototypic corium using the Calphad
method (Al-Ca-Fe-Si-U-Zr-O) and the development of a specific high tem-
perature setup dedicated to the measurement of phase equilibria at high
temperature (up to 2400 K) on interesting corium sub-systems.
To reach such high temperatures, this setup uses an aerodynamic
levitation device and a CO2 laser heating technique that makes it pos-
sible to melt metallic or oxide samples at temperatures above 3000 K.
This technique avoids the interactions between the sample and the
crucible and permits to observe the formation of miscibility gaps that
often forms in such high temperature liquids.
In this framework, new phase equilibria data on the Fe-Zr-O system
and on the Al-Ca-Si-Zr-O system were carried out. The thermal arrest
measurements together with the composition and microstructure ana-
lyses will be presented for some metallic and oxide samples re-
presentative for invessel and ex-vessel samples. These experimental
results will be compared to the thermodynamic calculations from the
thermodynamic database under development.
O64
Coupled Nonlinear Ginzburg-Landau andMechanics Model for
Martensitic Transformations in Polycrystals
Guanglong Xu1, Yuwen Cui1,2
1
Computational Alloy Design Group, IMDEA Materials Institute,
Madrid 28906, Spain
2
Institute for Advanced Metallic Materials & School of Materials
Science and Engineering, Nanjing Tech University, Nanjing 210009,
China
Martensitic transformation, in a narrow sense, is defined as the change
of crystal structure to form a coherent phase or multi-variant domain
structures out from parent phase with the same composition by the small
shuffles or co-operative atom movements. It often competes with other
diffusional transformations in real processes. To elucidate the displacive-
diffusion effect recently manifested by atom probe tomographic analysis
whereatomic relaxation and short range diffusion occurduring martensitic
transformations while long range atomic movement dominates the diffu-
sional transformations, we develop a 2D multi-field model upon the non-
linear Landau model with irreducible representation formed strains and the
inertia dynamics for polycrystals. Incorporated with CALPHAD-based real-
time diffusion potentials, chemical mobility and grain boundary relaxing of
heterogamous nucleation, our new model represents the microstructure
evolution of polycrystallinecarbon steels during the quenching and parti-
tioning process [1].
To further account for the morphology in steels different from the shape
memory alloys, we put forward to the nonlinear coarse-grained dislocation
model in the context of continuum theory of dislocation. With the simu-
lations, we describe the mixed microstructure and composition distribution
comparable with the experiments, and demonstrate that the dislocations
account for the distinguishing microstructure morphology among carbon
steels, nickel steels and shape memory alloys undergoing same symmetry
breaking in transformation. We also discern that the difference of diffusion
mobility between austenite and martensite primarily contributes to the
partitioning in carbon steels. Based on the works, a prototype framework of
multi-field model is preliminary built up, which is characterized in cov-
ering microstructure and property control and physical inherent commu-
nication among some different scales, e.g. thermodynamics and continuum
mechanics at the macroscale together with phase field/Landau model at
the mesoscale[1].
Reference
[1]Guanglong Xu,Coupled Nonlinear Ginzburg-Landau and
Mechanics Model for Martensitic Transformations in Polycrystals, PhD
dissertation, Universidad Politécnica de Madrid & IMDEA Materials
Institute, Madrid, Spain, 2016.
 Calphad xxx (xxxx) xxx–xxx

O65 temperatures below 575 ˚C, which indicates the existence of the mis-
Application of CALPHAD for rapid solidification and metal cibility gap between the ordered δ1k-FeZn7 and disordered δ1p-FeZn10
additive manufacturingof Ti-Al and Cu-Sn based alloys phases. In this study, phase equilibria related to the (αFe), Γ-Fe3Zn10,
Christian Leinenbach1, Christoph Kenel1, Xiaoshuang Li1 Γ1-Fe11Zn40, δ1k, δ1p, ζ, (Zn) and liquid phases were experimentally
1
Empa-Swiss Federal Laboratories for Materials Science and determined by an alloying method, in which a multi-step melting pro-
Technology, Dübendorf, Switzerland cedure under a high level of vacuum (3×10-3 Pa) and heat-treatment at
Metal additive manufacturing (AM) techniques such as Selective Laser temperatures between 400 ˚C and 1000 ˚C under a 95% argon - 5%
Melting (SLM) or Direct Metal Deposition (DMD) have been identified as an hydrogen atmosphere were employed. Microstructures were examined
attractive option for the manufacture of novel functional components in and equilibrium compositions were analyzed by an FE-EPMA/WDS and
comparison with conventional manufacturing techniques. They allow EDS.
building components with complex 3D geometries layer by layer. The very
rapid consolidation of the base material in a small material volume and the
achieved high solidification rates allow for the manufacture of components
containing meta-stable materials which tend to decompose in conventional
casting or sintering processes. At the same time, these conditions may lead
to complex out-of-equilibrium microstructures, pronounced element seg-
regation and crack formation in the bulk alloy. Beside the stable phases and
elemental segregation, the phase transformation behavior, the formation of
metastable phases and extended elemental solubility under non-equili-
brium conditions in additive manufacturing (AM) are of great scientific
interest and technical importance. However, classical calculations based on
the CALPHAD approach are typically applied only for equilibrium states. In
the present work, some computational and experimental results on the
rapid solidification of TiAl-(Nb,Mo,V) and Cu-Sn-Ti as technical important
alloy systemswith an inherently complex phase transformation paths are
discussed. In order to model the influence of the highly non-equilibrium
characteristics of laser-based additive manufacturing, phase selection
hierarchy maps based on T0 (i.e. the temperature at which the Gibbs free
energies of two phases with the same composition are equal) temperatures
have been developed. The results are compared with the calculated soli-
dification paths of the alloys according to the Scheil-Gulliver model. The
simulations were experimentally validated for selected Ti-Al alloys using a
novel in situ method to study the behavior of alloys during rapid heating As shown in Fig.1, solubility ranges of the intermetallic compounds
and cooling combining laser heating with synchrotron microXRD and high- in the Zn-rich portion were critically determined, and it was confirmed
speed imaging[1]. that those considerably deviate to the Fe side in comparison with the
Reference phase diagram assessed by Burton and Perrot [2]. The miscibility gap
[1]C.Kenelet al.,Scripta Materialia,114(2016)117-120. between δ1k and δ1p was detected at 450 ˚C and 500 ˚C by the micro-
structure examination and the EPMA analysis. The δ1p phase, however,
disappeares at 445 ˚C, which suggests that the eutectoid reaction, δ1p →
O66
δ1k + ζ, exists at a temperature between 450 ˚C and 445 ˚C.
Experimental Determination of Phase Diagram of the Zn-Fe
References
Binary System
[1] R. Kainuma and K. Ishida, ISIJ Int., 47 (2007), 740.
K. Han1), I. Ohnuma2), K. Okuda1,3), R. Kainuma1)
1) [2] B.P. Burton and P. Perrot, “Phase diagram of Binary Iron
Department of Materials Science, Tohoku University, Sendai,
Alloys”, ed. H. Okamoto, ASM Int., Material Park, OH, (1993), 459.
Japan
2)
Computational Materials Science Unit, National Institute for
Materials Science (NIMS), Tsukuba, Japan O67
3)
Steel research laboratory, JFE steel Co., Kawasaki, Japan Application of CALPHAD Modeling in the Development of Light
Phase equilibria of the Zn-Fe binary system have been studied re- Metals
peatedly for several decades because of their importance for the high- Alan A. Luo, Weihua Sun, Emre Cinkilic, Zhi Liang
corrosive coating formed by the hot-dip galvanizing (GI) or galvan- The Ohio State University, Columbus, OH 43210, USA
nealing (GA). It is well-known that the boiling point of Zn (TbZn=906 ˚C In the last few decades, the discovery and development of new
at 1.013×105 Pa) is much lower than the melting point of Fe materials have gradually migrated from meticulous experimental ex-
(TmFe=1536 ˚C), which causes difficulty in preparing Zn-Fe alloys by ploration using “trial-and-error” and “design of experiments” methods
the high-frequency induction melting and arc melting due to explosive to material design approaches based on computational thermodynamics
vaporization of Zn. As a result, most of the experimental data on the and kinetics. Advanced light metals are increasingly being used in the
phase equilibria, especially in the Zn-rich portion, were determined by automotive, aerospace and consumer industries for weight reduction
the diffusion couple (DC) method. In the phase equilibria determined and structural efficiency. This talk presents several examples of using
by the DC method, the local equilibria at the inter-phase boundaries as computational thermodynamics and CALPHAD modeling in the devel-
well as negligibly small diffusion across the interface, which depends on opment of new aluminum, magnesium and titanium alloys.
the reaction time actually, are usually assumed. According to Kainuma The first example is the development of Mg-Al-Sn-Si alloy using the
et al.[1], however, the interfacial compositions of the ζ-FeZn13 and li- CALPHAD approach. As cast microstructures including phase forma-
quid phases at 450 ˚C deviated to Fe-rich side during a short reaction tion, phase fractions, segregation of solutes are predicted by Scheil
time. Then, they change gradually to constant (equilibrium) composi- model. The solution temperatures for the intermetallics were calculated
tions with increasing reaction time. Furthermore, a tiny composition so as to figure out the heat treatment temperature for dissolving solutes.
gap at around 91 at.%Zn in a solid Fe/liquid Zn DC was observed at Moreover, by coupling to the magnesium atomic mobility database, the
solution time could also be estimated. The predictions are in agreement

23

with the experimental characterization, which demonstrates the cap-
ability of CALPHAD in Mg alloys development.
One important requirement for cast aluminum castings is the high
ductility which is needed for structural applications. Iron (Fe) is a
common impurity element and can form a brittle Fe-rich intermetallic
phase known as β-Al5FeSi in cast aluminum alloys. On the other hand, a
certain level of iron is desired in cast aluminum alloys for high pressure
die casting, since it reduces the tendency of die soldering and also
improves the hot-tearing resistance. It is a common practice to add
manganese (Mn) to aluminum alloys to modify β-Al5FeSi intermetallic.
The CALPHAD simulation results and experimental validation suggest
that a Fe-to-Mn ratio less than 1 can effectively eliminate β-Al5FeSi
phase in the as-cast microstructure. This forms an important basis for
controlling the ductility of aluminum castings.
Titanium alloy is attractive to industries because of its combination
of lightweight and high strength. However, its applications are limited
due to the high costs of materials and manufacturing processes.
CALPHAD approach is used to design new cost-effective titanium alloys.
Ti-Al-Fe-Mn system is explored to replace the current workhorse alloy
Ti-6Al-4V. In this presentation, Ti-Al-Mn ternary system is investigated
in both thermodynamic and kinetic aspects to provide reliable basis for
the simulation of Ti-Al-Fe-Mn quaternary system.
O68
Plenary lecture
Mg/CaO reactions and thermodynamic assessment of the Mg-
Ca-O system
Rainer Schmid-Fetzer1, Song-Mao Liang1, Artem Kozlov1
1 hexAlN, and the experimentally observed crossover point between
Institute of Metallurgy, Clausthal University of Technology,
Robert-Koch-Str. 42, D-38678 Clausthal-Zellerfeld, Germany
Understanding the reactions between liquid Mg and CaO is im-
portant for melting and casting of magnesium alloys. Previous attempts
based on chemical reaction equations between stoichiometric phases
[1] cannot capture the "CaO dissolution" process properly. This work
presents the complete thermodynamic assessment of the Mg-Ca-O
ternary system. It includes:
• Significant revision of the thermodynamic data of key oxides, CaO
and MgO, based on original experimental work [2] so far not con-
sidered in thermodynamic databases or tabulations.
• Revision of the pseudobinary MgO-CaO phase diagram.
• Thermodynamic assessment of the Mg-O and Ca-O binary phase
diagrams.
• Combination with the binary Mg-Ca data to form the first quanti-
tative thermodynamic description of the Mg-Ca-O ternary phase
diagram.
In contrast to previous reports [1] the formation of a liquid Mg-Ca-
[O] alloy and some MgO during the reaction of liquid Mg with CaO is
predicted from the thermodynamic calculations at melting tempera-
tures. Solidification simulations are also performed. These predictions
from thermodynamic simulations are validated by experimental data
using in situ synchrotron radiation diffraction [3].
References
[1] K. Kondoh, J. Fujita, J. Umeda, H. Imai, K. Enami, M. Ohara, T.
Igarashi, Mater. Chem. Phys., 129 (2011), 631-640.
[2] K. V. Gourishankar, M. K. Ranjbar, and G. R. St. Pierre, J. Phase
Equilib., 14 (5) (1993) 601-611.
[3] R. Schmid-Fetzer, A. Kozlov, B. Wiese, C.L. Mendis, D. Tolnai ,
K.U. Kainer, N. Hort: Thermodynamic description of reactions between
Mg and CaO, in Magnesium Technology 2016, Edited by: A. Singh, K.
Solanki, M.V. Manuel, and N.R. Neelameggham,TMS (The Minerals,
Metals & Materials Society), 67-72 (2016)
24
Calphad xxx (xxxx) xxx–xxx
O69
A Revised Phase diagram of Ti-Al-N
J. Ullbrand1, K. Grönhagen1, M. Selleby2, M. Odén1
1
IFM, Linköping University, SWEDEN
2
KTH Royal Institute of Technology, SWEDEN
Ti-Al-N is an important system due to its applications. TiN is used as
a commercial hard coating in the cutting tool industry, and is also used
for its biocompatible properties. AlN has applications within the
semiconductor industry, and the ternary phases have various potential
applications [1,2]. The ternary phase diagram of Ti-Al-N, from Chen et
al. 1998 [3] refined by Gao et al. 2008 [4] using data by Saunders, is
here revised based on the new knowledge regarding the miscibility gap
between fcc-TiN and fcc-AlN, and the stoichiometric hex-AlN phase.
Intense research on the miscibility gap between fcc-TiN and fcc-AlN has
been carried out, since metastable thin films of fcc-(TiAl)N in solid
solution grown by PVD, are successfully used in the cutting tool in-
dustry as hard, wear resistant coatings. It is known that the metastable
solid solution decomposes spinodally, and form domains of the more
stable phase’s fcc-TiN and fcc-AlN during cutting. The decomposition is
accompanied by age hardening, highly beneficial for its application.
Unfortunately, the fcc-AlN undergoes a phase transition into the soft,
stable hex-AlN upon annealing, showing detrimental effects on the
hardness. Due to the industrial interest in these two phases, several ab
initio calculations of the free energies of the phases have been reported
e.g. [5,6]. The ternary phases in Ti-Al-N, assessed by [3], are based on,
at the time, limited information of the fcc-(TiAl)N miscibility gap, and
the hex-AlN phase, both mentioned above. Their information on the
phases are the Gibbs energies of the stable endpoints; fcc-TiN and
growth of fcc-(TiAl)N and the two phase region fcc-TiN and hex-AlN.
From this information the phases are described as ideal solutions and
compared to calorimetric measurements of the fcc phase by [7]. We
report an assessment including ab initio calculations of fcc-(TiAl)N, and
hex-AlN [6]. The fcc-(TiAl)N is assessed and the metastable endpoint,
fcc-AlN, can now be set with reasonable confidence. The hex-AlN phase
is optimized to fit the calculated ab initio values at high Al content [6] .
The optimization of the ternary phases are based on the new informa-
tion of the fcc-(TiAl)N and hex-AlN phases as well as new information
regarding the ternary phases.
References
[1] Y. Zhang, J. Am. Ceram. Soc., 98 (2015) 2570–2578.
[2] W. Yu, Acta Mater., 80 (2014) 421–434.
[3] Q. Chen, J. Phase Equilibria, 19 (1998) 146–160.
[4] J. Gao, J. Univ. Sci. Technol. Beijing, 15 (2008) 420–424.
[5] P.H. Mayrhofer, Appl. Phys. Lett., 88 (2006) 071922.
[6] B. Alling, Appl. Phys. Lett., 95 (2009) 181906.
[7] H. Stolten, Doktorarbeit, RWTH Aachen University, 1991.
O70
Is the use of DFT a sufficient condition to improve the physics
of CALPHAD?
Suzana G. Fries
ICAMS, STKS, Ruhr-Universität Bochum, Universitätsstraße 150,
44801 Bochum, Germany
About almost 20 years ago a call was done for integrating more
physics into CALPHAD type of modelling. Since then an immense
progress is done on the use of the Density Functional Theory (DFT) and
now a days, it is very rare that a CALPHAD assessment does not take
into account DFT calculated results. Contrary to experimental data, the
results obtained by DFT are very often not evaluated with respect to the
used approximation. It is then valid to question if the present descrip-
tions are truly richer in theory just by the fact that DFT calculated
values are taken into account in the modelling
In this lecture I analyze the effect in the predictions of models that
use DFT calculated configuration enthalpies of end-members of

complexes phases, the enthalpies of solid solutions and enthalpies of
formation of defects, at Zero and at finite temperature.
O71
New thermodynamic descriptions of Pb and Sn and a re-
assessment of data for the Pb-Sn system
Ondrej Zobac1, Alexandra Khvan1, Alan Dinsdale1
1 several challenges, which will be outlined.
National University of Science and Technology MISiS, Moscow,
Russian Federation ondrej.zobac@gmail.com
Data for unaries are essential for the modelling of binary and higher
order systems. Thermodynamic data for the pure elements were pub-
lished in the SGTE pure element database in 1991 [1]. Over last few
years an international collaborative activity has started towards the
development of a new generation of data for the pure elements. We
have assessed the thermodynamic data for the crystalline and liquid
phases of a number of elements. In this paper we will report the work
we have carried out on Pb and Sn. The assessments are based on pub-
lished and new experimental values of the heat capacity (Cp) of these
pure elements over the whole temperature range.
The Einstein model was chosen to represent the thermodynamic
properties of solid crystalline phases down to 0 K [2] supplemented by
terms to represent the correction of Cv to Cp, corrections due to an-
harmonicity and contributions from electronic effects. The thermo-
dynamic description was constrained also to the assessed value of S298.
Extrapolations of the heat capacity data above the melting point were
carried out to prevent that the crystalline phase becoming incorrectly
stable at high temperatures.
A two state model was used for the description of the liquid phase to
enable the extrapolation of the heat capacity below the melting point.
This model assumes that the liquid notionally contains solid-like and
liquid-like atoms which mix together ideally [3].
We measured the heat capacity of metals having a purity higher
than 5N using a Setaram LabSys Evo 1600 calorimeter under an inert
atmosphere. The heat capacity of the liquid phase and solid phases was
measured independently.
The phase diagram for the Pb-Sn system is characterized by three
solid phases FCC_A1 (Pb), BCT_A5 (Sn), DIAMOND_A4 (Sn) and a liquid
phase. There is eutectic at a temperature 183.0 ˚C and composition x
(Sn)=0.269. The data for the Pb-Sn system were reassessed using the
Parrot module in ThermoCalc software. Data were developed to re-
present the composition dependence of the thermodynamic properties
of the FCC_A1 and BCT_A5 phases using composition dependent
Einstein temperatures and the liquid phase using the two state model.
References
[1] A. T. Dinsdale, SGTE data for pure elements, CALPHAD, 1991,
15, 317-425.
[2] M.W. Chase, I. Ansara, A. Dinsdale, G. Eriksson, L. Höglund and
H. Yokokawa, Heat Capacity Models for Crystalline Phases from 0 K to
6000 K, CALPHAD, 1995, 19/4, 437-447
[3] J. Agren, B. Cheynet, M.T. Clavaguera-Mora, K. Hack, J. Hertz,
F. Sommer, U. Kattner, Extrapolation of the heat capacity in liquid and
amorphous phases, CALPHAD, 1995, 19/4, 449-480
O72
Thermodynamic Modeling of the Fe–O and Al–Fe–O Systems
Sergei A. Decterov1, Denis Shishin2, Evgueni Jak2
1
Centre de Recherche en Calcul Thermochimique, Dép. de Génie
Chimique, École Polytechnique, Montréal, Québec, Canada
2
School of Engineering, The University of Queensland, Brisbane,
Queensland, Australia
The Fe–O and Al–Fe–O systems are of primary importance for the
steelmaking industry, ceramic applications and development of re-
fractory materials. These are the key systems to thermodynamic mod-
eling of multicomponent spinel, slag and wüstite, as well as to the de-
scription of the solubility of oxygen in matte and alloys.
25
Calphad xxx (xxxx) xxx–xxx
A vast amount of experimental data of various types is available,
which may be internally consistent or contradictory, but thermo-
dynamic functions of phases are still not completely constrained by the
experimental information and the optimized thermodynamic properties
must rely on physically meaningful models. Furthermore, the modeling
of the Fe–O and Al–Fe–O systems has to be done keeping in mind the
ultimate goal of developing multicomponent databases. This presents
O73
Experimental investigation and Calphad modelling of the Fe-
Ce-Mn system
A V Khvan1, I V Fartushna1, E A Syutkin1, A T Dinsdale1
1
Thermochemistry of Materials SRC, NUST MISIS, 4, Leninsky
prosp, 119049, Moscow Russia
Partial isothermal sections of the Fe-Ce-Mn system had previously
been investigated experimentally by Kalychak et al [1] at 400 and 600
˚C. Recently we have studied the liquidus and solidus projections and
also an isothermal section at 900 ˚C [2-3]. However, there is still a lack
of thermodynamic data on the stability of ternary intermetallic com-
pounds, Fe11Mn6Ce2 (τ1) and Fe5Mn7Ce (τ2), which are characterized
by large homogeneity ranges on the (Fe-Mn) side of the system with a
constant Ce content. In the present work the enthalpies of formation of
these (τ1) and (τ2) phases and their dependence with the composition of
the compounds were measured using a high temperature solution ca-
lorimetric technique with an AlexSys 1000 isoperibol microcalorimeter.
The experiments were carried out on single phase samples, verified by
XRD analysis.
An attempt to assess the Fe-Ce-Mn system was made taking into
account our experimental thermodynamic properties and phase equi-
librium data.
References
[1] Y.M. Kalychak, et al., Visn. Lviv. Derzh. Univ. Ser. Khim 16
(1974) 11-15
[2] I Fartushna, et al, J Alloy Compound 654 (2016) 424-434
[3] I Fartushna, et al, J Alloy Compound 658 (2016) 331-336
O74
Key experiments and thermodynamic reassessment of Li-Si
system
Song-Mao Liang1, Artem Kozlov1, Franziska Biedermann2, Jürgen
Seidel2, Florian Mertens2, Rainer Schmid-Fetzer1
1
Institute of Metallurgy, Clausthal University of Technology,
Robert-Koch-Str. 42, D-38678 Clausthal-Zellerfeld, Germany
2
Institute of Physical Chemistry, TU Bergakademie Freiberg,
Leipziger Str. 29, D-09599 Freiberg, Germany
A consistent thermodynamic description of the Li-Si system is of
great importance for the Liion battery development. In 2013, we de-
veloped a thermodynamic description of Li-Si system based on available
experimental data at that time [1]. However, since then, many more
crucial experimental results have been published [2-5], and Braga et al.
[6] also published a new thermodynamic description. However, several
key shortcomings in that thermodynamic description [6] prompted a
thorough revision presented in this work.
In the present work, the enthalpy of formation of the key inter-
metallic phases are evaluated by linking precise experimental heat ca-
pacity (Cp) and entropy data [5] with unpublished equilibrium pressure
measurements for the hydrogenation of the silicides. The Gibbs energy
of the intermetallic phases are described with absolute reference state
and the Cp functions reflect real experimental data as opposed to the
Neumann-Kopp rule, which was adopted in [6]. A newly developed LET
function [7] is applied to describe the interaction parameters of the
liquid phase, and the inverted miscibility gap shown in [1, 6] has been
successfully eliminated by that inherently consistent LET function. In
addition, we emphasize that all the original experimental data and ab

initio calculation data must be evaluated properly. Generally, we should
put more weight on original experimental data, less weight on ab initio
calculation data, and never use the derived enthalpy data, such as from
Electromotive force (EMF) measurement. Braga et al. [6] put more
weight on their own first principle calculations rather than real ex-
perimental results published by other researchers. Consequently, their
Calphad calculation results disagree with the real original experimental
EMF data, and only agree with the derived enthalpy of formation data
[6] from the EMF experiments.
References
[1] P. Wang, A. Kozlov, D. Thomas, F. Mertens, R. Schmid-Fetzer,
Intermetallics, 42 (2013) 137-145.
[2] M. Zeilinger, I.M. Kurylyshyn, U. Häussermann, T.F. Fässler,
Chem. Mater., 25 (2013) 4623-4632.
[3] M. Zeilinger, D. Benson, U. Häussermann, T.F. Fässler, Chem.
Mater., 25 (2013) 19601967.
[4] M. Zeilinger, V. Baran, L. van Wüllen, U. Häussermann, T.F.
Fässler, Chem. Mater., 25 (2013) 4113-4121.
[5] D. Thomas, M. Zeilinger, D. Gruner, R. Hüttl, J. Seidel, A.U.B.
Wolter, T.F. Fässler, F. Mertens, J. Chem. Thermodyn., 85 (2015) 178-
190.
[6] M.H. Braga, A. Dębski, W. Gąsior, J. Alloys Compd., 616 (2014)
581-593.
[7] S.M. Liang, P.S. Wang, R. Schmid-Fetzer, Inherently consistent
temperature function for interaction parameters demonstrated for the
Mg–Si assessment, to be submitted to Calphad.
O75
Thermodynamic optimization of Si-Zr-N system along with re-
assessment of Si-N system
Soumya Sridar, Ravi Kumar and K C Hari Kumar
Department of Metallurgical and Materials Engineering, Indian
Institute of Technology Madras, Chennai-600036, India
e-mail: soumya_sridar@yahoo.co.in
Addition of silicon into Zr-N thin films has shown to improve the
hardness along with considerable enhancement in oxidation resistance
[1]. This improvement in properties is attributed to the formation of
silicon nitride along with zirconium nitride in these coatings. Hence,
the knowledge of phase equilibria and thermochemistry of Si-Zr-N
system will be useful in understanding the phase stability of such
coatings. Experimental isothermal sections plotted at 1273 and 1573 K
for Si-Zr-N system by [2] shows a U-type invariant reaction occurring
between these two temperatures.
In this work, we report the thermodynamic optimization of Si-Zr-N
system using Calphad approach combined with ab initio calculations.
The thermodynamic descriptions of Si-Zr and Zr-N is taken from lit-
erature [3, 4]. Thermodynamic description of Si-N by [5] was revised
with thermochemical data obtained using ab initio phonon calculations
for each stable polymorph of Si3N4 and experimental data from litera-
ture. This was necessary in order to have better fit of the ternary in-
26
Calphad xxx (xxxx) xxx–xxx
formation. Si-Zr-N system is optimized using finite temperature ther-
modynamic properties of Zr5Si3N (solid solution of N in Zr5Si3) phase
obtained by ab initio phonon calculations and constitutional data from
[2].
References
[1] M. Nose et al., Surface and Coatings and Technology, 132
(2000) 163-168.
[2] P. Rogl et al., Phase diagrams Ternary Boron Nitride Silicon Nitride
Systems, ASM International, Ohio, 1992, 215-218.
[3] H.M. Chen et al., Journal of Alloys and Compounds, 468 (2009)
209-216.
[4] Soumya. S et al., Calphad (in communication)
[5] X.Ma et al., Calphad, 27 (2003) 383-388.
O76
Thermodynamic modeling of PbX (X=S,Te) using five sub-lat-
tice model developed explicitly for semiconductors
M. C. Peters1, J. W. Doak2, J. E. Saal2, G.B. Olson2, P.W. Voorhees1
1
Department of Materials Science and Engineering, Northwestern
University, Evanston, IL
2
QuesTek Innovations LLC, Evanston, IL
Thermoelectric (TE) materials provide a viable option to our
growing energy needs, due to their unique ability to convert waste heat
into electricity. To date, TE materials remain in limited use due to their
low efficencies, measured by a parameter known as ZT. Recent research
has shown that the presence of sulfur can increase the ZT value of bulk
PbTe by nearly a factor of 2 [1]. This is done by increasing the scat-
tering of heat carrying phonons through nanostructures created by
nucleation and growth. To fully optimize this material, a clear ther-
modynamic understanding of the system is necessary.
A five-sublattice model has been used to describe the PbX (X=S,Te)
semiconductors using the CALPHAD method. This model, originally
developed by Chen et al [1] has three additional sublattices to explicitly
model interstitials, electrons, and holes. The model is based on fixed
physical parameters of the semiconductor i.e. the band gap, lattice
parameter, and effective masses of the charge carriers that allow for a
higher degree of physical accuracy. A recent study by Doak et al [2]
provides first-principle calcualtions on the formation energies of a
number of different point defects under Pb-rich and X-rich conditions.
These calculations offer guidance to what end members and defects
should be chosen in the PbX system. For each semiconductor, doubly
ionized vacancies have shown to be sufficient to model the charge
carriers. The physical parameters of the of semiconductor as well as the
ionzed defects are treated as fixed values in this model. The neutral
vacancy defect end-members, guided by first-principle calculations
are used as optimizing parameters. The model shows an improvement
over previous assessments of PbTe [3] that rely on interaction para-
meters for the off stoichiometric behavior and is the first time PbS
has not been treated as a stoichiometric compound in a CALPHAD as-
sessment.

References
[1] John Androulakis et al. Journal of American Chemical Society,
129 (2007) 9780-9788.
[2] Q. Chen et al. Journal of Electronic Materials, 27 (1998) pp. 961-
971.
[3] Jeff Doak, Kyle Michel, and Chris Wolverton, Journal of
Materials Chemistry C, 3 (2015) pp. 10630-10649.
[4] Saurabh Bajaj et al. Acta Materialia, 92, (2015) 72-80.
Poster
PA1
Using defect stability phase diagramsto identify bulk oxide
defects in an electrochemical environment
Mira Todorova and Jörg Neugebauer
Max-Planck-Institut für Eisenforschung GmbH, Max-Planck-Str. 1,
40237Düsseldorf, Germany
Theoretical and modelling concepts in semiconductor defect
chemistry and electrochemistry have hugely evolved over the last years
and are crucial for their respective fields such as optoelectronics,
semiconductor devices or corrosion and battery materials. Recently, we
developed an approach which is based on a fully grand-canonical de-
scription of both ions and electrons that unifies and “translates” theo-
retical concepts of these two fields [1]. It exploits the formal equiv-
alency between point defects in semiconductors and ions in solution
and quite naturally links ab initio calculations to experimental ob-
servables, such as pH and U (the electrode potential), whichchar-
acterisethe state of an electrochemical system. We employ the new
approach to construct defect stability phase diagrams [2], which depict
the dominant native point defects of band-gap materialsand re-
vealconditions under which the host may become thermodynamically
unstable. Such diagrams can be also used to identify areas of interest in
the context of electrochemical applications. As an example we will
consider the protective layer of galvanized steels which consists of ZnO.
Using the defect phase diagram we obtain direct insight into the
dominant defects that control the growth and dissolution of the oxide
barrier layer forming in corrosive environment [3].
References
[1] M. Todorova and J. Neugebauer, Phys. Rev. Appl. 1(2014)
014001.
[2] M. Todorova and J. Neugebauer, Surf. Sci. 631(2015) 190-195.
[3] M. Todorova and J. Neugebauer, Farad. Discussions 180(2015)
97-112.
PA3
On the lattice stability of copper under current stressing
Yu-chen Liu1, Yung-si Yu1, Shang-Jui Chiu2, Yen-Ting Liu2, Hsin-Yi
Lee2, and Shih-kang Lin1,*
1
Department of Materials Science and Engineering, National Cheng
Kung University, Tainan, Taiwan
2
National Synchrotron Radiation Research Center, Hsinchu, Taiwan
*linsk@mail.ncku.edu.tw
Abstract
The electromigration (EM) effect describes the phenomenon of
atomic diffusion under current stressing, which was firstly discovered in
the early 20th century. Various mechanisms for this phenomenon have
been proposed over the past 50 years. Huntington et. al. [1] proposed
the “semiballistic model” based on momentum transfers between
electrons and ions. The net force exerted on metal ions is the sum of
electrostatic forces and so-called “electron-wind forces”. A character-
istic index, effective charge z*, was invented as a measure of the ratio of
the two forces. Sorbello [2, 3] criticized that this model can only be
applied to a free electron gas system without considerations on complex
band structures in real materials. Stemmed from the “charge polariza-
tion model” proposed by Bosvieux and Friedel [4], he systematically
calculated theoretical effective charges based on the scheme of pseudo-
potentials and suggested that the force exerted on metal ions originates
27
Calphad xxx (xxxx) xxx–xxx
from the redistribution of the surrounding charges, namely the electron
perturbation owing to external electric fields. The calculated effective
charges agree closely with the experiments. However, none of the ex-
isting model has coupled the EM effect and lattice stability and thus
cannot describe the lattice distortion or diffusion in experiments. In this
work, ab initio calculations based on density functional theory (DFT)
and corresponding in situ synchrotron X-ray diffraction measurements
for pure Cu stripes under current stressing were performed. Ab initio
calculations predict that electron perturbation would cause lattice ex-
pansion. Since the electrons at the cathode possess higher energy and
would induce larger extent of electron perturbation than those at the
anode, the voltage drop would establish a tensile strain gradient from
the cathode toward the anode. This ab initio prediction agrees closely
with the in situ measurement of synchrotron X-ray diffraction for cur-
rent stressing experiments: At early stage of current stressing, unequal
lattice expansions were observed along the stripes. Therefore, the
conclusion can be drawn that the electric perturbation would induce a
strain gradient, which could be the driving force for EM. This combi-
natorial research with in situ synchrotron X-ray radiation and ab initio
calculations reveals the thermodynamic foundation of the EM effect.
References
1. Huntington, H.B. and A.R. Grone, Current-induced marker motion
in gold wires. Journal of Physics and Chemistry of Solids, 1961. 20(1–2):
p. 76-87.
2. Sorbello, R.S., Theory of Electromigration, in Solid State Physics, E.
Henry and S. Frans, Editors. 1997, Academic Press. p. 159-231.
3. Sorbello, R.S., A pseudopotential based theory of the driving forces
for electromigration in metals. Journal of Physics and Chemistry of Solids,
1973. 34(6): p. 937-950.
4. Bosvieux, C. and J. Friedel, Sur l'electrolyse des alliages metalliques.
Journal of Physics and Chemistry of Solids, 1962. 23(1–2): p. 123-136.
PA4
The third generation CALPHAD databases: segmented model
for pure Al, Cr, Ge, Ir, Mo, Nb, Re, W, Fe, Ni and Ta
Irina Roslyakova1, Setareh Zomorodpoosh1, Lijun Zhang2, Bo
Sundman3, Holger Dette4, Ingo Steinbach1
1
ICAMS, Ruhr-University Bochum, Germany
2
State Key Laboratory of Powder Metallurgy, Central South
University, Changsha, P.R. China
3
CEA, Sacley, France
4
Faculty of the Mathematics, Ruhr-University Bochum, Germany
A novel physically-based model for the description of the thermo-
dynamic properties of the pure elements down to 0K has been proposed.
The proposed model based on the fitting of the heat capacity data and
considered physical several contributions (e.g. electronic, vibrational,
etc.) [1]. Since these contributions appear in different temperature ranges
and can be described by different functions, the segmented regression
methodology [2] has been applied for the contraction of the physically-
based mathematical model for the heat capacity of pure elements. The
thermodynamic properties of pure Cr, Al and Fe have been modelled by
the proposed segmented model and the obtained results have been pre-
sented during annual CALPHAD 2014 meeting [3]. Currently, we ex-
tended the proposed segmented approach for the description of the heat
capacity data [4] of such pure elements as Ir, Mo, Nb, Re, W, Ni and Ta.
The obtained results show a good agreement between experimental data
for the entire temperature range down to 0K. Moreover we validate the
consistency of underlying fitting results, by calculating other physical
properties of interest, such as the enthalpy and the entropy and compared
them to the available experimental data. The obtained results fit well the
data on the S298 and the enthalpy.
References
[1] G. Grimvall, Thermophysical properties of materials, Elsevier, 1986.
[2] G. A. F. Seber, C. J. Wild, Nonlinear Regression, John Wiley &
Sons. Inc., Hoboken, New Jersey, 1989.

[3] I. Roslyakova, B. Sundman, H. Dette, Modeling of thermo-physic
properties for pure elements using segmented regression methodology.
CALPHAD XLIII, Changsha, China, 2014.
[4] Y. S.Toulouklin, Thermophysical properties of matter: The TPRC
Data, Volume 4: Specific Heat, Metallic Elements and Alloys, 1975.
PA5
CALPHAD database of composition-dependent elastic proper-
ties of biocompatible Ti-alloys from first-principles calculations
Cassie Marker1, ShunLi Shang1, Ji-Cheng Zhao2, Zi-Kui Liu1
1 special quasirandom structures (SQS) to mimic the behavior of
Department of Materials Science and Engineering, The
Pennsylvania State University, University Park, PA 16802, USA
2
Department of Materials Science and Engineering, The Ohio State
University, Columbus, OH 43210, USA
In recent years there has been an increasing interest in finding
better materials for loadbearing implants due to the increase in total
knee and hip arthroplasties. Krutz et al. [1] predicted that the total
number of hip replacements would grow by 174% from 2005 to 2030.
The primary considerations for biomedical implants, such as load-
bearing knee and hip implants, are elastic modulus, biocompatibility,
and fatigue strength [2], since there have been issues with the cyto-
toxicity and stress shielding with the most common implant materials.
Stress shielding occurs when the elastic modulus of the implant is
higher than that of bone. Due to the elastic difference, load application
to the joint results in the implant material absorbing all of the stress and
causing the bone surrounding the implant to atrophy, which leads to a
loss in bone density implant loosening and failure [2].
28
Calphad xxx (xxxx) xxx–xxx
The present study aims at investigating the elastic properties of the
Ti-Mo-Nb-Ta-Sn-Ta-Zr system using an integrated first-principles cal-
culations and CALPHAD modeling (CALculation PHAse Diagram) ap-
proach. First-principles calculations based on Density Functional
Theory were used to predict the single crystal elastic stiffness con-
stants (cij’s) of the bcc phase for the pure elements, five binary systems
of Ti-X (Mo, Nb, Sn, Ta, Zr) and ten Ti-X-Y ternary systems. In addi-
tion, polycrystalline aggregate properties such as bulk modulus, shear
modulus, Young’s modulus, and Poisson ratio are calculated. For each
binary or ternary system, the properties were computed for three
random structures and then for the binary systems the properties of
five dilute structures were also calculated. The calculated elastic
properties were compared to available experimental data to ensure the
accuracy. For example, the fitted Young’s moduli of the binary alloys
are shown in figure 1 in terms of the Redlich-Kister polynomial used
commonly in CALPHAD modeling approach. Figure 1 indicates that it
is possible to design biocompatible Ti-alloys with their Young’s moduli
matching that of bone (～20 GPa).
References
[1] S. Kurtz, K. Ong, E. Lau, F. Mowat, M. Halpern, J. Bone Jt.
Surgery-American Vol. 89A (2007) 780–785.
[2] M. Long, H.J. Rack, Biomaterials. 19 (1998) 1621–1639.
PA6
Liquidus and Solidus Phase Boundaries of Fe-Cr-Ni-Mo system
Y. Hosaka1, N. Ueshima1, K. Oikawa1
1
Department of Metallurgy, Graduate School of Engineering,
Tohoku University, Aoba-6-6-02, Aramaki, Aoba-ku, Sendai, 980-8579,
Japan
Fe-Cr-Ni-Mo system is fundamental subsystem of high-alloyed
steels such as stainless steels. The solidus and liquidus phase bound-
aries of this system is important to understand the solidification path
and control the microstructure. In this study, the solidus and liquidus
phase boundaries of NiCr, Ni-Cr-Mo, Fe-Cr-Mo and Fe-Cr-Ni-Mo
system has been investigated using the differential scanning calor-
metry (DSC). And based on the experimental results, thermodynamic
assessment has been conducted. The experimental results showed that
the liquidus and solidus phase boundaries of Ni-Cr-Mo and Fe-Cr-Mo
systems were quite different from the previous calculated thermo-
dynamic parameters [12] because of lack of experimental information
as shown in Fig. 1. Present thermodyamic assessment results could
reproduce the experimental results of quaternary alloys as well as
ternary systems.

References
[1] J-O. Andersson, Metall. Trans. A, 19A(1988), 1385.
[2] K. Frisk, Calphad, 14(1990), 311.
PA7
On the excess Gibbs-energy parameters of the liquid Ag-Zr and
Ag-Cu-Zr alloys
A. Dezső 1, 2; P. Baumli 1, 2; G. Kaptay 1, 2
1
Bay Zoltan Nonprofit Ltd, 2 Igloi, Miskolc, Hungary-3519
2
University of Miskolc, Egyetemvaros, Miskolc, Hungary-3515
The Ag-Zr system is investigated in this presentation. The high silver
containing alloys occur in several applications, for example in the
electrical industry, medicine, and amorphous metal alloys [1-2]. The
silver-zirconium system contains two intermetallic phase areas, with
peritectic reactions [3]. Near the silver side, beside the lowest tem-
perature euctectic reaction, a metastable liquid separation zone is
found. The zone is well described by excess Gibbsenergy parameters [4-
5], but these parameters lead to the formation of inverse miscibility gap
during high temperature calculations.
In this work the different excess Gibbs-energy models are compared.
It will be shown which models and equations are more acceptable and
which ensure the disappearing of the inverse miscibility gap. The re-
sults can be used to reassessment the multicomponent systems based on
binary Ag-Zr system. The Ag-Cu-Zr system will be shown as an example.
References
[1] Y.Y. Cui, T.L. Wang, K.P. Tai, B.X. Liu: Non-equilibrium alloy
formation in the Ag–Zr system by ion beam mixing, Journal of Alloys
and Compounds 488 (2009) 223–226
[2] D. Janovszky, K.Tomolya, A.Sycheva, G. Kaptay, Stable mis-
cibility gap in liquid Cu-ZrAg ternary alloy, J Alloys Compds, 2012,
vol.541, pp.353-358.
[3] I. Karakaya-W.T. Thompson: The Ag-Zr (Silver-Zirconium)
System, Journal of Phase Equilibria Vol. 13 No. 2 1992
[4] X.C. He, H. Wang, H.S. Liu, Z.P. Jin: Thermodynamic description
of the Cu–Ag–Zr system, CALPHAD 30 (2006) 367–374
[5] D. H. Kang, I.-H. Jung: Critical thermodynamic evaluation and
optimization of the Ag–Zr, Cu–Zr and Ag–Cu–Zr systems and its appli-
cations to amorphous Cu–Zr–Ag alloys, Intermetallics 18 (2010)
815–833
PA8
Re-assessment of binary Fe-Si system
Senlin Cui and In-Ho Jung
Department of Mining and Materials Engineering, McGill
University, 3610 University Street, Montreal, Quebec, H3A 0C5,
Canada
Silicon steels (electric steels) combines low magneto-striation and
high saturation magnetization has been broadly used as soft magnetic
materials. Electrical steels is the fundamental material for both elec-
tromagnetic energy conversion and energy transportation. As the re-
quirements for environmental conservation and energy saving has
driven the expansion of the industries of green energy generation and
electric vehicle manufacturing, there is an increasing market for silicon
steels. Thermodynamics and kinetics are two vital factors need to be
considered during silicon steel design. Thus, a better study of the
thermodynamics of Fe-Si system is helpful for the understanding of the
various phenomena in the whole chain of the silicon steel preparation.
Several assessments have been done for the Fe-Si system. However,
a certain thermodynamic data in this system were not accurately re-
produced in the previous thermodynamic assessments. In the current
work, all the thermodynamic and phase diagram data of the Fe-Si
system available in the literature were critically evaluated and re-op-
timized to obtain thermodynamic parameters reproducing all the reli-
able experimental data. In particular, the thermodynamic properties of
liquid phase were modeled using both the Modified Quasi-chemical
29
Calphad xxx (xxxx) xxx–xxx
Model (MQM) and the Bragg-Williams-Gorski (BWG) model to provide
two sets of parameters. The orderings in bcc phase were reproduced
with compound energy formalism. The improved thermodynamic de-
scription of the Fe-Si system is presented in comparison with the ex-
perimental information and previous assessments.
PA9
A coupled experimental and thermodynamic study of the Al-Cr-
Mg system
Senlin Cui, and In-Ho Jung
Department of Mining and Materials Engineering, McGill University
3610 University Street, Montreal, Quebec, H3A 0C5, Canada
Al 6XXX series alloys is being considered as extruded materials for
automotive applications due to its high strength, formability and duc-
tility, weld ability, corrosion resistance, and low cost. Suitably con-
trolled alloying elements and precipitates during extrusion process are
one key determinant of the extrusion ability of Al alloys. Cr is a dis-
persoid former added to Al alloys for grain refinement. The addition of
Cr promotes the formation of Al7Cr and Al18Cr2Mg3 dispersoid phases
which can inhibit the generation and growth of recrystallization and
thus slow down the kinetics of recrystallization, and improve the super-
plasticity.
The phase relation in the Al-rich corner of the Al-Cr-Mg system was
revisited at 400, 450 and 500 ᵒC via solid/solid diffusion couples and
equilibrium/quenching experiment. In particular, the homogeneity
range of Al18Cr2Mg3 phase is determined to be Al-(8.7±0.6) at.% Cr-
(13.0±2) at.% Mg. A complete thermodynamic modeling for the binary
Al-Cr and ternary Al-Cr-Mg system was carried out based on the criti-
cally evaluated experimental data in literature and new experimental
phase diagram data.
PA10
Phase transformation and thermodynamic assessments
ofIn2O3-TiO2-Nb2O5 ternary system
Liumei Su, Xing Fan, Gemei Cai*, Zhanpeng Jin*
School of Materials Science and Engineering, Central South
University, Changsha, 410083, China
* E-mailaddresses: caigemei@csu.edu.cn (Gemei Cai),jin@csu.e-
du.cn (Zhanpeng Jin).
Due to the indispensable application in optical devices, developing
novel luminescence materials hastremendously triggered many re-
search efforts in recent years.Aspecial group of marterials with general
formula as A3+B4+C5+O6, for example, RETiNb/TaO6 (RE=La-Yb, Y,
Sc) [1] have been comprehensively investigated for their luminescent
properties, but little information associated with In2O3-TiO2-Nb2O5
ternary system was reported. In order to explore novel luminescence
materials, phase relationship of In2O3-TiO2-Nb2O5 system was system-
atically investigated via solid-state reaction in this study. Five three-
phase regions, ten two-phase regions, and six single-phase solid solu-
tions were determined by powder X-ray diffraction (XRD), scanning
electron microscopy (SEM), and electron probe micro-analysis (EPMA).
A novel solid solution In1-xNb1-xTi2xO4 (0 ≤ x < 0.45) with composi-
tion-driven phase transformation was observed in this work. In the
range of x = 0-0.35, In1-xNb1-xTi2xO4 crystallizes in the monoclinic
space group (S.G. P2/c)and　is isostructural with wolframite-type
InNbO4.　When x > 0.35, the ordered wolframite-type structure
transforms to a disordered α-PbO2 type structure (S.G. Pbcn). The
driving force for phase transformation stems from the ordering of ca-
tions Nb5+ and In3+. Both of these two structures were refined by the
Rietveld method and reasonably confirmed to be constructed by mixing
(Nb/Ti)O6, (In/Ti)O6, or (In/Nb/Ti)O6 octahedral polyhedrons in the
form of corner-sharing or edge-sharing in three-dimensional space. The
ever reported ternary compound InTiNbO6 [2] with an orthorhombic α-
PbO2 type structure was amended to be a monoclinic wolframite-type
structurein this work. Combining the experimental results in present

investigation with data on literatures, Nb2O5-TiO2, In2O3-Nb2O5, and
In2O3-TiO2 quasibinary systems have been evaluated to assess the
thermodynamic parameters of all the phases by means of the CALPHAD
method. The twosublattice ionic solution model [3] was used to de-
scribe the liquid phase. All the solid intermediate compounds have been
treated as stoichiometric compounds and their Gibbs energy is modeled
following Neumann–Kopp's rule [4]. The assessments was conducted
using the Thermo-calc software package [5] and a set of self-consistent
thermodynamic parameters for these quasibinary systems are obtained.
Present investigations will be useful for the whole ceramic community
working with In2O3-TiO2-Nb2O5 ternary system as well as for the de-
velopment of functional materials.
Acknowledgments
Financial supports by grants from the Major State Basic Research
Development Program of China (No. 2014CB6644002), the National
Natural Science Foundation of China (No. 51472273) and Hunan
ProvincialScience & Technology Department (No. 2014FJ4099).
References
[1] Y. Zhang, D. Geng, X. Li, et al.,J. Phys. Chem. C, 118 (2014)
17983-17991.
[2] G. Blasse, Mater. Res. Bull., 2 (1967) 497-502.
[3] M. Hillert, B. Jansson, B. Sundman, J. Ågren, Metall. Trans. A,
16 261-266.
[4] H. Kopp, Philos. Trans. R. Soc. London, 155 (1865) 71-202.
[5] B. Sundman, B. Jansson, J.-O. Andersson, Calphad, 9 (1985)
153-190.
PA11
Simplify the calculations of the entropy of formation for va-
cancy defects
Pinwen Guan1, Zi-kui Liu1
1
Department of Materials Science and Engineering, The
Pennsylvania State University, University Park, Pennsylvania 16802,
USA.
The thermodynamics of point defects is important for understanding
the properties of materials. The formation energy due to vibrational
entropy of one point defect can be as large as 1.3 eV [1]. However,
theoretical calculations on the entropy of formation for point defects
are very scarce, probably because this kind of calculations is very
computationally demanding [2]. An efficient approach for calculating
the formation entropy of vacancies, the Configuration-based Estimation
(CBE) method, is proposed in the present work. The CBE method makes
full use of static configurations and does not require phonon calcula-
tions for the defective crystal, leading to a huge reduction of compu-
tation time. Applying the CBE method, entropies of formation of va-
cancies in Cu, Mg and ZnS are calculated, and the results are found in
excellent agreement with those from phonon calculations. Its applica-
tion to the Zn-S system is also demonstrated, and the derived defect
chemistry is in agreement with the experimental data.
References
[1] E. Rauls et al., Physical Review B, 69 (2004) 155213.
[2] J. Rogal et al., Physica Status Solidi B-Basic Solid State Physics,
251 (2014) 97-129.
PA12
First-principles calculations and thermodynamic modeling of
the Ru-W binary system
Yong-Jie Hu1, Xuan L. Liu1, Laszlo J. Kecskes2, and Zi-Kui Liu1
1
Department of Materials Science and Engineering, The
Pennsylvania State University, University Park, PA 16802, USA
2
Materials and Manufacturing Sciences Division, US Army Research
Laboratory, Aberdeen Proving Ground, MD 21005, US
Ru-W alloys are currently being researched as involving compo-
nents for Ni-base superalloy systems and for applications in consumer
electronics. An accurate phase diagram of the Ru-W binary system is
30
Calphad xxx (xxxx) xxx–xxx
desired to help researchers minimize the experimental work required to
fully understand the system and the phases involved. In the present
work, a thermodynamic description of the Ru-W system is developed by
the means of the CALPHAD approach in combination with first-prin-
ciples calculations based on density functional theory and available
experimental data in the literature. The intermetallic σ phase is de-
scribed based on a five sublattice model, using the formation enthalpies
of all the end-members from first-principle calculations. Special quasi-
random structures (SQS) are used to investigate the mixing of the solid
solution phases. Finite temperature thermodynamic properties of the
end-members of the σ phase are predicted based on the quasi-harmonic
approach using the Debye–Grüneisen model. The calculated phase
diagram agrees well with selected experimental phase equilibrium data
in the literature.
PA13
On the linear-exponential model for the temperature depen-
dence of excess Gibbs energy of solutions applied for the re-as-
sessment of the Mg-Si system
Fan Zhang1, Ying Tang1, Yong Du1, George Kaptay2
1
State Key Laboratory of Powder Metallurgy, Central South
University, Changsha, Hunan, 410083, P. R. China
2
University of Miskolc, Egyetemvaros, Miskolc, Hungary 3515 and
Bay Zoltan Applied Research Ltd, 2 Igloi, Miskolc, Hungary 3519
A new linear-exponential model for the temperature dependence of
excess Gibbs energy of solutions is developed in this paper in the fra-
mework of the Redlich-Kister polynomials. The whole temperature in-
terval is divided into two intervals by a special T* value. This value can
be selected in an arbitrary way, such as T* = 0 K (if the linear term is
actually not used), or the room temperature (T* = 298 K) or as the
lowest liquidus temperature in the system, or as the lowest temperature
with the known experimental data for the excess Gibbs energy. The low-
temperature interval is described by a linear equation, ensuring zero
excess heat capacity at zero Kelvin and excluding the appearance of
low-temperature artefacts (if any). The hightemperature interval is
described by an exponential equation, ensuring that the excess Gibbs
energy tends towards zero with increasing temperature and excluding
the possibility to form high-temperature artifacts. The two intervals are
connected at temperature T* ensuring that at this temperature the
linear and exponential intervals have the same values and the same
slopes. Only the high-temperature interval (the exponential equation) is
used for assessment, the lowtemperature linear interval is found only
after the assessment, and is used only to moderate the behavior of the
exponential equation at low temperatures. This new method is de-
monstrated here on the example of the Mg-Si system. It is shown that
the Mg-Si phase diagram is well reproduced, without any low-tem-
perature or high-temperature artifacts. The method is recommended for
other systems.
References
1. G.Kaptay. Calphad, 28 (2004) 115.
2. X.Yuan, W.Sun, Y.Du, D.Zhao, H.Yang. Calphad, 33 (2009) 673.
3. Y. Tang, X. Yuan, Y. Du. JMM B 37 (2011) 1.
4. Y. Tang, Y. Du, L. Zhang, X. Yuan, G. Kaptay. Thermochim Acta
527 (2012) 131.
5. G.Kaptay, Metall. Mater Trans 43A (2012) 531.
6. G.Kaptay. Calphad, 44 (2014) 81.
PA14
Energetic assessment on formation of Mg-LPSO structure
Shigeto R. Nishitani and Motoyuki Kiyohara
Department of Informatics, Kwansei Gakuin Univ., Sanda 669-1337,
Japan.
 Calphad xxx (xxxx) xxx–xxx

at first introduced by the thermal stress, collect solute atoms, which forms
clusters marked as 'キ' in the left panel of Fig.2. The additional solute atoms
are swept out from the stacking faults and concentrated on the few layers
away from the first stacking fault. The condensed solute atoms lead the
other stacking faults occurrence, as illustrated in the right panel of Fig.2.
The repeated loop of these steps makes the stacking faults periodically.
References
[1] Y. Kawamura, K. Hayashi, A. Inoue, T. Masumoto, Mater. Trans.,
42, (2001) 1172.
[2] Y. Yamamoto，Y. akamoto，Y. Masaki and S. R. Nishitani ,
Mater. Trans., 54, (2013), 656.
[3] Y. Sakamoto, C. Shirayama, Y. Yamamoto, R. Kubo, M.
Kiyohara, and S. R. Nishitani, Mater. Trans., 56, (2015), 933.
[4] H. Yokobayashi, K. Kishida, H. Inui, M. Yamasaki, Y. Kawamura,
Acta Mater., 59, (2011), 7287.
[5] D. Egusa, E. Abe, Acta Mater., 60, (2012), 166.

PA15
Parameter Conversion of Gibbs Energy Function between
Different Sublattice Models for Interstitial Solutions
Minami Tai, Daigen Fukayama
Research Center of Computational Mechanics, Inc., Tokyo 142-
0041, Japan
In this work, we present a conversion equation between two different
sublattice configurations for interstitial solutions. This would be useful to
LPSO(Long Period Stacking Order) structure in the Mg-Zn-Y alloy
construct a database for a multi-component system from assessed binary
was first found by Kawamura in 2001[1]. It's superior mechanical
databases. It is impossible to combine directly the binary databases, when
properties and lightness attract attention as the next generation struc-
different models are used to express the same phase. Normally, one has to
tural materials for the flight vehicle. The authors have performed the
optimize parameters again to change to the proper model, and it is often
energetic assessments of the first principles calculations on each step of
difficult. Abe et al. [1] described a parameter conversion between different
the formation mechanism of LPSO[2,3]. We've found that the L12
sublattice configurations for dilute interstitial solid solutions without mag-
clusters locating at the stacking faults shows repulsive energy against
netic contribution. This relation gives us an easy way to change the models.
the solution atoms of Zn and Y. We will report the calculation details
We added a magnetic term to their relation and applied it to the BCC
and the induced scenario of the LPSO formation at this conference.
phase of the Fe-H binary system. The BCC phase which is represented by the
We use VASP for the first principles calculations. We made slab models
two-sublattice model (Fe)1(H,Va)1 given by [2] can be converted to
including two stacking faults and a L12 cluster, which is observed by
(Fe)1(H,Va)3. Furthermore, we extended the efficient density of interstitial
Yokobayashi et al.[4] and Egusa and Abe[5]. Zn and Y pair is locating in
elements by estimating the error of approximations in [1]. This improved
the same layer separating from the cluster. The atomic configurations are
conversion can be applied to the Ti-H system, which hydrogen dissolves up
fully relaxed. As shown in Fig.1, the total system energy shows monotonous
to nearly 0.50 in the BCC titanium. We determined the Gibbs energy
decrease with increasing the distance between the cluster and the solution
parameters of (Ti)1(H,Va)3 from those of (Ti)1(H,Va)6 which Ukita et al.
pair. The energy difference reached about 0.2 eV, which means the Zn-Y
optimized [3] . Fig.1 shows the original and the converted Gibbs energy
pair is swept out from the cluster locating at the stacking fault.
functions. The converted function by this method agrees well with the
We now adapt a scenario illustrated in Fig.2. A stacking fault, which is
original function at high hydrogen density.

31

References
[1] T.Abe et al., Material Transactions, Vol. 55, No. 11 (2014) 1683-
1688.
[2] M.Zinkevich et al., Journal of Alloys and Compounds 339
(2002) 118-139.
[3] S.Ukita et al., J. Japan Inst. Met., Vol. 71, No. 9 (2007) 721-729.
PA16
Experimental study and thermodynamic modelling of the Fe-B-
Cr system
Viera Homolová1, Lucia Čiripová1, Peter Repovský1, Aleš Kroupa2,
Ján Kepič1
1
Institute of Materials Research, Slovak Academy of Sciences,
Watsonova 47 Košice 040 01 Slovakia
2
Institute of Physics of Materials, Academy of Sciences of Czech
Republic, Žižkova 22 Brno, 616 62 Czech Republic
The phase equilibria of the Fe-B-Cr ternary system over entire
composition were studied by theoretical and experimental methods.
Phase composition of the Fe-B-Cr model alloys after long term an-
nealing (1688-2300h) at 1353 and 873 K were investigated experi-
mentally. X-ray diffraction and scanning electron microscopy equipped
with EDXS analyzer were used for determination of equilibrium phases
in the system. Two iron borides FeB and Fe2B, six chromium borides
Cr2B, Cr5B3, CrB, Cr3B4, CrB2 and CrB4 and also intermetallic σ phase,
iron and chromium solid solutions and β-rhombohedral B were found in
alloys. CrB phase with orthorhombic structure was observed not only
for 1353 K and also for 873 K despite the fact that the phase in binary
Cr-B system exists in equilibrium only for high temperatures. High so-
lubilites of the third element in binary borides and no ternary phase
were found. The experimental results were used for modelling of phase
diagram of the ternary system by CALPHAD method. Thermodynamic
parameters for binary Fe-B, B-Cr and Fe-Cr systems were taken from the
literatures [1], [2], [3] and the data for pure elements were taken from
Dinsdale [4]. Boron is modelled as an interstitial element in the FCC
and BCC solid solution phases.
Acknowledgement
The work has been supported by Slovak Grant Agency (VEGA)
under grant No. 2/0153/15, No. 2/0113/16 and bilateral project
(MAD) SAV-AV ČR 15-11.
References
[1] T. Van Rompacy et al, J. Alloys Compd. 334 (2002) 173-181.
[2] E. Campbell et al, Calphad 26 (2002) 477-490
[3] A. Kroupa at al STEEL16-database
[4] A.T. Dinsdale, Calphad 15 (1991) 317-425.
PA17
An experimental investigation and thermodynamic modeling
of the Fe-Te and Fe-Ni-Te systems for the evaluation of fission
product induced corrosion of MOX fuel pin steel cladding.
Carl-Magnus Arvhult1, Malin Selleby2, Christine Guéneau3,
Stéphane Gossé4
1,2
KTH Royal Institute of Technology, Dept. of Materials Science
and Engineering, 10044 Stockholm, Sweden
3,4
DEN,DANS,DPC,SCCME, CEA Saclay, 91191 Gif-sur-Yvette
Cedex, France
E-mail:1 arvhult@kth.se, 2 malin@kth.se, 3christine.gueneau@
cea.fr
4
stephane.gosse@cea.fr
In the scope of the development of Generation IV Sodium-Cooled
Fast Reactors, tellurium and caesium fission products have been found
to be involved in a complex corrosion process of the stainless steel
cladding material of the Mixed Oxide Fuel pins. To develop a model of
this corrosion process, a thermodynamic assessment of the Fe-Ni-Cr-Te-
Cs-O sub-systems is in progress via the CALPHAD method.
The Fe-Te phase diagram is fairly well known from previous work
[1,2]; some phase boundaries are however unknown or conflicting, and
32
Calphad xxx (xxxx) xxx–xxx
thus we performed Differential Thermal Analysis and Isothermal Heat
Treatments followed by EDS analysis and X-Ray Diffraction to improve
the phase diagram and clarify uncertainties of crystallography and
defect ordering. More importantly were these analyses performed on
the Fe-Ni-Te ternary system, for which only one isothermal phase dia-
gram has been previously produced [3,4].
Coupled with ab-initio calculations to estimate formation energies,
the data were used to assess the thermodynamics of the systems via the
CALPHAD method. The calculated and experimental results will be
presented, together with an outlook of future experiments to resolve
remaining issues.
References
[1] Ipser, H., Komarek, K. L. & Mikler, H., 1974. Transition Metal-
Chalcogen Systems, V.:The iron-Tellurium Phase Diagram. Monatshefte
für Chemie, Volume 105, pp. 1322-1334.
[2] Okamoto, H. & Tanner, L. E., 1990. Fe-Te (Iron-Tellurium).
Binary Alloy Phase Diagrams, Volume 2, pp. 1781-1783.
[3] Raghavan, V., 1992. The Fe-Ni-Te (Iron-Nickel-Tellurium)
System. Phase Diagrams of Ternary Iron Alloys, Volume 6B, pp. 1081-
1085.
[4] Røst, E. & Åkesson, G., 1972. On the system Fe-Ni-Te. Acta
Chemica Scandinavica, Volume 26, pp. 3662-3670.
PA18
Theoretical study of Z-phase behavior in Ta-containing steels
A. Kroupa1, T. Káňa1, A. Zemanová1
1
Institute of Physics of Materials, ASCR, Zizkova 22, 616 62, Brno,
The Czech Republic
Recently, strong attention was given to the development new creep-
resistant martensitic 9%-12%Cr steels (wt.%) for steam power plant
applications. The aim of this effort was to increase operating steam
temperatures up to 600-650 ˚C which would allow higher efficiency of
the power production. New alloys are under development currently to
improve steam oxidation resistance, and creep strength. There was a
tendency towards increasing of Cr content from original 9% to max. of
11– 12%Cr. However, this type of steels lead to the precipitation of Z-
phase, Cr(V,Nb)N nitride, which adversely affect the creep strength [1].
Main reason of this behaviour was found to be the dissolution of small
and finely distributed V and Nb rich M(C,N) carbo-nitrides. They are
substituted by much larger Z-phase, which dissolves the same elements
and has adversarial influence on the creep strength of these steels. [2].
The Z-phase was modelled by the CALPHAD approach to be able to
predict the behaviour of the phase in dependence on the composition of
material [3,4].
In the scope of further development, Ta has been added to the steel,
replacing Nb and/or V, but Ta is also known form as Z-phase [5]. The
objective of this study was to prepare the thermodynamic model of Ta
containing Z-phase and enable to predict its behaviour in this type of
material. The tendency to strong nonstoichiometricity was found [5]
and therefore significant reassessment of current model is necessary
[6].
Acknowledgement
This study was supported by the Czech Science Foundation in the
scope of the project 14-15576S.
References
[1]H.K. Danielsen, J. Hald,Energy Mater., 1 (2006), pp. 49–57
[2] A. Strang, V. Vodarek,Mater. Sci. Technol., 12 (1996), pp.
552–556
[3] H.K. Danielsen, J. Hald, CALPHAD, 31(2007), pp. 505-514
[4] A. Kroupa, et al., CALPHAD XXXIX conference, Book of
Abstracts, p. 77, Jeju, Korea, June 2010
[5] H.K. Danielsen, J. Hald,Scripta Materialia,60(2009),pp.811–813.
[6]A. Kroupa, presented at Z-ULTRAWorkshop, Kyiv, Ukraina,
March, 2015

PA19
Ab initio evaluation of the enthalpy of solution of light ele-
ments in bcc iron
M. Souissi1,2, Y. Chen3, M. H. F. Sluiter4, H. Numakura1,2
1
JST-CREST, Gobancho 7, Chiyoda-ku, Tokyo 102-0076, Japan
2
Department of Materials Science, Osaka Prefecture University,
Gakuen-cho 1-1, Naka-ku, Sakai 599-8531, Japan
3
Department of Nanomechanics, School of Engineering, Tohoku
University, Aoba 6-6-01, Aramaki, Aoba-ku, Sendai 980-8579, Japan
4
Department of Materials Science and Engineering, Delft University
of Technology, Mekelweg 2, 2628 CD Delft, The Netherlands
When performing calculations for a defect in a host supercell, an
array of images is created around it under periodic boundary condi-
tions. Such images introduce a spurious long-range elastic interaction
affecting the evaluation of isolated defect properties. In this study, the
enthalpy of solution of B, C, N, and O in α iron has been evaluated using
supercell approach with subtracting the elastic image interaction from
the initial ab initio calculations [1]. Three configurations with a single
solute were used for each species, where the solute is introduced as an
interstitial in octahedral and tetrahedral sites, and as a substitutional by
replacing a host atom. Supercell calculations were made under the zero-
strain condition, where only the atom positions are optimized but the
supercell is kept fixed, and under the zero-stress condition, where the
atom positions and the supercell are fully optimized. To compare the
theoretical evaluation with experiment, the reference states are chosen
to be the same as those used in phase-diagram assessments: β boron for
B [2, 3], graphite for C [4], and diatomic molecules for N [5] and O [6].
The magnitude of the elastic interaction depends on the used ap-
proach and the supercell size. Under zero-strain (zero-stress) condition,
and using a Fe54 host supercell, the uncorrected enthalpy of solution of
interstitial C in octahedral configuration, for example, is about ～ 0.972
eV (0.805 eV). The elastic interaction energy is equal to 0.110 eV
(−0.060 eV). The corrected enthalpy of solution is then about ～ 0.862
eV (0.865 eV). The corrected values under both conditions are almost
equal to each other and define the enthalpy of solution of an isolated C.
The corrected enthalpy of solution is comparable with the experimental
enthalpy of solution of C (～ 1.1 eV [7]). For the substitutional con-
figuration, the correction is relatively unimportant in magnitude be-
cause of the small elastic distortion due to the solute in this case. The
correction does not change the relative stability of these solutes: C, N,
and O form octahedral interstitial solution, while B is more stable as
substitutional solution. In every case, the evaluated enthalpy of solution
is comparable to the experimental value.
References
[1] C. Varvenne et al., Phys. Rev. B, 88 (2013) 134102.
[2] T. Van Rompaey et al., J. Alloy. Compd., 334 (2002) 173.
[3] K. Yoshitomi et al., ISIJ Int., 48 (2008) 835.
[4] R. Naraghi and M. Selleby, J. Ågren, Calphad, 46 (2014) 148.
[5] K. Frisk, Calphad, 15 (1991) 79.
[6] M. Selleby and B. Sundman, Calphad, 20 (1996) 381.
[7] J. Chipman, Metall. Trans., 3 (1972) 55.
PA20
First-Principles Investigation on the Binary σ Phase Systems
Wei Liu1,4, Xiao-Gang Lu1,2, Qing-Miao Hu3, Pascal Boulet4, Marie-
Christine Record5
1
School of Materials Science and Engineering, Shanghai University,
200444 Shanghai, P.R. China
2
Materials Genome Institute, Shanghai University, 200444
Shanghai, P.R. China
3
Titanium Alloy Laboratory, Institute of Metal Research, Chinese
Academy of Sciences, 72 Wenhua Road, Shenyang 110016, China
4
MADIREL, UMR 7246 CNRS – Université Aix-Marseille, av
Normandie-Niemen, 13397 Marseille Cedex 20, France
5
IM2NP, UMR 7334 CNRS – Université Aix-Marseille, av
33
Calphad xxx (xxxx) xxx–xxx
Normandie-Niemen, Case 142, 13397 Marseille Cedex 20, France
The sigma phase is a non-stoichiometric intermetallic compound
designated as tetragonal structure (space group P42/mnm) with 30
atoms distributed on five inequivalent sites (2a, 4f, 8i1, 8i2, 8j). It is a
hard brittle phase mostly formed between transition elements and de-
teriorates various properties of stainless and other high-alloy steels as
well as Ni-based superalloys [1]. It’s obvious of great significance to
investigate the atomic ordering and its influence on physical properties
of the sigma phase for both technological and academic interests and
it’s known that a better understanding of physical properties can be
achieved by DFT calculations [2]. In this connection, the influence of
electronic factor on atomic ordering has been discussed and Cr-Co, Cr-
Fe, Cr-Mn, Mo-Co, Mo-Fe, Mo-Mn, Mo-Os, Mo-Re, Nb-Al, Nb-Ir, Os-Cr,
Re-Cr, Re-Mn, Re-V, Ru-Cr, Ta-Al, V-Co, V-Fe, V-Mn, V-Ni, W-Ir binary
sigma systems have been chosen to conduct EMTO_CPA calculations to
reveal the influence of the degree of orderness on the volume of the
sigma phase. The comparison of volumes of transition elements in the
sigma phase structure between the EMTO_CPA calculations and the
CALPHAD assessments [3] shows that for most elements the difference
between these two results are within 10%. The calculated results which
are consistent with the experimental data show that for most binary
systems, sigma phase of ordered state has a smaller volume than that of
disordered state. Only for Mo-Re system, the calculated results show a
different trend. In addition, the DOS calculations have also been con-
ducted on several binary sigma systems to investigate the bonds be-
tween constituent elements by using the EMTO_CPA method. The cal-
culation results show that both metallic and covalent bonding exist in
the sigma phases.
References
[1] J.-M. Joubert, Progress in Materials Science, 53 (2008) 528-583.
[2] J.-C. Crivello et al., CALPHAD, 34 (2010) 487–494.
[3] W. Liu et al., Computational Materials Science, 95 (2014)
540–550.
PA21
A 2NNMEAM+Qeq interatomic potential for the Fe-O system
Yongmin Kim1, Eunkoo Lee1, Byeong-Joo Lee1
1
Department of Material Science and Engineering, Pohang
University of Science and Technology, Pohang 790-784, Korea
An interatomic potential for the Fe-O binary system has been de-
veloped on the basis of the 2NNMEAM+Qeq potential formalism. The
2NNMEAM+Qeq is a recently developed interatomic potential form-
alism that can describe metallic, covalent and ionic bonding materials
simultaneously, by implementing a charge equilibration scheme that
can describe dynamic charge and electrostatic energy depending on the
local environment of individual atoms to the second nearest-neighbor
modified embedded-atom method (2NNMEAM) potential model. The
potential can describe structural (crystal structure, lattice parameter),
elastic (elastic constants) and thermodynamic (enthalpy of formation,
thermal stability) properties of iron-oxide compounds such as hematite
and magnetite in reasonable agreements with experiments. This po-
tential can be utilized for atomic scale investigations for oxidation
processes in steels and also for the effect of iron on the performance of
cathode materials for lithium ion batteries.
PA22
Thermodynamic assessment of Fe-Ti-S ternary phase diagram
by using cluster variation method
Kenji Hirata1, Satoshi Iikubo1, Hiroshi Ohtani2
1
Graduate School of Life Science and Systems Engineering, Kyushu
Institute of Technology, Kitakyushu 808-0196, Japan
2
Institute of Multidisciplinary Research for Advanced Materials,
Tohoku University, Sendai 980-8577, Japan
The Fe-Ti-S ternary phase diagram is not fully understood, although
it is a basic ultra-low-carbon steel system. For example, discrepancies in

reported experimental results regarding the solubility of Fe in TiS,
which has NiAs structure, have been noted [1-3]. Further, there is no
consensus regarding the solubility products estimated by experiments
[4]. As reported previously, our group has developed a Fe-Ti-S ternary
thermodynamic database by using first-principles calculations and the
Debye-Grüneisen model, which have been applied for some sulfides of
the Ti-S binary system [5]. In this work, we evaluated the Gibbs en-
ergies for the Ti-S binary solid solution and (Fe,Ti)S by using the cluster
variation method to improve the Fe-Ti-S ternary thermodynamic da-
tabase.
The Gibbs energy curve of (Fe,Ti)S between FeS and TiS is found to
be a convex downward curve. It is characteristic of an isomorphic solid
solution due to the attractive interaction between Fe and Ti in (Fe,Ti)S.
The vertical phase diagram between FeS and TiS obtained by using the
thermodynamic database is in good agreement with the experimental
results of Mitsui et al. [1]. Furthermore, the very low solubility of the Ti
solid solution in the Ti-S system as reported by Murray [6] agrees with
our calculated results. The solubility products of (Fe,Ti)S have been
experimentally estimated in previous studies [4]. The solubility product
estimated by using this thermodynamic database will be discussed in
this presentation.
References
[1] H. Mitsui, T. Sasaki, K. Oikawa and K. Ishida, ISI Int., 49(2009)
936.
[2] H. Kaneko, T. Nishizawa and K. Tamaki, J. Japan Inst. Met.
Mater., 27(1963) 312.
[3] R. Vogel and G. W. Kasten, Arch. Eisenhutt., 19(1948) 65.
[4] N. Mizui, T. Takayama, K. Sekine, ISI Int., 48(2008) 845.
[5] T. Tokunaga, H. Fujimoto, S. Iikubo, H. Ohtani, CALPHAD XLI in
Berkeley, (2012).
[6] J. L. Murray, Phase Diagrams of Binary Titanium Alloys, ASM
International, (1987) 275.
PA23
Current status of CaTCalc development
Kazuhisa Shobu1, Hiroshi Yamada2 and Mitsuhiro Hasebe1
1
Research Institute of Computational Thermodynamics, 807-1
Shuku, Tosu 841-0052, Japan
2
Advanced Industrial Science and Technology, 807-1 Shuku, Tosu
841-0052, Japan
We have been working on further development of the thermo-
dynamic software, CaTCalc, since its first release in 2008. New version
is almost ready for shipping, and some important features of the soft-
ware are outlined.
1. Advantage of the CaTCalc software in calculation of ceramics system
Some difficulty remains in thermodynamic calculation of ceramics
systems, which is, we believe, due to the fact that chemical poten-
tials of all elements of the system are sometimes not fully de-
termined by the Gibbs energy minimization. More specifically, au-
tomatic selection of stable phases is difficult in such cases, and
proper manual selection of them by the user is usually necessary
prior to the calculation. CaTCalc has a unique feature that it always
determines chemical potentials of all elements of the system, so that
stable phases are correctly and automatically determined. For in-
stance, Ca2SiO4-Mg2SiO4 section diagram can be readily calculated
without prior selection of phases by the user. This capability is
prerequisite for reliable calculation of ceramics system, and is one of
the major advantages of CaTCalc.
2. Database development and new optimization module
Commercial thermodynamic databases sometimes lack important
components and/or sufficient quality for practical industrial applica-
tions. In such cases, database development by the user are necessary.
Thus, we are developing a module for database development for
34
Calphad xxx (xxxx) xxx–xxx
CaTCalc, with which original CALPHAD database for oxides, in which
the modified quasi-chemical model is adopted for liquid, is being de-
veloped. Databases for metallic systems are also being developed.
Acknowledgement
This research is partially supported by the Cross-Ministerial
Strategic Innovation Promotion Program under the auspices of the
Council for Science, Technology and Innovation, Cabinet Office,
Government of Japan.
PA24
Thermodynamic modelling of Z-phase in ferritic-martensitic
steels
Deepak Kamal, Soumya Sridar and K C Hari Kumar
Department of Metallurgical and Materials Engineering, Indian
Institute of Technology Madras, Chennai-600036, India
e-mail: deepukamal@gmail.com
The global demand for increased performance and low emission
from power plants has resulted in the need to increase its operational
temperature. The major challenge native to such a change is the in-
crease in the tendency of the alloy for hot corrosion and oxidation.
Solving this would require an increase in the Cr content in the ferritic-
martensitic steels used. However, increased Cr content is accompanied
by an accelerated nucleation and growth of thermodynamically stable
Z-phase [1]. This phase originates from the Cr-V-N system and con-
sumes beneficial MX precipitates, leading to mechanical failure at op-
erating temperatures.
In the present work, we have obtained temperature dependent
thermodynamic properties of all stable end members of the sublattice
formulation of the Z-phase ((Cr,Fe)1:(Mo,Nb,Ta,V)1:(N,Va)1) using first
principles. The properties are calculated using harmonic phonon ap-
proximation as implemented in Phonopy [2] combined with DFT im-
plementation in VASP [3]. Results obtained this way are converted into
Gibbs energy functions with respect to the so-called Stable Element
Reference (SER). Finally an attempt is made to model the ternary
system Cr-V-N using Calphad method, primarily focusing on the ther-
modynamic description of the Z-phase.
References
[1] H.K. Danielsen and J. Hald. Materials Science and Engineering:
A, 505 (1-2), 169-177 (2009).
[2] 2A. Togo, L. Chaput, I. Tanaka, G. Hug, Phys. Rev. B, 81(17),
174301-1-6 (2010).
[3] VASP, Software, 1995 http://www.vasp.at/
PA25
A reassessment of the Si-Ti system considering association in
the liquid phase
F. Beneduce1, A. Costa e Silva2
1
Polytechnic School – USP, Av. Prof. Mello Moraes, 2463, São Paulo
SP, Brazil
2
EEIMVR - UFF, Av dos Trabalhadores 420, Volta Redonda RJ,
Brazil
The Si-Ti system presents many intermediate solid phases and an
asymmetric liquidus line in the TiSi2.region of the diagram. Previous
assessments have considered a disordered liquid [1,2] in their de-
scriptions. Seifert [2] has indicated that short range ordering (SRO) in
the liquid was a distinct possibility but preferred the disordered liquid.
In this work an attempt is made to improve the description of the liquid
by incorporating associates to the liquid according to Sommer asso-
ciation model [3] as well as more recent data on the system. The results
of the present assessment are compared with the results of the previous
assessments using disordered liquids (substitutional solution model).
The calculated results show the good agreement with the experimental
data.
References
[1] T Tokunaga, K Nishio and M Hasebe: Collected Abstracts of the

2001 Autumn Meeting of the Japan Inst. Metals, pp. 250, cited in T
Tokunaga, K Hashima, H Ohtani, M Hasebe. Materials transactions JIM.
2004;45(5):1507–14.
[2] HJ Seifert, HL Lukas, G Petzow, G. Zeitschrift fuer Metallkunde,
1996; 87(1): 2-13
[3] F Sommer. Zeitschrift fuer Metallkunde. 1982;72(2):72–6.
PA27
Structure and dehydriding properties of NaMgH3 and
Na0.9K0.1MgH3 hydrides
Song Tao, Zhong-min Wang*, Zhen-zhen Wan, Jian-qiu Deng,
Huaiying Zhou, Qingrong Yao
School of Material Science and Engineering, Guilin University of
Electronic Technology, Guangxi, Guilin 541004, China
Abstract: NaMgH3 hydride is a potential candidate for hydrogen
storage due to its high gravimetric and volumetric H densities (6 wt. %
and 88 kg / m3) [1, 2]. Perovskite-type NaMgH3 and Na0.9K0.1MgH3
hydrides have been synthesized by a high-energy ball milling method in
this work. The replacement of Na by 10 at. % of K results in a slight
increase of lattice parameters of NaMgH3 phase and the decrease of
activation energy of decomposition reactions. In comparison with
NaMgH3 hydride, Na0.9K0.1MgH3 hydride presented better dehydriding
kinetic properties, the onset desorption-temperature of which is greatly
decreased from 581K to 430K, the hydrogen-desorbed amount is about
3.0 wt. % within 6 mins at 638 K, and the maximum amount is 5.25 wt.
% (about 87.5 % of the theoretical value) after 40 mins. Further the-
oretical calculations, based on DFT, suggest that higher formation en-
thalpy and s-p-d hybridized orbitals (instead of s-p hybridized orbitals)
in Na0.9K0.1MgH3 hydride maybe contribute to the improved dehy-
driding properties by reducing its structure stability.
Keywords: NaMgH3, Na0.9K0.1MgH3, Peroveskite-type, Dehydriding
kinetic property, Hydrogen-desorbed amount
Acknowledgments
This project is financially supported by the National Natural
Foundations of China (51261003 and 51471055), the Natural
Foundations of Guangxi Province (2012GXNSFGA060002).
References
[1] A.H. Reshak, Int. J Hydrogen Energy 40(2015)16383-16390
[2] Zhong-min Wang, Jia-jun Li, Song Tao, et al., J. Alloys Compd.
660 (2016) 402-406.
PA28
Experimental Investigationand thermodynamic calculation of
the B-Fe-Mo Ternary System
Fucheng Yin*, Yongxiong Liu, Xuemei OuYang, Manxiu Zhao
Key Laboratory of Materials Design and Preparation Technology of
Hunan Province, School of Materials Science and Engineering, Xiangtan
University, 411105, Hunan, P.R. China
*Corresponding author.E-mail address:fuchengyin@xtu.edu.cn
The liquidus projection of the B-Fe-Mo system in the Fe-rich region
35
Calphad xxx (xxxx) xxx–xxx
has been proposed based on the liquidus temperatures obtained from
the DSC analyses and the microstructural characterization of arc-melted
alloys obtained by means of SEM-WDS, EMPA, DSC, and XRD.Five
different primary solidification regions and threeternary invariant re-
actions are proposed to occur in the region of Fe-rich corner. A ther-
modynamic optimization of the B-Fe-Mo system was performed based
on thermodynamic models of the three constitutional binary systems
and the experimental data from the literature [1-2] and the present
work. A set of thermodynamic parameters for the B-Fe-Mo system was
obtained with a reasonable agreement between the experimental and
calculatedresults.
Acknowledgments
This work was supported by national Natural Science Foundation of
china (No. 51471141), Scientific Research Fund of Hunan Provincial
Science and Technology Department (No. 2014FJ2010).
References
[1] E.I. Gladyshevskiiet al., Powder Metall. Met. C., 4(1966)55-60.
[2] A. Leithe-Jasperet al., J. Jpn. Inst. Met., 64(2000)154-162.
PA29
Ground state predictions for the sulfide electrolytes
Satoshi Iikubo1, Hiroshi Ohtani2
1
Graduate School of Life Science and Systems Engineering, Kyushu
Institute of Technology, Kitakyushu 808-0196, Japan
2
Institute of Multidisciplinary Research for Advanced Materials,
Tohoku University, Sendai 980-8577, Japan
Solid electrolytes comprising lithium superionic conductor mate-
rials exhibit good safety and stability characteristics, and high Li-ion
conductivity, thus they are expected to perform well in lithium-ion
batteries. The past few decades have seen an ongoing search for new
solid electrolyte materials. The lithium superionic conductor,
Li10GeP2S12, shows an extremely high lithium ionic conductivity of 12
mS/cm at 27 ˚C [1], which is comparable to or higher than the

conductivities of the organic liquid electrolytes used currently in li-
thium-ion batteries. Additional information about the phase stabilities
of related compounds would serve as a guide to the discovery of novel
lithium ion conductor materials. Therefore, the phase stabilities of the
sulfide electrolytes have been comprehensively investigated as mate-
rials for the development of high performance lithium-ion batteries.
In order to identify ground-state structures of the sulfide system that
are stable under ambient conditions, an evolutionary algorithm was
used to determine the total energies, optimized lattice structures, and
their corresponding electronic structures. The evolutionary algorithm
was implemented using the USPEX code [2] and was coupled with first-
principles calculations made within the framework of density func-
tional theory (the Vienna Ab initio Simulation Package, VASP)[3,4]. As
a first step, we examined whether the evolutionary algorithm could
generate the several crystal structures experimentally reported as a
stable under ambient conditions. For a Li:P:S atomic ratio of 3:1:4, one
crystal structure was obtained as a result of the ground state search.
This structure was quite similar to that reported for γ-Li3PS4, although
the calculated structure had a small amount of lattice distortion. This
result indicates that the evolutionary algorithm employed here works
well when used to search for ground states for this Li-P-S system.
References
[1] N. Kamaya, et al., Nat. Mater. 10 (2011) 682-686.
[2] Modern Methods of Crystal Structure Prediction, ed. A. R.
Oganov, Wiley, 2011.
[3] G. Kresse and J. Furthmüller, Phys. Rev. B: Condens. Matter,
1996, 54, 11169-11186.
[4] G. Kresse and J. Furthmüller, Comput. Mater. Sci., 1996, 6, 15-
50.
PA30
Thermodynamic assessment of the Fe-RE (RE= Dy, Gd, Tb, Lu)
binary systems
Xiaolong Chen1, Jiang Wang1,2*, Mmaohua Rong1,2, Gguanghui
Rao1,2, Huaiying Zhou1,2
1
School of Material Science and Engineering, Guilin University of
Electronic Technology, Guilin, 541004, P.R. China
2
Guangxi Key Laboratory of Information Materials, Guilin
University of Electronic Technology, Guilin, 541004, P.R. China
E-mail: waj124@guet.edu.cn, wangjiang158@163.com
Nd-Fe-B permanent magnets with excellent comprehensive mag-
netic properties have been used in many industrial applications such as
hard disk, electric vehicle and wind power [1,2]. The Nd2Fe14B-based
magnets with heavy rare earth elements (e.g. Dy, Tb) have much better
temperature stability, higher energy product and coercivity [3,4]. In
order to better understand the mechanism of the Nd-Fe-B permanent
magnets with heavy rare earth elements, the investigation on the phase
relations and phase diagrams of RE-Fe-B systems are necessary. As the
key sub-binary systems in the RE-Fe-B ternary systems, the Fe-RE
binary systems should be studied firstly.
In this work, based on the critical review of the reported experi-
mental phase equilibria data and thermodynamic data [5], the Fe-RE
(RE= Dy, Gd, Tb, Lu) binary systems were assessed using the CALPHAD
method [6]. The self-consistent thermodynamic parameters obtained
finally to describe the Gibbs energies of various phases in the Fe-RE
binary systems can be used to reproduce well the reported phase
equilibria and thermodynamic data, which is indispensable to develop
the thermodynamic database of the multi-component RE-Fe-B perma-
nent magnetic materials.
References
[1] N. Poudyal, J.P. Liu, J. Phys. Appl. Phys. 46 (2013) 043001.
[2] O. Gutfleisch, M.A. Willard, E. Bruck, C.H. Chen, S.G. Sankar,
J.P. Liu, Adv. Mater. 23 (2011) 821-842.
[3] Z.H. Hu, F.Z. Lian, M.G. Zhu, W. Li, J. Magn. Magn. Mater., 320
(2008) 1735-1738.
36
Calphad xxx (xxxx) xxx–xxx
[4] A. Chrobak, G. Ziółkowski, N. Randrianantoandro, J. Klimontko,
D. Chrobak, K. Prusik, J. Rak, Acta Mater. 98 (2015) 318-326.
[5] M. Ivanov, V. Berezutski, N. Usenko, N. Kotova, Int. J. Mater.
Res. 103 (2012) 1-9.
[6] H.L. Lukas, S.G. Fries, B. Sundman, Computational
Thermodynamics: The Calphad Method Cambridge University Press,
2007.
Acknowledgements
This work was supported by National Basic Foundation of China
(Grant No. 2014CB643703), Guangxi Natural Science Foundation
(Grant Nos. 2014GXNSFBA118235, 2013GXNSFCA019017,
2012GXNSFGA060002) and National Natural Science Foundation of
China (Grant No. 51461013).
PA31
Thermodynamic calculation of the Ce/Pr-Fe-B ternary systems
Jiang Wang1, 2*, Taili Chen1, Maohua Rong1, 2, Guanghui Rao1, 2,
Huaiying Zhou1, 2
1
School of Material Science and Engineering, Guilin University of
Electronic Technology, Guilin, 541004, P.R. China
2
Guangxi Key Laboratory of Information Materials, Guilin
University of Electronic Technology, Guilin, 541004, P.R. China
E-mail:waj124@guet.edu.cn,wangjiang158@163.com
Nd2Fe14B-based sintered permanent magnets with high energy
products are still major practical obstacles in the application of wind
power generators [1-2], due to the relatively low intrinsic coercivity
and low operating temperature of Nd-Fe-B magnets. The most effective
solution of the improvement of the coercivity is the addition of ex-
pensive heavy rare earth elements (e.g. Dy, Tb) to Nd2Fe14B-based
magnets. On the other hand, in order to the balance utilization of the
rare earth elements, the effect of the light rare earth elements (e.g. La,
Ce, Pr) on the magnetic properties of Nd-Fe-B magnets is also in-
vestigated [3-6]. Phase equilibria and thermodynamic properties of the
related RE-Fe-B ternary systems are necessary to understand the re-
lationships among composition, crystal structure, phase transformation
and magnetic properties of magnets.
In this work, based on the critical review of the sub-binary systems
(e.g. Fe-Ce, Fe-Pr) in the Ce/Pr-Fe-B ternary systems, thermodynamic
calculations of the Ce-Fe-B and Pr-Fe-B ternary systems were performed
using the CALPHAD method [7] combined with the experimental in-
formation. Self-consistent thermodynamic parameters to describe the
Gibbs energies of various phases in the Ce/Pr-Fe-B ternary systems were
obtained. The liquidus projection and several vertical sections of the
Ce/Pr-Fe-B ternary systems were calculated, which are in reasonable
agreement with the experimental data.
References
[1] N. Poudyal, J.P. Liu, J. Phys. Appl. Phys. 46 (2013) 043001.
[2] K. Loëwe, C. Brombacher, M. Katterb, O. Gutfleisch, Acta.
Mater. 83 (2015) 248-255.
[3] A.K. Pathak, M. Khan, K.A. Gschneidner , R.W. Mccallum, L.
Zhou, K.W. Sun, K.W. Dennis, C. Zhou, F.E. Pinkerton, M.J. Kramer,
V.K. Pecharsky, Adv. Mater. 27 (2015) 2663-2667.
[4] M.G. Zhu, W. Li, J.D. Wang, L.Y. Zheng, Y.F. Li, K. Zhang, H.B.
Feng, T. Liu, IEEE Trans. Magn. 50 (2014) 1-4.
[5] M. Zhang, Z.B. Li, B.G. Shen, F.X. Xu, J.R. Sun, J. Alloys Compd.
651 (2015) 144-148.
[6] K. Pei, X. Zhang, M. Lin, A. Yan, J. Magn. Magn. Mater. 398
(2016) 96-100.
[7] H.L. Lukas, S.G. Fries, B. Sundman, Computational
Thermodynamics: The Calphad Method Cambridge University Press,
2007.
Acknowledgements
This work was supported by National Basic Foundation of China
(Grant No. 2014CB643703), Guangxi Natural Science Foundation
(Grant Nos. 2014GXNSFBA118235, 2013GXNSFCA019017,

2012GXNSFGA060002) and National Natural Science Foundation of
China (Grant No. 51461013).
PA32
Experimental determination of the Nd-Mn-Ge/Si isothermal
sections at 673 K
Shidong Lin1, Jiang Wang1,2*, Maohua Rong1, 2, Gguanghui Rao1,2,
Huaiying Zhou1,2
1
School of Material Science and Engineering, Guilin University of
Electronic Technology, Guilin, 541004, P.R. China
2 the quasi-harmonic approximation to estimate the temperature depen-
Guangxi Key Laboratory of Information Materials, Guilin
University of Electronic Technology, Guilin, 541004, P.R. China
E-mail:waj124@guet.edu.cn,wangjiang158@163.com
The rare-earth (RE)-transition metal compounds in the RE-Mn-X
(X= Ge, Si, Sn etc.) system have been investigated because of their
interesting magnetic properties, resulting from the interesting interplay
between the 3d and 4f magnetism and the strong dependence of the
magnitude of the Mn moment and the magnetic state of the Mn sub-
lattice on the Mn-Mn interatomic distances [1,2]. For example, the
intermetallic compounds REMn2X2 shows magnetocaloric effect and
REMn6X6 compounds have magnetoresistive properties, while REMnX
compounds shows magnetoelasticity [3-5]. Information of phase equi-
libria and crystal structures of stable intermetallic compounds in the
RE-Mn-X systems is contributes to understand the relationships among
composition, crystal structure, phase transformation and physical
properties.
In this work, the Nd-Mn-Ge and Nd-Mn-Si alloy samples annealed at
673 K were investigated by means of X-ray diffraction (XRD) and
scanning electron microscopy (SEM) equipped with energy dispersive
X-ray spectroscopy (EDS). Based on the experimental results, phase
relations of the Nd-Mn-Ge and Nd-Mn-Si ternary systems at 673 K were
determined.
References
[1] S. Gupta, K.G. Suresh, J. Alloys Comp. 618 (2015) 562-606.
[2] J. L. Wang, L. Caron, S. J. Campbell, S. J. Kennedy, M. Hofmann,
Z. X.Cheng, M. F. Md Din, A. J. Studer, E. Brück, S. X. Dou, Phys. Rev.
Lett. 110 (2013) 217-211.
[3] J.L. Wang, S.J. Kennedy, S.J. Campbell, M. Hofmann, S.X. Dou,
Phys. Rev. B 87 (2013) 104401.
[4] Y.Y. Gong, L. Zhang, Q.Q. Cao, D.H. Wang, Y.W. Du, J. Alloys
Comp. 628 (2015) 146-150.
[5] P. Lemoine, A. Vernire, J.F. Marêché, B. Malaman, J. Alloys
Compd. 508 (2010) 9-13.
Acknowledgements
This work was supported by National Natural Science Foundation of
China (Grant No. 51461013), National Basic Foundation of China (Grant
No. 2014CB643703) and Guangxi Natural Science Foundation (Grant Nos.
2014GXNSFBA118235, 2013GXNSFCA019017,2012GXNSFGA060002).
PA33
Thermodynamic Assessment of Ag-Cu-Se System
Zhi Li1, Jianyun Shen2, Chris Muzzillo, Shun-Li Shang3, Po-Hsin
Liao1, Zi-Kui Liu3, and Tim Anderson1
1 Sn is a common additional element in Zr-alloys used as nuclear
University of Florida, Gainesville, Florida, USA
2 cladding materials. It is found that the stabilities of the binary com-
General Research Institute for Nonferrous Metals, Beijing 100088,
PR China
3 modynamic models mainly based on phase equilibrium data.
The Pennsylvania State University, University Park, PA 16802,
United States
The chalcopyrite alloy Cu(In,Ga)Se2 has received tremendous suc-
cess as an absorber for thin film PV devices, demonstrating the highest
efficiency of any polycrystalline thin film material [1]. The absorber
composition of this champion cell, however, is not at the bandgap en-
ergy. This has motivated research on alloying Ag with Cu to increase
the bandgap energy while also increasing cell efficiency. In addition to
increasing the bandgap, researchers have begun investigating (AgxCu1-
37
Calphad xxx (xxxx) xxx–xxx
x)(InxGa1-x)Se2 alloys as a means to reduce processing temperature,
improve crystalline quality, improve wetting, and to attain greater
power conversion efficiencies [2, 3]. A thermodynamic description of
ACGISe system is of interest to better understand the absorber synthesis
process.
The Cu-Se system has been assessed by our group [4], while the Ag-
Cu system is reassessed based on the initial work of Subramanian and
Perepezko [5] but modified based on new experimental data, as well as
an assessment of the Ag-Cu-Ga-In system. [6] The first optimization of
the Ag-Se was performed as part of this study, requiring application of
dence of the Gibbs energy of formation of Ag2Se, for which there was
insufficient experimental information.
An assessed description of the ternary Ag-Cu-Se system was estab-
lished base on the binary assessments and available ternary experi-
mental data. [3] Similar to estimation for Ag2Se, the temperature de-
pendence of the Gibbs energy of formation of AgCuSe was predicted by
quatsi-harmonic aproximation. The calculated ternary phase diagram
was compared with the experimental equilibrium results. In addition,
the solid phase relation of pseudo-binary Ag2Se-Cu2Se system was in-
vestigated by annealing a stacked Ag2Se/Cu2Se layer. [7]
References
[1] P. Jackson, D. Hariskos, R. Wuerz, O. Kiowski, A. Bauer, T. M.
Friedlmeier, et al., "Properties of Cu(In,Ga)Se2 solar cells with new
record efficiencies up to 21.7%," physica status solidi (RRL) – Rapid
Research Letters, vol. in press, 2014.
[2] J. Boyle, G. Hanket, and W. Shafarman, "Optical and quantum
efficiency analysis of (Ag,Cu)(In,Ga)Se2 absorber layers," in
Photovoltaic Specialists Conference (PVSC), 2009 34th IEEE, 2009, pp.
001349-001354.
[3] Y. Tauchi, K. Kim, H. Park, and W. Shafarman, "Characterization
of (AgCu)(InGa)Se2 absorber layer fabricated by a selenization process
from metal precursor," IEEE Journal of Photovoltaics, vol. 3, pp. 467-
471, 2013.
[4] J. Y. Shen, W. K. Kim, C.-H. Chang, S. J. Wilson, and T. J.
Anderson, "Thermodynamic optimization of the Cu-Se binary system,"
in preparation, 2016.
[5] P. Subramanian and J. Perepezko, "The Ag-Cu (silver-copper)
system," Journal of Phase Equilibria, vol. 14, pp. 62-75, 1993.
[6] C. P. Muzzillo, "Chalcopyrites for Solar Cells: Chemical Vapor
Deposition, Selenization, and Alloying," PhD, Chemical Engineering,
University of Florida, 2015.
[7] L. Chen and W. Shafarman, "Ag content induced secondary
phase formation in (Ag,Cu)(In,Ga)Se2 thin film grown by three-sttage
co-evaporation," in preparation, 2016.
PA34
First Principle Study on Zr-Sn Thermodynamic Model
Jianyun Shen1,2, Zhi Li2, Xuankai Feng3, Jiaqing Pen1
1
General Research Institute for Nonferrous Metals, Beijing 100088,
PR China
2
University of Florida, Gainesville, Florida, USA
3
Shanghai University, Shanghai 200444, PR China
pounds in Sn-Zr system maybe over estimated in the published ther-
Information concerning thermodynamic properties of this system is
very limited. It leads difficulties to establish thermodynamic models of
the ternary systems including both Sn and Zr.
A series of G(T) expressions is obtained by phonon calculations
based on first principles. Thermodynamic model for the Sn-Zr system is
re-established by combining the first principle calculation and the
available experimental information. Most G(T) expressions obtained
from phonon calculation for line compounds (Zr4Sn and ZrSn2) and

end-members in sub-lattice models for non-stoichiometric compounds
(Zr5Sn3_ƞ) match well with the available experimental data in the new
Sn-Zr thermodynamic model.
PB1
Application of Al2O3-Y2O3-Tl2O3 long range order for anti-
corrosion coatings
Oleg Chizhko1
1 2
Association of German Engineers, Foreign Department, Post-Box
88, Cherkessk, Russia, e-mail: Oleg.Chizhko@alumni.uni-karlsruhe.de
The left figure is the surface of the standard Gibbs energies for the
stable phases, which were produced from the oxide components. The
influence of Tl2O3 on formation of YAlO3 is confirmed with existence of
the YTl2Al3O9 compound. The deep area corresponds to the variation
of content of the oxide conglomerate. The two and three phase fields of
the right figure are the projections of the Gibbs energy diagram. They
were calculated with minimization of chemical potentials for the stoi-
chiometric reactions.
In the following abstract, we are occupied with crystallization of
sub-lattices from ionic liquids of combustion ashes, with substitution of
oxide composites in solid solutions [1-2], with phase transformations,
with measurements of excess energies after formation of new com-
pounds [3], and with thermal treatment of materials for prevailing of
mono-crystalline structure. The last task seems to be complex because
the chemically stable substances have higher heat conductivity and we
conserve a content of temperature phases with rapid cooling. There is a
danger of becoming of amorphous bodies with disordered defects. In
the case of increased enthalpy, we eliminate short range and the size of
grains stays bigger.
For prediction of properties of anti-corrosion protectors, the data-
sets of experimental results were deposited in correspondence with the
conditions [4]:
- Data Quality for thermodynamic Properties of pure Substances;
- Selection and Precision of comprehensive Values for thermo-
chemical Functions;
- Standardization of Databases for Treatment of experimental
Results;
- analytical Presentation of Tables and Visualization of Phase
Diagrams;
- Commercialization of Program Software and Data Management in
Internet;
- Information Society and on-line operational Systems for
Simulation on Materials.
References
[1] H.J. Seifert et al., Journal of European Ceramic Society, 34
(2014) 3835-3840.
[2] Bo Sundman et al., Journal of American Ceramic Society, 88
(2005) 2544-2551.
[3] Zi-Kui Liu et al., Calphad, 48 (2015) 113-122.
[4] Tetsuo Mohri, Shuichi Iwata, Ying Chen, Calphad, 26 (2002)
583-589.
38
Calphad xxx (xxxx) xxx–xxx
PB2
High-throughput Investigation of Diffusion and Micro-
Mechanical Properties over Multicomponent Arrays in Co-Al-V
System
Chuanyun Wang1, Bin Tang2, Guanglong Xu1, Yi Chen1, Yuwen
1,3
Cui
1
Computational Alloy Design Group, IMDEA Materials Institute,
Getafe (Madrid) 28906, Spain
State Key Laboratory of Solidification Processing, Northwestern
Polytechnical University, Xi’an 710072, China
3
Institute for Advanced Metallic Materials & School of Materials
Science and Engineering, Nanjing Tech University, Nanjing 210009,
China
High-throughput screening technique, enabling effective and reli-
able studies of phase diagram and composition-structure-properties
relationship of bulk materials, has accelerated the discovery of ad-
vanced materials and the research of properties controlling [1-2]. In
current work, interdiffusion behaviors and mechanical variations of Co-
Al-V alloy system were fast screened by the combination of quantitative
diffusion-couple technique and nanoindentation approach over the ar-
rays of composition. Extensive inter/impurity diffusion coefficients
were reliably extracted for the fcc Co-Al-V ternary alloys via Whittle-
Green and generalized Hall methods respectively, based on the EPMA
composition profile represented by an errorfunction expansion. The
composition and temperature dependences of the calculated diffusion
coefficients were detailed in view of mutual consistency of all available
diffusion data, and a consequence of interpolation enables a mapping of
diffusion coefficients of technologically important for the new genera-
tion Co-based high-temperature alloys [3-4]. A quantitative description
of variation in mechanical properties of Co-Al-V ternary alloys with
composition was also presented.
References
[1]. Xiang X-D, Sun X, Briceno.G, et al. Science, 268 (1995) 1738-
1740.
[2]. Zhao J-C. Progress in Materials Science, 51(2006) 557-631.
[3]. Zhou G, Tang J, Zhou Y, et al. Journal of Alloys and
Compounds, 602 (2014) 49-52.
[4]. Liu X, Zhu Y, Yu Y, et al. Journal of Alloys and Compounds, 509
(2011) 5740-5747.
PB3
High-throughput determinationof the composition-dependent
interdiffusivity matricesin Ni-rich fcc Ni–Al–X(Rh, Ta, W, Re and
Ir) alloys at elevated temperatures
Juan Chen, Jing Zhong, Weimin Chen, Yong Du, Lijun Zhang
State Key Laboratory of Powder Metallurgy, Central South
University, Changsha, 410083, China

Owing excellent high-temperature mechanical properties and high
resistance to creep and fatigue at elevated temperatures, Ni-based su-
peralloys are widely used in both aviation and land-based gas turbine
environments. Knowledge of both thermodynamic and diffusion char-
acteristics in Ni-based superalloys is of critical importance in quanti-
tative description of various materials processes. In order to establish
the accurate atomic mobility of Ni-based superalloys, a large amount of
reasonable experimental data [1, 2] is needed. However, few experi-
mental diffusivities exist in the key ternary systems, like Ni–Al–X (X =
Rh, Ta, W, Re and Ir) systems, which needs to be remediedurgently.
Based on the recently developed pragmatic numerical inverse
method [3], high-throughput determination of the interdiffusivities in
Ni-rich fcc Ni–Al–X (X = Rh, Ta, W, Re and Ir) alloys at 1473,1523 and
1573K was performed in the present work.Thetypical compositionde-
pendent interdiffusivity surfaces in ternary Ni-Al-Ta system at three
temperatures are demonstrated in Fig. 1. The reliability of the inter-
diffusivities determined by the pragmatic numerical inverse method
was first validated by reproducing the composition profiles for each
diffusion couple. In order to further validate their reliability, a direct
comparison between the interdiffusivities due to the pragmatic nu-
merical inverse method and those by the traditional Matano–Kirkaldy
method was then made. Based on the determined temperature-depen-
dent interdiffusivity surfaces at different temperatures, the activation
energies for the main interdiffusivities were evaluated, from which the
activation energy surface over the investigated composition range was
then constructed.
Acknowledgments
The financial support from the National Natural Science Foundation
for Youth of China (Grant No. 51301208), the National Natural Science
Foundation of China (Grant Nos. 51474239 and51429101).
References
[1] J. Chen, et al., CALPHAD 50 (2015) 118–125.
[2] J. Chen,et al.,J.Alloys Compds.657(2016) 457–463.
[3]W.M. Chen, et al., Scripta Mater. 90–91 (2014)53–56.
PB4
Construction of atomic mobility database for fccphase in the
39
Calphad xxx (xxxx) xxx–xxx
Ag-Cu-Sn-Sb-BiPbsolder system
Huixia Xu*, Weimin Chen, Yong Du, Lijun Zhang
State Key Laboratoryof Powder Metallurgy, Central South
University, Changsha, Hunan 410083, PR China
*Corresponding author. E-mail address:huixiaxu923@csu.edu.cn
By integrating the diffusion couple technique, EPMA measurement
and the newly-developed pragmatic numerical inverse method [1],
high-throughput determination of the interdiffusivity matrixes along
the entire diffusion paths of five fcc-phase Cu-Ag-Sn diffusion couples
was firstly performed. The reliability of the obtained interdiffusivities
was then verified by comparing with the results obtained by the tra-
ditional Matano-Kirkaldy method [2]. Subsequently, based on the ex-
perimental data obtained in the present work and in the literature to-
gether with the reliable thermodynamic database [3], the atomic
mobility database for fcc phase in the Ag-Cu-Sn-Sb-Bi-Pb solder system
was constructed via DICTRA software. The reliability of the established
atomic database was validated by comprehensively comparing various
diffusion coefficients of sub-binary and ternary systems with the ex-
perimental data. In order to further validate the reliability of the pre-
sent atomic mobility database, the concentration profiles of different
single fcc-phase diffusion couples were well reproduced. The good
agreement between the calculated/simulated and the experimental data
indicates the high quality of the present atomic mobility database. It is
expected the presently developed kinetic database can be used for fu-
ther investigations on the diffusion controled phenomenon in the solder
systems.
Acknowledgments
The financial support from the National Natural Science Foundation
for Youth of China (Grant No. 51301208) and the National Natural
Science Foundation of China (Grant Nos. 51474239, 51531009) is
greatly acknowledged.
References
[1] WeiminChen et al., Scripta Materialia.90–91 (2014) 53–56.
[2] HuixiaXuet al., Journal of Alloys and Compounds. 644 (2015)
687-693.
[3] U. Kattner, Solder Database (solder. tdb) available from NIST
(http://www.metallurgy.nist.gov/phase/solder/solder.html.).
PB5
Difference in transformation kinetics and microstructural
evolution between ferrite and austenite transformations in
medium manganese steel
Nobuo Nakada1, Kouji Mizutani2, Toshihiro Tsuchiyama3, Setsuo
Takaki3, Masanori Kajihara1
1
Department of Materials Science and Engineering, Tokyo Institute
of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama, Kanagawa,
226-8503 JAPAN
2
Graduate student, Department of Materials Science and
Engineering, Kyushu University, 774 Moto-oka, Nishi-ku, Fukuoka 819-
0395, JAPAN(Now at Maruichi Steel Tube Ltd.)
3
Department of Materials Science and Engineering, Kyushu
University, 744 Moto-oka, Nishi-ku, Fukuoka 819-0395, JAPAN
Recently, medium-Mn steel containing 5-8 mass% Mn has been paid

attention as one of new generation high strength automotive steels [1].
Since the medium-Mn steel never has an austenitic single-phase struc-
ture at ambient temperature due to insufficient Mn content, the mi-
crostructure of this steel is usually controlled to be a α+γ dual-phase
structure through a heat treatment. In this study, the transformation
kinetics and microstructural evolution were compared between γ→α
and α’→γ transformations at T0 temperature in a 0.1%C-5%Mn steel to
clarify which is more appropriate to obtain thermally stable austenite as
a second phase in medium-Mn steel.
After the first austenitization at 1173 K for 1.8 ks, 0.1%C-5%Mn
steel was subjected to two different heat-treatment routes. One was
isothermal holding at 909 K for up to 50 hours after reaustenitization to
form ferrite within an austenite matrix (γ→α transformation). The
other was intercritical annealing at the same temperature to form
austenite within a martentite matrix (α’→γ transformation). Since the
temperature of 909 K corresponds to transition temperature T0 of this
material, the total driving force for the transformation is the same be-
tween γ→α and α’→γ transformations. However, it is worth to note that
there is significant difference in transformation kinetics between them
as shown in Fig.1. The γ→α transformation (a) is such a slow reaction
that very littele ferrite phase forms even after a lengthly annealing time
of 50 hours. On the other hand, the α’→γ transformation (b) is a re-
laticely fast reaction, and thus the asutenite fraction rapidly increased
and eventually reaches the equilibrium value. In the CALPHAD
meeting, we will discuss the difference in transformation kinetics based
on local ecuilibrium theory using DICTRA simulation and then point
out some advantages in kinetics of α’→γ transformation in medium-Mn
steel.
Reference
[1] H.N. Han, C.S.Oh, G. Kim and O. Kwon: Mat. Sci. Eng. A,
499(2009), 462.
PB6
Estimation of softening behavior of BF burden materials using
computational phase diagrams for multicomponent systems
Eetu-Pekka Heikkinen1, Antti Kemppainen1, Mikko Iljana1, Olli
Mattila2, Timo Paananen2, Ko-Ichiro Ohno3, Kazuya Kunitomo3,
Takayuki Maeda3, Timo Fabritius1
1
University of Oulu, Process metallurgy research group, PO Box
4300, FI-90014 University of Oulu, Finland.
2
SSAB Europe, Raahe Steelworks, PO Box 93, FI-92101 Raahe,
Finland.
3
Kyushu University, Department of Materials Science &
Engineering, Moto-oka 744, Nishi-ku, Fukuoka 819-0395, Japan.
One of the first and the most obvious uses of phase diagrams has
been to estimate the softening and melting behavior of different
40
Calphad xxx (xxxx) xxx–xxx
materials. Current computational thermodynamics (CTD) software to-
gether with thermodynamic databases make it possible to study the
behavior of different materials in various conditions with phase dia-
grams created for multicomponent systems. The purpose of this study
was to determine what are the possibilities to estimate the effect of
compositional changes on the softening behavior of blast furnace (BF)
burden materials using multicomponent phase diagrams computed with
a commercial CTD software (FactSage v. 6.4 & v. 7.0) and its databases.
Furthermore, a correlation between the computed phase diagrams and
gas permeability of the material bed was estimated.
The sample materials investigated in this study were acid and oli-
vine fluxed pellets. The softening behavior of these materials was stu-
died using two different experimental setups. In the first setup, the
materials were first pre-reduced using a blast furnace simulator (BFS; cf.
[1] for more detailed description) after which the softening behavior
was studied using a cohesive zone simulator (CZS; cf. [2] for more
detailed description). In the second setup, an Advanced reduction under
load -test (ARUL; cf. [3] for more detailed description) was used to
study the softening behavior and gas permeability in simulated BF-
conditions by measuring pressure drops through the material bed. The
results of these experiments were compared with the computed phase
diagrams.
According to the results, the estimation of the softening behavior of
the BF burden materials is possible using computational phase diagrams
computed for Ca-Fe-Mg-Si-O-systems. However, it was noticed that the
diagrams computed to illustrate the behavior of oxide systems in inert
atmosphere were not sufficiently accurate for practical purposes, since
the conditions inside the BF vary considerably as a function of location.
Hence, it was necessary to compute diagrams in which temperature as
well as partial pressure of oxygen were used as variables.
References
[1] Iljana M et al., ISIJ Int., 52(2012), 1257-1265.
[2] Kemppainen A et al., ISIJ Int., 55(2015), 2039-2046.
[3] Iljana M et al., Int. J. Min. Proc. 141(2015), 34-43.
PB7
The influence of Co and Ti elements on mechanical properties
for Ni-base superalloys
Young-Kwang Kim1, Hong-Kyu Kim2, Woo-Sang Jung3 and Byeong-
Joo Lee1
1
Department of Materials Science and Engineering, Pohang
University of Science and Technology (POSTECH), Pohang 790-784,
Republic of Korea
2
The 4th (Energetics and Defense Materials) R&D Institute – 3,
Agency for Defense Development (ADD), Daejeon 305-600, Republic of
Korea
3
High Temperature Energy Materials Research Center, Korea
Institute of Science and Technology, Seoul 136-791, Republic of Korea
The influences of Co and Ti atoms on mechanical properties for Ni-
base superalloys have been investigated using atomistic simulation
based on (semi-)empirical interatomic potential. An interatomic po-
tential for Ni-Al-Co ternary system [1] is now available. However, since
an interatomic potential for Ni-Al-Ti ternary system is not available, the
first done in the present work is to develop an interatomic potential for
Ni-Al-Ti ternary system. The potential can describe the phase trans-
formation between γ (fcc) and γ′ (L12 Ni3Al) phases and the site pre-
ference of Ti atoms in the γ′ phase correctly. By using atomistic simu-
lation based on these interatomic potentials, the second done in the
present work is to investigate the atomic-scale behaviors of Co and Ti
atoms: segregation to stacking faults, interface and grain boundaries,
and the change of lattice mismatch, interfacial energy and antiphase
boundary energy. Based on the present results, we discuss to clarify the
effects of Co and Ti atoms on mechanical properties for Ni-base su-
peralloys.
Reference

[1] Y-K Kim et al., Model. Simul. Mater. Sci. Eng., 23 (2015)
055004.
PB8
Molecular Dynamic Modeling of Natural Rubber (NR)
Myung Shin Ryu1, Hyoung Gyu Kim1,2, Hyuck Mo Lee1,*
1 mance, the CALPHAD methodology was applied to gain various stra-
Department of Materials Science and Engineering, Korea
Advanced Institute of Science and Technology, 291 Daehak-ro,
Yuseong-gu, Daejeon 305-701, Republic of Korea
2 loys were observed to be significantly out-of-equilibrium and highly
Material Research Team 1, Hankook Tire Co., Ltd., 112
Gajeongbuk-ro, Yuseong-gu, Daejeon 305-725, Republic of Korea *e-
mail: hmlee@kaist.ac.kr
The car industry has been expanding tremendously since the 20th
century; while there were 50 million vehicles worldwide in 1950, but at
present over 800 million vehicles and by 2050 1500million vehicles are
expected to be running. The massive expansion of vehicle usage causes
car accidents with 50 million severely injured people every year. Since
most of car accidents occur during driving, the technologies for en-
hancing driving stability of the vehicle are actively being developed.
Among many aspects that contribute to driving stability, the most im-
portant one is the stability of tires. 50% of tires for vehicles are made of
various types of natural rubber (NR) with added carbon black filler to
increase viscoelasticity. While driving stability of tire is measured by
numerous criteria including balance, cornering force, dry & wet trac-
tion, rolling resistance and stopping distance, in the material scientific
point of view these criteria can be predicted by Young’s modulus, glass
transition temperature and diffusivity of fillers.
The simulation on polymer that has a very large amount of atoms in
the system commonly uses the bead-spring model to describe the vis-
coelasticity. We fitted the parameters of the force field in the system of
bead-spring simulation, since they are used in reduced units. And, we
fitted the parameters of polymer-polymer interaction by using the
density and glass transition temperature of natural rubber to solve the
issues mentioned above. Furthermore, we fitted the parameters of
polymer-filler interaction by using the diffusion coefficient of fillers in
the natural rubber. Finally, we compared the computed stress-strain
curve in uniaxial elongation with the experimental data of the Hankook
Tire Co.
Keyword: Natural Rubber, Carbon black Filler, Molecular dynamic
simulation, Tire, Bead-Spring simulation
PB9
CALPHAD assisted design of metal-diamond composites for
selective laser melting
Christian Leinenbach1, Xiaoshuang Li1,3, Christoph Kenel1,3,
Adriaan B. Spierings2, Konrad Wegener2,3
1 applications of Calphad approach in the design of HEAs will be dis-
Empa, Swiss Federal Laboratories for Materials Science and
Technology,Dübendorf, Switzerland
2
Inspire AG -Innovation Center for Additive Manufacturing
Switzerland, St. Gallen, Switzerland
3
ETH Zurich, Institute of Machine Tools and Manufacturing, Zurich,
Switzerland
Selective laser melting (SLM) as one of the advanced beam based
additive manufacturing (AM) processes is a promising candidate for
fabrication of novel metal matrix composites (MMC) with tailored
properties. They allow building components with complex 3D geome-
tries layer by layer. The base material in a small melt pool rapidly
consolidates at a considerably high solidification rate allowing for the
manufacture of composites containing metastable materials like dia-
mond which tend to decompose in conventional casting or sintering
processes. At the same time, these conditions may lead to complex out-
of-equilibrium microstructures, pronounced element segregation and
crack formation in the bulk alloy. Despite AM of metallic materials is a
commonly established processing technology, the materials science in
AM is only at its infancy.
41
Calphad xxx (xxxx) xxx–xxx
In a recent work, we could show that during SLM processing CuSnTi
brazing alloys reinforced with diamond particles using appropriate
processing parameters, a majority of the diamond particles survived
without graphitization and were well bonded with the matrix [1]. To
further optimize the matrix alloy in terms of chemical composition,
microstructure etc. for a better processability and material perfor-
tegies for alloy design, especially complex ternary or even quaternary
systems. For the same composition, the microstructures of CuSnTi al-
depend on the cooling rates, which were characterized mainly using
scanning electron microscopy (SEM), X-ray diffraction (XRD) techni-
ques.
Reference
[1] A.B. Spierings et al., Rapid Prototyping Journal 21(2) (2015)
130-136
PB10
Design of High Entropy Alloys: The Calphad Approach
Chuan Zhang1, Fan Zhang1, Shuanglin Chen1, Weisheng Cao1, Jun
Zhu1, Haoyan Diao2, Rui Feng2, and Peter K. Liaw2
1
CompuTherm LLC, 437 S. Yellowstone Dr., Suite 217, Madison, WI
53719, USA
2
Department of Materials Science and Engineering, the University
of Tennessee, Knoxville, TN 37996, USA
The novel concept of high entropy alloy (HEAs) has revolutionized
the traditional alloy design that is usually based on one or, at most two
key elements. The so-called HEAs contain multi-principal components
(5‫ )ﭪ‬in equal or near-equal atomic ratios and form a simple solid so-
lution structure. This concept greatly broadens the compositions of
alloy design, yet, arbitrary mixing of elements in the period table does
not, at least not always, render formation of solid solution but com-
posite structures. Identifying alloy compositions that form HEAs in the
multi-component systems is costly and time-consuming solely by ex-
perimental methods, while the Calphad approach can play a significant
role in the design of HEAs.
In this talk, the rules of developing HEAs with simple micro-
structures will be elucidated using the Calphad approach. Comparisons
were made between thermodynamic calculations and experimental re-
sults for a few systems, such as Al-Co-Cr-Fe-Ni and Co-Cr-Fe-Mn-Ni. The
calculated results, such as primary solidified phases, fraction of each
stable phase at different given alloy compositions, will be compared
with the published experimental observations. In addition, coupling
thermodynamic database with the molar volume database, one can also
plot the density contour diagrams in combination with phase diagrams
to guide the design of light-weight HEAs. Finally, the challenges for the
cussed.
PB 11
Thermodynamics and kinetics of oxide glass/metal interfacial
interactions
Aniekan Ukpong1, Nicolas Nowak2, Glenn Jones1, and Jon Booth2
1
Johnson Matthey Technology Centre, Room B161, Building 22,
Council for Scientific and Industrial Research, Pretoria, South Africa
2
Johnson Matthey Technology Centre, Blounts Court, Sonning
Common, Reading, Oxfordshire RG4 9NY, United Kingdom
Interfaces occur in a number of important applications of materials.
Therefore, the development of a fundamental understanding of their
formation and temperature-time evolution is essential for implementing
intelligent designs and optimization of associated industrial processes.
In this talk, a semi-empirical thermodynamic method for studying in-
terfacial reactions is presented. Thermochemical information are de-
rived from CALPHAD modelling of associated phases and used topredict
possible diffusion paths across the oxide glass/active metal interface,

and mechanisms for interfacial reactivity are proposed. Results are
presented to characterize the possible interface reactions in selected
glass/active-metal systems. Equilibrium calculations of activity dia-
grams are also used to understand the complex reactions that occur at
the interface during the active metal brazing of silica-based glasses. It is
demonstrated that the relative proportion of the base metal component
at the interface determines the nature of the thermochemical interac-
tions during joining operations.
PB12
Kinetics of Solid-state Reactive Diffusion between Sn-base
Alloys and Conductor Metals
Masanori Kajihara and Misako Nakayama
Tokyo Institute of Technology, Nagatsuta 4259, Midori-ku,
Yokohama 226-8502, Japan
In the electronics industry, various Sn-base alloys are widely used as
Pb-free solders. They are Sn−Ag, Sn−Cu, Sn−Ni, Sn−Zn, Sn−Bi al-
loys, etc. If such a Sn-base solder is interconnected with a conductor
metal like Cu, Cu−Sn compounds are produced at the interconnection
owing to reactive diffusion between the solder and the conductor
during soldering and then gradually grow during energization heating
at solid-state temperatures. Since the Cu−Sn compounds are brittle and
possess high electrical resistivities, their growth deteriorates the me-
chanical and electrical properties of the interconnection. The alloying
component in the solder may influence the growth behavior of the
compound. However, reliable information on the influence is rather
limited. To obtain such information, kinetics of solid-state reactive
diffusion between various Sn-base alloys and conductor metals is ex-
perimentally studied by a metallographical technique in our research
group. Among these studies, attention was focused on the reactive
diffusion between binary Sn−Ni alloys and pure Cu in the present
work.
For the experiment, sandwich (Sn−Ni)/Cu/(Sn−Ni) diffusion
couples with Ni concentrations of y = 0.01 and 0.03 were isothermally
annealed in the temperature range of 433−473 K for various periods
up to 1152 h, where y is the mol fraction of Ni. After annealing, a
compound layer consisting of Cu6Sn5 and Cu3Sn was recognized be-
tween the Sn−Ni alloy and the Cu specimen in the diffusion couple.
Here, the thickness of the Cu3Sn layer is smaller than that of the Cu6Sn5
layer. The (Cu,Ni)6Sn5 grains were transformed from the Ni3Sn4 grains
in the Sn−Ni alloy in the neighborhood of the Cu6Sn5 layer, and then
adhered to the Cu6Sn5 layer. The overall growth of the compound layer
including the (Cu,Ni)6Sn5 grains is remarkably accelerated by the ad-
hesion, but that of the compound layer excluding the (Cu,Ni) 6Sn5
grains is slightly decelerated by the adhesion. The mean thickness of
each layer increases in proportion to a power function of the annealing
time. Since the exponent of the power function is equivalent to each
other between the Cu6Sn5 and Cu3Sn layers, the same rate-controlling
process works for both layers. For annealing at 433−473 K, the ratio
between the thicknesses of the Cu6Sn5 and Cu3Sn layers is hardly af-
fected by the addition of Ni into Sn up to y = 0.03.
PB13
Thermo-kinetics simulation of non-parabolic solidification be-
haviors in liquidphase bonding (TLP) of Ni-based alloys
Kewu Bai1, Adele Lim1, Fern Lan Ng2, Tao Li2, Teck Leong Tan1 and
Dayou Pan2
1 [1] T. Nagase, M. Suzuki, T. Tanaka, Journal of alloys and com-
Institute of High performance Computing, 1 Fusionopolis Way,
#16-16 Connexis, Singapore 138632
2
Singapore Institute of Manufacturing Technology, 71 Nanyang
Drive, Singapore 638075
The transient liquid phase (TLP) bonding, also known as diffusion
brazing, is widely used as repairing technique in aerospace engine in-
dustry. In order to improve the yields and to decrease the operational
cost of the repair brazing process, a thermo-kinetic study on TLP
42
Calphad xxx (xxxx) xxx–xxx
process of Ni-based alloys is necessary. However, the conventional
models in the literature, based on the continuous diffusion in the base
metal without precipitations, fail to produce non-parabolic solidifica-
tion kinetics and the microstructures in the multi-component Ni-based
alloys. A model of TLP process describing the complex isothermal so-
lidification behavior in the brazing process is still lacking.
In this paper, the optical microscope and scanning electron micro-
scope (SEM) are used to examine the microstructures of the TLP process
of Ni-based alloys, the diffusion model parameters of boron in NiCr
binary alloys is optimized by moving boundary model in the DICTRA
software. Using the optimized model parameters, we simulated the
isothermal solidification kinetics of TLP process AWS A5.8 BNi-9
(filler)/Inconel 718 (multi-component) using different homogenization
models. We found that the non-parabolic solidification kinetics existed
in the AWS A5.8 BNi-9/Inconel 718, which is consistent with our ex-
periment and literature data. The predicted isothermal solidification
rates for Inconel 718 at 1090 ºC are fast at the initial stage and lower at
the final stage of brazing process with the much shorter total solidifi-
cation time, which is also in an agreement with experiment data. We
further proposed that post homogenization at 1090ºC for 3500s will
eliminate boride phases formed in the joint thus increasing joint
strength.
Acknowledgements
The project is supported by the aerospace program of A-STAR
Singapore. Thermo-calc and DICTRA software from Sweden is used in
the simulation.
PB14
Alloy design and microstructure analysis of Fe-rich and Cu-rich
Fe-Cu-based immiscible alloys with an amorphous phase
T. Nagase1,2
1
Research Center for Ultra-High Voltage Electron Microscopy,
Osaka University, 7-1, Mihogaoka, Ibaraki, Osaka 567-0047, Japan
2
Division of Materials and Manufacturing Science, Graduate School
of Engineering, Osaka University, 2-1, Yamada-Oka, Suita, Osaka 565-
0871, Japan
The solidification process of immiscible alloys offers a unique op-
portunity in designing composites with spherical particles dispersed in
a matrix. The formation of an amorphous phase in the immiscible alloys
induces a decrease in the size of the spherical precipitates because of
the high-degree of undercooling during the nucleation of the liquid
minority phase in the form of spheres. Fe-based FeNb-B-Cu and Cu-
based Cu-Ag-La-Fe alloys were designed for a quaternary alloy system
that exhibits liquid-phase separation and an amorphous phase forma-
tion simultaneously. The alloy design [1] was accomplished using
empirical rules based on the combination map of the mixing enthalpy
(ΔHmix) for binary atomic pairs of the constituent elements in qua-
ternary alloy systems, a predicted quaternary phase diagram based on
ab-initio calculations, and thermodynamic calculations using FactSage.
The microstructure of Fe-based (Fe0.75Nb0.10B0.15)100-xCux and Cu-Ag-
based (Cu0.54Ag0.40La0.06)100-xFex alloys was investigated focusing on
the liquid phase separation behavior and amorphous-phase formation.
Acknowledgments
A part of this work was supported by the scientific grants from the
Japan Foundry Engineering Society (JFS) and the Kansai Research
Foundation for technology promotion (KRF).
Reference
pounds, 619 (2015) 267-274 (2015).
PB15
Diffusion behavior and Kirkendall void in interfacial region of
Fe/Ni-based alloy
Shohei Takekawa1, Ikuo Ohnuma2, Shun-ichi Tachibana3, Kaneharu
Okuda3.4, Toshihiro Ohmori4, Ryosuke Kainuma4

1
Graduate student, department of Material Science, Tohoku
University, Sendai, Japan
2
Computational Material Science Unit, National Institute for
Material Science (NIMS), Tsukuba, Japan
3
Steel research laboratory, JFE steel Co., Kawasaki, Japan
4
Department of Material Science, Tohoku University, Sendai, Japan
The use of more corrosive crude oil is proceeded in order to satisfy
recent oil demand, and it is required to heighten corrosion-resistance of
crude pipe. Ni-based alloys are widely used for high corrosion-re-
sistance materials. Especially, alloy 625 and alloy 825 with high Cr
composition are effective for corrosive oil well. On the other hand, the
cladding of the Ni-based alloys and steels is in the limelight for the
crude pipe because of high corrosion-resistance and low cost. The
cladding is usually carried out by the hot-rolling and the joined mate-
rials are annealed in the temperature range between 950 ˚C and 1150
˚C. In this process, the atomic diffusion is progressed in accordance with
the Fick’s first low, and Kirkendall voids are sometimes formed in the
vicinity of interface, when the diffusivities of the joined materials are so
different. Because the volume defects such as voids affect the me-
chanical and chemical properties, the formation of the Kirkendall voids
is one of the important issues to improve the bonding strength in the
cladding materials.
In this study, the diffusion behavior including the formation of
Kirkendall voids was studied by the diffusion couple (DC) technique
and the DICTRA simulation. Ni-based alloys; Ni-19wt.%Cr, Ni9wt.%
Mo, and pure Fe were employed instead of Alloy 625/825 and steels,
respectively, to simply analyze the basic diffusion behavior. Alloys were
bonded at 1000 ˚C with Thermo-mechanicalsimulator, and annealed at
1300 ˚C for 24hrs. Microstructure and compositions were analyzed by
FE-EPMA/WDS.
The penetration-concentration profiles experimentally obtained are
basically consistent with those predicted by DICTRA. In the Fe/Ni DC,
however, the profiles show many Kirkendall voids, deviated from the
calculated profiles only in the diffusion region with the voids as shown
43
Calphad xxx (xxxx) xxx–xxx
in Fig. 1. On the other hand, those in the Fe/Ni-Cr based alloy exhibit
neither the Kirkendall void nor the deviation from the DICTRA profiles.
PB16
Experimental Investigation and Computer Simulation of
Diffusion in Fe˗Mo and Fe˗Mn˗Mo
Alloys with Different Optimization Methods
Weisen Zheng1,2, John Ågren2, Lars Höglund2,3, Hao Wang1, Xiao-
Gang Lu1,4
1
School of Materials Science and Engineering, Shanghai University,
200444 Shanghai, P.R. China
2
Department of Materials Science and Engineering, KTH Royal
Institute of Technology, SE-100,44 Stockholm, Sweden
3
Thermo-Calc Software AB, Norra Stationsgatan 93, SE-113 64
Stockholm, Sweden
4
Materials Genome Institute, Shanghai University, 200444
Shanghai, P.R. China
In order to simulate the diffusional phase transformations involving
the fcc and bcc phases for microalloyed steels, the diffusion mobilities
for fcc and bcc Fe˗Mo and Fe˗Mn˗Mo alloys were experimentally in-
vestigated and critically assessed. The diffusion-couple technique was
employed to extract the interdiffusion coefficients in Fe˗Mo and
Fe˗Mn˗Mo alloys with the Sauer-Freise and Whittle-Green methods.
Based on the present experimental interdiffsivities, the mobility para-
meters for the fcc and bcc phases in the Fe˗Mo and Fe˗Mn˗Mo systems
were optimized using the DICTRA software [1]. This kind of optimi-
zation using the DICTRA software is referred to as the traditional
method in the present work. Meanwhile, a direct method was proposed
and utilized to fit mobilities to the diffusion profiles directly rather than
the diffusivities. The direct optimization method is based on the ap-
plication programming interface (TC-Toolbox for MATLAB) [1] for the
Thermo- Calc and DICTRA software. Through the programming inter-
face, thermodynamic and kinetic quantities can be retrieved from
Thermo-Calc and DICTRA as input to the MATLAB program. As the
direct method is based primarily on experimental diffusion profiles, it is
more suitable for the optimization of mobility interaction parameters. It
should be noted that experimental diffusivities can also be considered
in the direct method. This is an improvement of the work by Höglund.
The present MATLAB program can fit diffusion mobilities to experi-
mental diffusion profiles and diffusivities simultaneously. Without the
need of extracting interdiffusion coefficients, the direct method can
optimize mobility parameters in the multicomponent system using less
diffusion couple experiments. Because it is more difficult to determine
interdiffusion coefficients in multicomponent systems from just one
experimental diffusion profiles. Moreover, the direct method can ef-
fectively optimize the diffusion mobility using concentration profiles
from the dual-phase diffusion couple. The satisfactory description of the
diffusion behavior in the Fe˗Mo and Fe˗Mn˗Mo systems has confirmed
the reliability of the direct method. Particularly, the two sets of diffu-
sion mobilities obtained with both methods could simulate the diffusion
phenomenon between the fcc and bcc phases in the Fe˗Mo and
Fe˗Mn˗Mo systems successfully.
Reference
[1]J.-O. Andersson et al., CALPHAD, 26 (2002) 273-312.
PB17
Prediction of Martensite Start Temperature and Type of
Martensite
Won-Mi Choi, Byeong-Joo Lee
Department of Material Science and Engineering, Pohang University
of Science and Technology, Pohang 790-784, Korea
Steel properties are highly dependent on the type and amount of
martensite. Therefore, prediction of martensite start temperature (Ms
temperature) and the amount is important for designing steels.
Martensite starts forming when the temperature reaches the Ms

temperature during quenching. α’martensite (BCT) and ε-martensite
(HCP) is competitively transformed from austenite (γ, FCC) depending
on the chemical compositions and cooling conditions. The aspect of
competition is predictable by comparing the α’ and ε Ms temperatures.
The main factors affecting the Ms temperature are chemical composi-
tion of the steel and prior austenite grain size (pAGS).
Various empirical equations to predict the Ms temperature can be
found in literature [1-2]. Most equations are applicable only to a
narrow range of alloying elements and composition. To overcome the
limitation, advanced models based on computational thermodynamics
have been developed [3, 4, 5]. However, large number of model
parameters often prohibit the extension of the model into wider range
of alloying elements and composition.
This research aims at developing a thermodynamics-based model to
predict α’ and ε Ms temperatures in a wider constituent elements and
composition range of steels, by reducing the number of model para-
meters, maintaining the quality of prediction. The prediction capability
is improved by considering the pAGS dependency. This model can be
used for predicting which type of martensite is to be formed by com-
paring the Ms temperatures of α’ and ε.
References
[1] J. Wang et al., Mater. Trans. Jim, 41 (2000) 761.
[2] C. Y. Kung et al., TMS-AIME, Warrendale, PA (1978) 229-248.
[3] G. Ghosh et al., J. Phase Equilibria, 22 (2001) 199-207.
[4] S. Cotes et al., J. Alloys and Compounds, 280 (2001) 168-177.
[5] H.-S. Yang et al., CALPHAD, 36 (2012) 16-22.
PB18
Compound Growth due to Solid-state Reactive Diffusion in the
(Sn−Cu)/Ni System
Misako Nakayama and Masanori Kajihara
Tokyo Institute of Technology, Nagatsuta 4259, Midori-ku,
Yokohama 226-8502, Japan
Owing to high electrical conductivity, Cu-base alloys are widely
used as conductor materials in the electronics industry. If the Cu-base
conductor is interconnected with a Sn-base solder, Cu6Sn5 and Cu3Sn
are formed at the interconnection between the conductor and the solder
during soldering and then gradually grow during energization heating
at solid-state temperatures. Since the Cu−Sn compounds are brittle and
possess high electrical resistivities, their growth deteriorates the me-
chanical and electrical properties of the interconnection. To inhibit the
formation of the compounds, the Cu-base conductor is usually plated
with a Ni layer. The price is much lower for Cu than for Ag, and hence
Sn−Cu alloys are more preferentially used as a low-cost Pb-free solder
than Sn−Ag alloys. In the Sn−Cu solder, small particles of Cu6Sn5 are
dispersed in the Sn matrix. The dispersion of Cu6Sn5 in the solder may
influence the kinetics of the reactive diffusion between the Sn matrix
and the Ni layer at the interconnection. Unfortunately, however, reli-
able information on such influence is rather limited. To examine this
influence, the kinetics of the reactive diffusion in the (Sn−Cu)/Ni
system was experimentally observed at solid-state temperatures of
453−473 K using sandwich (Sn−Cu)/Ni/(Sn−Cu) diffusion couples
with Cu mol fractions of 0.01−0.03 in the present study.
Binary Sn−Cu alloys with Cu concentrations of y = 0.01−0.03
were made as 25 g button ingots by argon arc melting from pure Sn and
Cu with purity of 99.99 %, where y is the mol fraction of Cu. Plate
specimens with a size of 15x5x2 mm3 were prepared from the button
ingot. Sheet specimens with dimensions of 20x7x0.2 mm3 were cut
from a pure Ni commercial sheet with purity of 99.97 %. One Ni sheet
specimen was sandwiched between two Sn−Cu plate specimens and
then heat treated for diffusion bonding in an oil bath with silicone oil
for 69 h and 44.5 h at 453 K and 473 K, respectively, by the technique
used in previous studies [1, 2]. After the heat treatment, the diffusion
couples were isothermally annealed at 453−473 K for various times up
44
Calphad xxx (xxxx) xxx–xxx
to 1903 h. For each annealed diffusion couple, the cross-sectional mi-
crostructure was observed by differential interference contrast optical
microscopy (DICOM), and the chemical composition of each phase was
measured by electron probe microanalysis (EPMA).
The DICOM and EPMA observations indicate that an intermetallic
layer composed of the (Cu, Ni)6Sn5 and Ni3Sn4 phases is formed at the
original (Sn−Cu)/Ni interface in the diffusion couple during isothermal
annealing. The total thickness of the intermetallic layer is proportional
to a power function of the annealing time. The exponent of the power
function takes values of 0.37−0.44 at 453 K and those of 0.63−0.69 at
473 K. Therefore, the growth of the intermetallic layer is controlled by
boundary and volume diffusion at 453K. In constant, at 473 K, interface
reaction as well as interdiffusion contributes to the rate-controlling
process of the layer growth. The addition of Cu into Sn accelerates the
intermetallic growth within the experimental annealing times.
References
[1] M. Mita, M. Kajihara, N. Kurokawa and K. Sakamoto, Mater. Sci.
Eng. A, 403 (2005) 269-275.
[2] T. Takenaka, S. Kano, M. Kajihara, N. Kurokawa and K.
Sakamoto, Mater. Sci. Eng. A, 396 (2005) 115-123.
PB19
The effect of α recrystallization on γ nucleation in continuous
heating in ferritepearlite structures
Shohei Yabu1, Koutarou Hayashi1, Nobuo Nakada2
1
Nippon Steel & Sumitomo Metal Corporation, Reserch &
Development, 20-1 Shintomi, Futtsu, Chiba, 293-8511 Japan
2
Department of Materials Science and Engineering, Tokyo Institute
of Technology, 4529 Nagatsuta-cho, Midoriku, Yokohama, Kanagawa,
226-8502 Japan
1. Introduction
Cold-rolled steels are often heated to above the Ac1 temperature at
various heating rates. The nucleation of austenite is promoted by the
retention of deformed ferrite-pearlite microstructures. This could be
attributed to several microstructural properties such as high stored
energy, frangmented pearlite lamellae and /or spherodized carbides,
defomed pearlite colonies, and a large population of ferrite grain
boundaries [1]. The dominant rate-controlling process, however, has
not been clarified yet. In this study, austenite formation from cold-
rolled ferrite and pearlite microstructures during continuous heating
was investigated in a Fe―0.1 mass % C―2 mass % Mn alloy. The
emphasis is placed on to investigate the effect of deformed ferrite-
pearlite microstructure on the nucleation of austenite.

2. Experimental
Sheet specimens with ferrite and pearlite microstructures were
prepared by a hot-rolled method. The chemical composition was 0.10
mass % C, 2.0 mass % Mn, 0.01 mass % Si, 0.01 mass % P and 0.003
mass % S. Sheet specimens were cold-rolled with a reduction of 52 %.
Cold-rolled sheet specimens were annealed at 650 ˚C for 3.6 ks.
Hereafter, the cold-rolled and annealed specimens are called CR and
HT, respectively. The austenitization behavior of the specimen was
analyzed by dilatometry curve. The specimen was heated up to 950 ˚C
at a heating rate of 28 ˚C /s. The initial and heated microstructures were
observed by scanning electron microscope.
3. Result and discussion
The dilatometry curves for the specimen of CR and HT at a heating
rate of 28 ˚C /s are shown in Fig. 1 (a). The calculated first derivative of
these curves are plotted in Fig. 1 (b). One can recognize in these figures
four and five stages in continuous heating for the specimen of CR and
HT, respectively. Azizi et al. reported that the microstructural evolution
during continuous heating were separated into several stages, as well.
The formation of austenite proceeds in the stage III. Although the value
of the derivative drops sharply in this stage for the specimen of CR, such
behavior does not occur for the specimen of HT. According to the ob-
servation, most deformed ferrite grains are remained at 712 ˚C for the
specimen of CR. Therefore, the specimen heated at the stage III has fine
ferrite and cementite microstructures. Austenite nuclei form pre-
ferentially at cementite on the ferrite grain boundary. As a con-
sequence, it is suggested that the sharp drop is due to acceleration in the
nucleation of austenite. On the basis of thermodynamics, the effect of
the grain boundary on austenitization behavior will be discussed.
Reference
[1]H.Azizi-Alizamini, M.Militzer, and W.J.Poole, Metall. Mater.
Trans. A, vol.42A(2011), 1544-1557
PB20
CALPHAD-assisted morphology control of manganese sulfide
inclusions in free-cutting steels
Shih-guei Lin1, Yen-Hao Su2, Ku-Ling Chang2 and Shih-kang Lin1,*
1
Department of Materials Science and Engineering, National Cheng
Kung University, Taiwan
2
China Steel Corporation, Taiwan
*e-mail: linsk@mail.ncku.edu.tw
Steel is one of the most important and the most widely used mate-
rials in civilization. Although steels are mainly composed of iron (Fe),
various types of steels have been invented for industrial applications
ranging from aircraft and offshore construction to automotive industry
[1]. Among the steels, various major and minor alloying elements are
added for controlling the phases, grain structures, and size and dis-
tribution of inclusions in the steels. Free-cutting steels with the cap-
ability of high-speed cutting are demanding for bolts, nuts, certain
automobile parts, and instruments. In order to improve efficiency of
cutting process in the industry, development of new free-cutting steels
with good machinability is desired. Addition of sulfur (S) can improve
the machinability of steel by forming manganese sulfide (MnS) inclu-
sions with low shear strength such that the cutting resistance of steels is
reduced with MnS being the stress raiser. In addition, the formation of
MnS suppresses the formation of iron sulfide (FeS), so the hotshortness
phenomenon can be prevented. Since the morphology and the uni-
formity of the MnS inclusions, i.e., the shapes, sizes, and distributions of
MnS, critically determine the cutting properties of steels [2], the reac-
tions involving MnS formation during solidification need to be crucially
assessed. These reactions are either stable eutectic or metastable
monotectic reactions [3]. In the study, we focus on establishing the
45
Calphad xxx (xxxx) xxx–xxx
relationships between doping elements and solidified microstructures
by utilizing both thermodynamic modeling based on the CALPHAD
method and high-temperature experiments with an atmosphere-con-
trolled high-frequency induction furnace. Based on the TCFE7 database,
we systematically evaluate the effect of alloying elements on the mi-
crostructure of MnS. These alloying elements can be categorized into
three groups: Si, C, Cr, Nb, and Ta are eutectic-stabilizer, Ni (>3 wt.%),
W, Al, Cu, and O are monotectic-stabilizer, and Ni (<3 wt.%), V, Mo, B,
N, H, Ar, Zr, P, and Co are inert dopant, which do not noticeably change
the microstructure of MnS. Among the doping elements, oxygen (O) is
identified to be a super-strong monotectic-stabilizer, that oxygen ad-
dition can drastically enhance the monotectic-type structure, which is
desirable for free-cutting steels. The thermodynamic predictions agree
closely with high-temperature experiments. With the combined efforts
of thermodynamic modeling and high-temperature experiments, the
morphology, size, and uniformity of MnS inclusions can be optimized
for the development of free-cutting steels.
References
[1] J. Szekely, ISIJ International, Vol. 36 (1996) pp. 121-132.
[2] G. Anan et al., Kobe Steel Engineering Reports, Vol. 56 (2006)
pp. 44-47.
[3] K. Oikawa et al., ISIJ International, Vol. 35 (1995) pp. 402-408.
PB21
Phase equilibria and glass forming ability in the Zr-Cu-Ni
ternary system
Mujin Yang 1, Shuiyuan Yang 1,2, Shaobo Tu 1, Cuiping Wang 1,2,*,
Xingjun Liu 1,2
1
Department of Materials Science and Engineering, College of
Materials, Xiamen University, Xiamen 361005, P.R. China
2
Research Center of Materials Design and Applications, Xiamen
University, Xiamen 361005, P.R. China
* Corresponding author. E-mail: wangcp@xmu.edu.cn
Both of the binary systems Cu-Zr and Ni-Zr show a very deep eu-
tectic point, many hundred degrees below the melting points of Zr and
Ni. Such extreme stabilization of the liquid phase towards low tem-
peratures is very rare and it has attracted considerable attention from
the fundamental point of view as well as for a number of technical
applications. Therefore the paper is devoted to an experimental in-
vestigation of phase equilibria in the Zr-Cu-Ni ternary system. 1373 K
and 1273 K isothermal sections were experimentally established as the
latter shown in Fig.1a. A new ternary intermetallic compound named τ3
was found. The glass forming ability in the new found liquid region was
experimentally determined and a large glass forming region was found
as shown in Fig.1b. The newly determined phase equilibria and com-
position dependence of glass forming ability in this system will provide
important information for the development of the Zr-based metallic
glass and for the thermodynamic assessment of the Zr-Cu-Ni ternary
system.
Acknowledgments
This work was supported by the National Natural Science
Foundation of China (Grant No. 51471138) and the Ministry of Science
and Technology of China (Grant No. 2014DFA53040).
PB22
Predicted Elastic constants of Bio-materials Zr-Nb-Mo alloys
with CALPHAD-type model
J.S. Liang1, L. B. Liu1,2, X. Wang1, L. G. Zhang1,3
1
School of Material Science and Engineering, Central South
University, Changsha, Hunan 410083, PR China
2
Key Laboratory of Non-ferrous Metallic Materials Science and

Engineering, Ministry of Education, Changsha, Hunan 410083, PR
China
3
ZIK Virtuhcon, TU Bergakademie Freiberg, Fuchsmühlenweg 9, D-
09596 Freiberg, Germany
The composition elastic constants of bcc solution phases in Zr-Nb-Mo
bio-materials were modeled by the CALPHAD method[1-2], which based
on available data from experiment[3] and first-principles calculations.
The elastic constants of Zr-Mo alloys were obtained by first-principles at
0K. The variation of single crystal elastic property (Fig. 1) with the
composition in the whole composition range of the Nb-Mo alloys was
predicted and was in agreement with experimental data, such as bulk
modulus, shear modulus and the Poisson ratio. All optimizations for ob-
taining the parameters work by utilizing a least square. The elastic
parameters obtained finally in the present work are summarized in
Table1. According to the calculated results, the Young's modulus is lowest
in the <100> direction at the Zr-rich end. Zr-(0~17 at%)Nb-(0~5 at%)
Mo alloys (Fig. 2) can be predicted to have a Young′s modulus in the
range of 10 GPa to 30 GPa, which matches that of the human bones. It
will be the potential implant materials for bio-medical uses.
References
[1] Z.K. Liu et al., Scripta Materialia, 63 (2010) 686-691.
[2] X. Wang et al., Calphad, 48 (2015) 89-94.
46
Calphad xxx (xxxx) xxx–xxx
[3] P. Bujard et al., Journal of Physics F: Metal Physics, 11 (1981)
775-786.
PB23
Interrelation between Crystal Structure of Co Solid Solution
Matrix and Precipitation of Intermetallic Phases in Co-rich Co-Nb
Alloys
Kohei Abe1, Toshiaki Horiuchi1, Frank Stein2 and Shunsuke
Taniguchi2,3
1
Division of Mechanical Engineering, Graduate School of
Engineering, Hokkaido University of Science, 7-15-4-1, Maeda, Teine,
Sapporo, Hokkaido 006-8585, Japan
2
Max-Planck-Institut für Eisenforschung GmbH Max-Planck-Straße
1, D-40237 Düsseldorf, Germany
3
Advanced Technology Research Laboratories, Nippon Steel &
Sumitomo Metal Corporation 1-8 Fuso-Cho, Amagasaki, Hyogo 660-
0891 Japan
The Co-Nb binary system is known for containing several complex
intermetallic phases which show interesting features [1,2]. The authors
have previously reported that the supersaturated Co solid solution of a
Co-3.9 at%Nb alloy retained the fcc high-temperature structure at room
temperature after solution heat treatment at 1240 ˚C and at the same

time a clear thermal reaction was observed by differential scanning
calorimetry analysis during cooling. Surprisingly, no precipitates were
visible in the microstructure by scanning electron microscopy. On the
other hand, an additional annealing treatment at 900 ˚C resulted in the
discontinuous precipitation of an intermetallic phase and a transfor-
mation of the crystal structure of the matrix to hcp [3]. Interestingly,
Nikolin et al. reported that Co(Nb) solid solutions sometimes show a
special kind of polytypism as a result of multiple phase transitions [4].
These phenomena are considered to be closely related to the Nb
content in the matrix and the precipitation of intermetallic phases. In
the present study, four Co-Nb binary alloys (0, 1.0, 2.0, 3.9 at%Nb)
were prepared and heat-treated at various conditions in order to elu-
cidate the relationship between crystal structure of the matrix and
precipitation of intermetallic phases. Microstructures were observed
and analysed by transmission electron microscopy and electron back-
scatter diffraction pattern analysis. Microhardness tests were also per-
formed for the samples after solution heat treatment at 1240 ˚C. High-
resolution transmission electron microscopy revealed the existence of
finely dispersed ordered regions with increased Nb content within the
supersaturated fcc matrix implying the possibility of the existence of
metastable intermediate phases in this system.
References
[1] F. Stein et al., Intermetallics, 16 (2008), 785-792.
[2] A. Leineweber et al., Intermetallics 25 (2012), 34-41.
[3] T. Horiuchi and F. Stein, Proc. Intermetallics 2015, Bad
Staffelstein, Germany (2015).
[4] B. I. Nikolin et al., Scripta Metallurgica, 22 (1988), 761-766.
PB24
Investigation of the glass forming ability of Al-based alloys
with the help of CALPHAD approach
Ligang Zhang1, Libin Liu1, Zhanpeng Jin1, Yun Jiang2
1
School of material science and engineering,Central South
University, Changsha, Hunan, 410083, P.R. China
2
College of Automotive and Mechanical Engineering,Changsha
University of Science and Technology, Changsha, Hunan, 410144, P.R.
China
Interest in aluminum alloys is increasing continuously due to their
properties such as the low density, high strength, high corrosion-re-
sistance as well as their potential applications in the automotiv and
aerospace industries. The study of amorphous Al-based alloys has at-
tracted much attention in recent years due to their high strength and
excellent magnetic properties. Scholars have proposed many criteria for
predicting the glass-forming ability (GFA) of metallic materials. The
criteria based on thermodyanimc and kentic are very useful. The key to
such kinds of approach is the reliable binary and ternary phase dia-
gram, thermodynamic properties, and kenetic properties. In this work,
the thermodyanmic database of Al-based alloys are constructed with
the help of CALPHAD methods. Based on these, the combined ther-
modynamic and kinetic method would be used to predict GFA of the Al-
based alloys.
Corresponding author: Ligang Zhang, liangzhang@csu.edu.cn
PB25
Hydrogen issues in steel processing- a preliminary approx-
imation
L. Verdan1, R.R. Avillez2, A. Costa e Silva1
1
EEIMVR-UFF, Volta Redonda, RJ, Brazil
2
PUC-RIO, Rio de Janeiro, RJ, Brazil
Hydrogen can be a source of difficulties in steel processing for
several reasons. In the present work, we focus on hydrogen that is ab-
sorbed during steelmaking operations and can be mostly responsible for
different types of porosities during casting, formation of blisters during
heating for rolling and formation of “flake” cracks in quenched and
tempered material.
47
Calphad xxx (xxxx) xxx–xxx
We performed a simple assessment of the solubility of hydrogen in
the liquid and solid phases of steel and merged this description to a
commercial steel database. Following a simplified procedure estab-
lished some decades ago, we made predictions of the combinations of
hydrogen and nitrogen in aluminum killed steels that would cause
surface porosity in continuous casting. Preliminary calculations were
also made for the redistribution of hydrogen between ferrite and aus-
tenite, in order to simulate the conditions for the formation of hydrogen
flakes in segregated areas of Q&T steels.
The results can be used as guidelines for the improvement of the
definition of safe ranges for steel processing, with the limitations as-
sociated to the complexity of the behavior and effects of hydrogen in
steel.
PB26
Phase equilibria investigation and thermodynamic assessment
of the dispenser cathode impregnated materials: the BaO-CaO-
Al2O3 system
Rui Zhang1, Huahai Mao2, Pekka Taskinen1
1
Aalto University, School of Chemical Technology, Metallurgical
Thermodynamics and Modelling Research Group, Espoo, Finland
2
Royal Institute of Technology (KTH), Department of Material
Science and Engineering, Stockholm, Sweden
The modern dispenser cathode consists, essentially, of a strongly-
bonded, continuous metallic phase or a refractory or refractory metals
[1]. One of the key factors determining the performance of a dispenser
cathode is the material and composition of the impregnated.The im-
pregnatedof the components, BaO-CaO-Al2O3, is widely employed in
modern times as it can reduce the barium sublimation and enhance the
emission properties. The ternary phase diagram information of the BaO-
CaO-Al2O3 system is significant in order to (i)understand the nature of
the impregnatedand to (ii) tailor the impregnatedcomposition to realize
the optimal operation conditions.However, the available information
about the BaO-CaO-Al2O3ternary system is insufficient and varies, and
most of the research is focused on the isothermal sections. More in-
formation is required on the vertical sectionsalong the planes of interest
where the commercial barium calcium aluminate impregnants
(BaO:CaO:Al2O3=5:3:2, 4:1:1 and 6:1:2) are positioned.
The present work aims at (i)experimentally investigate the iso-
thermal sections and vertical planes in parallel to the temperature axis
of the three dimensional prismatic volume of the BaO-CaOAl2O3
system, by using the high temperature equilibration-quenching tech-
nique, scanning electron microscopy/ energy dispersive spectroscopy
(SEM/EDS), X-ray powder diffraction (XRD) and electron probe X-ray
micro-analyzer (EPMA) and (ii) performing thermodynamic modelling
of the BaO-CaO-Al2O3 system to achieve a set of consistent thermo-
dynamic parameters that can well reproduce the experimental data
acquired. With the thermodynamic parameters available, more vertical
planes of the BaO-CaO-Al2O3 system can be predicted, helping to un-
derstand the crystallization path at certain impregnatedcompositions.
Reference
[1] O.I. Get’man, V.V. Skorokhod, Structural engineering of im-
pregnated dispenser cathodes, POWDER METALL MET C+, 53 (2015)
701-721.
PB27
Prediction of SFR fuel composition during irradiation by cou-
pling between Open Calphad software and GERMINAL V2 fuel
performance code
K. Samuelsson1, J-C. Dumas2, C. Guéneau3, N. Dupin4, B. Sundman5
1
KTH Royal Institute of Technology – Department of Physics –
Stockholm, Sweden
2
CEA, DEN/DEC – Centre de Cadarache – Saint-Paul lez Durance
Cedex, France
3
CEA, DEN/DANS/DPC – Centre de Saclay – 91191 Gif-sur-Yvette

Cedex, France
4
Calcul Thermo – 63670 Orcet, France
5
INSTN, Centre de Saclay - 91191 Gif-sur-Yvette Cedex, France
The uranium-plutonium mixed oxide fuel used in the Sodium-cooled
Fast Reactors (SFR) is subject to both high temperature and large
temperature gradients during operation. These extreme conditions are
the cause of many thermal, mechanical and chemical transformations in
the fuel. Moreover, the behavior of the fission products (FP) generated
by the irradiation strongly depends on their chemical nature as well as
conditions in the fuel (temperature, oxygen potential, …). Experimental
observations show the formation of a layer located between the fuel and
the cladding material for a burn-up of 6 to 8 ha%. This layer, called JOG
for “Joint Oxyde-Gaine” [1] is due to the release, migration and asso-
ciation of caesium, iodine, and tellurium mainly with oxygen and mo-
lybdenum created in the fuel pellet. At high burn ups, these FP com-
pounds can react with the cladding components (Fe, Cr, Ni) corroding
the inner part of the cladding material.
As the fuel and cladding chemical interaction is nowadays re-
cognized as one of the major factors determining integrity and lifetime
of pins in the SFR [2], it is important to model the physicochemical
behavior of the (U,Pu)O2 fuel under typical irradiation conditions. The
modelling of mixed oxide fuel pins has previously been improved by
CEA with the development of the GERMINAL V2 fuel performance code
[3] in the simulation platform PLEIADES. Currently, further improve-
ments are being implemented by integrating Open Calphad evaluations
of the fuel chemistry into GERMINAL V2. By performing these con-
tinuous evaluations, it will be possible to predict the amount of the
volatile FP being transported towards the JOG, and ultimately, the total
quantity of elements available for FCCI (Fuel Cladding Chemical
Interaction).
The motivation for choosing Open Calphad software [4] is both its
ability to use efficient models/descriptions and its compatibility with
the TAF-ID database [5], developed within the frame of the OECD/NEA,
where thermodynamic modelling of many different actinides and fis-
sion products systems based on the CALPHAD method are described
and implemented.
Calculations have been performed on (U0.78Pu0.22)O1.975 fuel irra-
diated to 13.6 ha% in the PHÉNIX reactor. The results show quite good
representative agreement with post-irradiation observations regarding
the chemical composition.
Next steps for the improvement of the thermodynamic description
of the irradiated mixed oxide fuel as well as the coupling between
thermodynamics and the fuel performance code GERMINAL will be
proposed and discussed.
References
[1] M. Tourasse, M. Boidron and B. Pasquet, J. Nucl. Mater., 188
(1992) 49
[2] K. Maeda, Comprehensive Guide Nucl. Mater. 3.16, Elsevier Ltd
(2012), 443
[3] M. Lainet, V. Bouineau, T. Helfer and M. Pelletier, FR13, Paris,
France, 4-7 March 2013
[4] B. Sundman, U.R. Kattner, M. Palumbo and S.G. Fries, IMMI
journal (2015), 4:1
[5] C. Guéneau et al., J. Nuc. Mat. 419 (2011) 145
PB28
Coalescence in nano-sized metallic systems
R. Novakovic1, S. Delsante1,2, G. Borzone1,2
1
Institute for Energetics and Interphases - National Research
Council (IENI-CNR), Via de Marini 6, I-16149, Genoa, Italy
2
Department of Chemistry and Industrial Chemistry, Genoa
University & Genoa Research Unit of INSTM, Via Dodecaneso 31, I-
16146, Genoa, Italy
Computational Materials Science
During heating, nanoparticles undergo to specific phenomena such
48
Calphad xxx (xxxx) xxx–xxx
as coalescence, which affect their phase stability. This aspect is of great
importance for the potential application of nanosized metallic system.
The driving force for the coalescence of two nanoparticles is the surface
energy reduction due to lower surface area of the new nanoparticle. In
fact, the process begins with the contact of nanoparticles and is fol-
lowed by the alignment of the coalescing planes at the interface and by
the subsequent growth of the neck. The studies of the coalescence
processes involve nanoparticles diffusion, nanoparticles properties re-
levant to the diffusion, such as melting points, volumes and diffusion
coefficients as well as overall coalescence mechanisms. The nano-
particles growth at high temperature by coalescence have been ana-
lyzed by means of the theoretical predictions; an important parameter
for predicting the final particle size is the rate of coalescence. The re-
sults obtained are compared to the experimental data available in lit-
erature.
PB29
Thermodynamic assessments and diffusion study of fcc phase
for the Ni-Co-Al-Wquaternary system
Yang Wang1, Hao Wang1, Xiao-Gang Lu1,2
1
School of Materials Science and Engineering, Shanghai University,
Shanghai 200072, China
2
Materials Genome Institute, Shanghai University, Shanghai
200072, China
As key knowledge to design Ni-Co-base superalloys, the Al-poor part
of the Ni-Co-Al ternary system has been studied experimentally and
theoretically in the present work. Alloy samples were prepared to de-
termine the phase equilibria among fcc (γ), L12 (γ') and B2 (β) phases
and thermodynamic assessments were performed to evaluate the ther-
modynamic properties and isothermal sections. Simultaneously,ternary
fcc Ni-Co-Al diffusion couples annealed at 1173, 1373 and 1573 K were
analyzed using electron probe microanalysis (EPMA). Then the inter-
diffusion coefficients were determined with the Sauer-Freise and
Whittle-Green methods based on the measured concentration profiles of
binary and ternary diffusion couples, respectively. All the available
experimental diffusion data were reviewed and utilized to optimize
diffusion mobilities in fcc Ni-Co-Al alloys and reasonable agreements
were reached. In addition, the thermodynamic parameters and diffu-
sion mobilities in the Ni-Al-W, Ni-Co-W and Co-Al-W ternary systems
were reassessed after critical evaluation of the previous assessments
and experiments [1-6]. Furthermore, thermodynamic and diffusion
behavior of Ni-Co-Al-W quaternary system have been investigated to
buildthermodynamic and kineticdatabase.
References
[1] Y. F. Cui, X. Zhang, G. L. Xu, W. J. Zhu, H. S. Liu, Z. P. Jin., J
Mater Sci 46 (2011) 26112621.
[2] Eric A. Lass, Maureen E. Williams, Carelyn E. Campbell, Kil-Won
Moon, and Ursula R. Kattner., JPEDAV 35 (2014) 711-723.
[3] Hui Chang, Guanglong Xu, Xiao-Gang Lu, Lian Zhou, Kiyohito
Ishida and Yuwen Cui., Scripta Materialia 106(2015) 13-16.
[4] J. Popovic, P. Broz, J. Bursík., Intermetallics 16 (2008) 884-888.
[5] Chong Chen, Lijun Zhang, Jinghua Xin, Yaru Wang, Yong Du,
Fenghua Luo, Zhongjian Zhang,Tao Xu, Jianzhan Long.,Journal of
Alloys and Compounds 645 (2015) 259-268.
[6] J. Zhu, M.S. Titus, and T.M. Pollock.,JPEDAV 35 (2014) 595-
611.
PB30
Predicting Critical Al Concentrations to Form Alpha-Alumina in
Ni-Fe-Al Alloys Using the CALPHAD Method
Austin J. Ross1, Huazhi Fang1, Greta Lindwall1, Wei Zhao2, Brian
Gleeson2, Zi-Kui Liu1
1
Department of Materials Science and Engineering, The
Pennsylvania State University, University Park, PA 16802, USA
2
Department of Mechanical Engineering and Materials Science,

University of Pittsburgh, Pittsburgh, PA 15261, USA
Often the ability of Ni-superalloys to survive in harsh environments
can be attributed to Al and Cr present in the alloy. These elements form
protective oxide layers (scales) by the selective reaction of oxygen with
Al and Cr near the alloy surface. These oxides will consist primarily of
Al2O3 and Cr2O3 which will prevent further influx of oxygen into the
alloy[1], [2]. Hence, establishing this protective oxide is the main ob-
jective in preventing gaseous attack at high temperatures. Furthermore
if the concentration of Al or Cr is too low the oxides formed by these
elements will precipitate into the alloy (internal oxidation) instead as
opposed to establishing an external oxide scale (external oxidation).
Such oxidation is more rapid than traditional oxidation of pure nickel
and is therefore undesirable. In this work the thermodynamics and O
mobility in the Al-NiFe-O system were modelled. This was done to
obtain inputs to models which can predict the critical concentration of
Al needed to form an external oxide scale. The models used to do this in
the present work were those developed my C. Wagner [3] and an ex-
tension of this model by W. Zhao[4]. Special attention was paid to the
solubility of O in the Nickel matrix since this and the O diffusivity were
used as inputs to these models. First principles calculations were used to
refine the energetics of the fcc Ni-O system in combination with the
compound energy formalism. The predicted critical Al concentration in
the Ni-Al system using the two selected models is given in Figure 1.
49
Calphad xxx (xxxx) xxx–xxx
References
[1] D. J. Young, High Temperature Oxidation and Corrosion of Metals:
Chapter 10, vol. 1. Elsevier, 2008.
[2] R. C. Reed, The Superalloys: Fundamentals and Applications.
Cambridge University Press, 2006.
[3] C. Wagner, “Reaktionstypen bei der Oxydation von
Legierungen,” Z. Elektrochem., vol. 63, p. 772, 1959.
[4] W. Zhao, Y. Kang, J. M. A. Orozco, and B. Gleeson, “Quantitative
Approach for Determining the Critical Volume Fraction for the
Transition from Internal to External Oxidation,” Oxid. Met., vol. 83, no.
3–4, pp. 187–201, Nov. 2014.
PB31
Interdiffusion and atomic mobility studies in Ni-richfcc Ni-Co-
Al alloys
YL.Yang1, Z.Shi1*, YS.Luo1, Y.Lu1, SY.Yang1, JJ.Han1, WB.Li2,
CP.Wang1, XJ.Liu1*
1
Department of Materials Science and Engineering, College of
Materials, Xiamen University, Xiamen 361005, P.R. China
2
Department of Aeronautics, Xiamen University, 361005, P. R.
China
* Corresponding author:shizhan@xmu.edu.cn
Abstract The ternary interdiffusion coefficients in fcc Ni-Co-Al al-
loys at 1373K were determined using Whittle and Green method to-
gether with electronic-probe microanalysis. With the help of DICTRA
software, the experimental diffusion coefficients were critically as-
sessed to obtain the atomic mobilities of Ni, Co and Al in fcc Ni-Co-Al
alloys.Comprehensive comparisons between calculated and experi-
mental diffusion coefficients (seen in Fig.1) showed that the experi-
mental data could be well reproduced by the atomic mobilities obtained
in the present work. The assessed diffusion mobilities were further
validated by the calculation of the concentration profiles and diffusion
paths in prepared diffusion couples. As can be seen in Figs.2 and 3, the
good agreement between the calculation and the experiment data in-
dicates that the presently obtained atomic mobilities are reliable, thus it
can be acted as a supplement of nickel-based superalloys diffusion da-
tabase.

Acknowledgements
This work thanks the support from the Industry-university research
project of Aviation Industry Corporation of China (No. CXY2014XD27),
the Fundamental Research Funds for the Central Universities
(No.20720140511), the National Natural Science Foundation of China
(No.51201145, and No.51301146) and the Ministry of Science and
Technology of China (No.2014DFA53040)
PB32
Phase-Field modeling of spinodal decomposition during poly-
crystalline film deposition
Yong Lu1*, Cuiping Wang1, Yuanyuan Cui1, Shuiyuan Yang1, Zhan
Shi1, Yunzhi Wang2, Xingjun Liu1*
1
Department of Materials Science and Engineering, College of
Materials, and Research Center of Materials Design and Applications,
Xiamen University, Xiamen, 361005, China
2 thermodynamic factors. According to the feature of bond-orientation
Department of Materials Science and Engineering, The Ohio State
University, 2041 College Road, Columbus, OH 43210, USA
*E-mail: luyong@xmu.edu.cn & lxj@xmu.edu.cn
Drastically different microstructures with concentration modulation
in polycrystalline film have been reported, including the lamellar
structures parallel and perpendicular to the grain boundary and ran-
domly oriented interconnected two-phase mixtures. To understand the
disparity of these microstructures we study their formation mechanisms
via spinodal decomposition during nucleation and growth of poly-
crystalline film with the aid of computer simulations. The effect of the
nucleation and growth rate on the microstructure evolution during film
deposition and the fast diffusion of solute atoms in grain boundaries
were systematically investigated. The microstructure evolutions of
various modulated structure were simulated, as shown in Fig. 1. It is
found that the relative speed between the growth of polycrystalline film
and spinodal decomposition therein resulted in the formation of dif-
ferent oriented lamellar structures. In addition, the simulation results
indicated that the migration of grain boundary and the segregation of
solute atoms at grain boundary can have considerable influence on the
film morphology. These obtained results could be useful in guiding the
choice of alloy chemistry and deposition conditions to obtain a desired
self-organized two-phase microstructure in polycrystalline thin films.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (Nos. 51301146) and (Nos. 51571168).
PB33
Abnormal correlation between phase transformation and
cooling rate for pure metals
J. J. Han1, C. P. Wang1, X. J. Liu1,2,*, Y. Wang3, Z.-K. Liu3, T.-Y.
Zhang4 and J. Z. Jiang5
1 This work focused on experimental investigation and thermo-
College of Materials, Xiamen University, Xiamen 361005, P. R.
China
2 croscopy (OM), X-ray diffraction (XRD), electron probe microanalysis
Collaborative Innovation Center of Chemistry for Energy
Materials, Xiamen University, Xiamen 361005, P. R. China
3 signed alloys, the invariant reactions, liquidus projection and several
Department of Materials Science and Engineering, Pennsylvania
State University, University Park, Pennsylvania 16802, U. S. A.
50
Calphad xxx (xxxx) xxx–xxx
4
Shanghai University Materials Genome Institute, Shanghai
University, 99 Shangda Road, Shanghai 200444, China
5
School of Materials Science and Engineering, Zhejiang University,
Hangzhou, 310027, P. R. China
*Corresponding author: lxj@xmu.edu.cn (X.J. Liu)
This work aims to achieve deep insight into the phenomenon of
phase transformation upon rapid cooling in metal systems and reveal
the physical meaning of scatter in the time taken to reach crystal-
lization. The total number of pure metals considered in this work ac-
counts for 14. Taking pure copper as an example, the correlation be-
tween phase selection of crystal or glass and cooling rate was
investigated using molecular dynamic simulations. The obtained results
demonstrate that there exists a cooling rate region of 6.3×1011-
16.6×1011 K/s, in which crystalline fractions largely fluctuate along
with cooling rates. Glass transformation in this cooling rate region is
determined by atomic structure fluctuation, which is controlled by
order at different cooling rates, we propose two mechanisms of glass
formation: i) kinetic retardation of atom rearrangement or structural
relaxation at a high cooling rate; and ii) competition of icosahedral
order against crystal order near the critical cooling rate.
Acknowledgments
This work was supported by the National Key Basic Research
Program of China (973 Program) (No. 2012CB825700), the
Fundamental Research Funds for the Central Universities (No.
20720150079), the Ministry of Education of China (No.
20120121130004) and the National Natural Science Foundation of
China (Nos. 51031003 and 51171159).
PC1
Experimental investigation and thermodynamic modeling
ofthe Co−Nb−W system
Mengde Pang1, Yafei Pan1, Yingbiao Peng2, Peng Zhou3, Yong Du1,*
1
State Key Lab of Powder Metallurgy, Central South University,
Changsha, Hunan410083,P. R. China
2
School of Metallurgical Engineering, Hunan University of
Technology, Zhuzhou, Hunan 412008, P. R. China
3
School of Mechanical and Electrical Engineering, Hunan
University of Science and Technology, Xiangtan, Hunan 411201, P. R.
China
E-mail: yong-du@csu.edu.cn
The knowledge on the thermodynamic behaviour of the Co−Nb−W
system is useful from the point of view that it is one of the Co-based
super-alloys and cemented carbides subsystems. Phase equilibria of this
system at 900, 1000, 1100 and 1200 ˚C have been experimentally in-
vestigated [1], [2]. However, information on invariant reactions and
liquidus projection of this system cannot be found in the literature.
dynamic modelingof theCo−Nb−W system. Based on the optical mi-
(EPMA) and differential scanning calorimetry (DSC) results of the de-
vertical sections have been determined. Thermodynamic modeling of
Co−W−Nb system was performed using CALPHAD technique with the

parameters of binary subsystems taken from widely accepted assess-
ments [3], [4], [5]. The present description can well reproduce the
experimental data.
Acknowledgments
The financial support from National Natural Science Foundation of
China (Grant No. 51371199) and Ministry of Industry and Information
Technology of China (Grant No. 2015ZX04005008) is greatly ac-
knowledged.
References
[1]I. I. Gerashchenko et al., Vestn. Mosk. Univ. Khim., 24 (1983)69.
[2]Xingjun Liu et al., Intermetallics, 31 (2012) 48.
[3]C. Heet al., MRS Proceedings, 1128 (2008)1128-U05-30.
[4]Markström A. et al.,J. Phase Equilib. Diffus., 26 (2005)152.
[5] Huang Wet al., Z. Metallkd., 88 (1997)55.
PC3
Thermodynamic evaluation on chemical reaction between UO2
and SiC in LWR conditions Noriko Shirasu1, Masaki Kurata1
1 concerning liquid-solid phase equilibria, making the calculated in-
Japan Atomic Energy Agency,2-4,Shirakata Tokai-mura, Ibaraki,
319-1195 Japan
After Fukushima Daiichi nuclear accident in 2011, enhancing the
accident tolerance of light water reactor (LWRs) fuels became a very
important issue and currently the development of accidenttolerant fuel
(ATF) are in progress. Silicon carbide (SiC) is an attractive candidate of
ATF cladding material because of its high chemical stability, high-
radiationresistanceand low neutron absorption. SiC reacts much less
than Zircaloy with steam, the generation of heat and hydrogen gas
would be extremely suppressed.
Thermodynamic evaluation on chemical interactions between UO2
and SiC were performed on various possible conditions of oxygen po-
tential and temperature in severe accident. The chemical interactions
insteamatmosphere also evaluated.
The thermodynamic calculation was carried out using Thermo-Calc
code [1]. The thermodynamic data of species and phases were quoted
from TAF-ID database [2]. The oxygen potentials were varied by-
changing the O2 or H2O content in the range of about -740 to -10 kJ/
mol for O2 and -740 to -300 kJ/mol for H2O at 1500 K, which cover the
conditions in severe accident in LWRs. The oxygen potential for H2O
containing system is controlled by H2/H2O equilibrium. The tempera-
tures of 1500 K and 2500 Kwereselected as typical temperatures ofac-
cidental conditions in LWR. The following results were obtained from
calculation:
(1) SiC is converted to SiO2 by reaction with O2.
SiC + O2 →SiO2 + C,
C + 1/2 O2 →CO.
(2) SiC is also converted to SiO2 by reaction with H2O. However, the
fraction of the sub-reaction for forming SiO increasesthan in the case of
reaction with O2 when comparingthe results at the same temperatures
and the same oxygen potentials. The amount of SiO gas increases
abruptly with increase in temperature.The chemical reaction is as fol-
lows.
SiC + 2H2O →SiO+ CO+ 2H2.
(3)Apart of UO2 and SiC reacteach other and formUSi2-x and UCin
reducing atmospheres. These results suggest the degradation me-
chanism of SiC.
References
[1] http://www.thermocalc.com.
[2] http://www.oecd-nea.org/science/taf-id.
PC4
Phase equilibria of the Fe-Co-Mo ternary system in the iron-rich
side above 900 °C
Annie Antoni-Zdziobek1,2, Paolo Galimberti1,2, Thierry Commeau3
1 at., respectively.
Univ. Grenoble Alpes, SIMAP, F-38000, Grenoble, France
2 Acknowledgements
CNRS, Grenoble INP, F-38000, Grenoble, France
51
Calphad xxx (xxxx) xxx–xxx
3
Eurotungstene Metal Powders, 9 rue André Sibellas, BP 152X,
Grenoble cedex 9, France
The Fe-Co-Mo system is likely to provide technologically appealing
alloys, in view of the significant improvements of the mechanical
properties, such as hardness and ductility, attainable by aging treat-
ments [1]. A thorough knowledge of the phase equilibria in the tem-
perature range of interest for the processes is required for making use of
the phase diagram as a roadmap, both to define potentially interesting
compositions and to improve the elaboration parameters and heat
treatment conditions selection. A recent thermodynamic assessment has
been proposed by Povoden-Karadeniz et al. [2], based on a critical
evaluation of the data available in the literature and on the evaluation
of formation enthalpies of ferrite phase from first principle results. Our
experimental results established in a previous study [3] on solid-solid
phase equilibria at 930 ˚C and 1250 ˚C are in fairly good agreement with
these calculations, although some discrepancies are noted, e.g. solubi-
lity of Mo in the µ and γ-austenite phases or location of α-ferrite/γ-
austenite/µ tie-triangle. However, there is a lack of experimental data
variant reactions conjectural. The main objective of the present study is
to carry out an experimental work to achieve the constitution of phase
equilibria involving the liquid phase in the iron-rich side of the ternary
system.
The experimental procedure chosen combines isothermal and
heating/cooling experiments. Phase relationships in the solid-liquid
range are established at selected temperatures by means of electro-
magnetic phase separation technique [4] complemented by Differential
Thermal Analysis experiments. Solidification paths of key samples are
determined and the position of univariant lines are specified on the
liquidus projection of the iron-rich corner of the ternary system. One
invariant reaction involving liquid, α-ferrite, γ-austenite and µ phases is
identified. This new set of key experimental data leads to a refinement
of the thermodynamic description of the Fe-Co-Mo ternary system and
serves as a guideline to support reliable metallurgical alloy optimiza-
tion.
References
[1] P. Galimberti et al., Intermetallics, 22 (2012) 33-40.
[2] E. Povoden-Karadeniz et al., J. Alloys Comp., 587 (2014) 158-
170.
[3] P. Galimberti, Ph.D. Thesis, SIMAP, INPGrenoble, 2007.
[4] A. Antoni-Zdziobek et al., J. Phase Equilib. Diffus., 35(6) (2014)
701-710.
PC5
Calorimetric measurements of Ga-Li system
A. Dębski, W. Gąsior
Institute of Metallurgy and Materials Science, Polish Academy of
Sciences 30-059 Kraków, 25, Reymonta Street, Poland
a.debski@imim.pl
The Ga-Li system was measured with the use of two calorimetric
techniques. For liquid Ga-Li alloys, the integral molar enthalpy of
mixing was determined by drop calorimetric method. The measure-
ments were conducted in the entire concentration range. Strong nega-
tive deviation was observed from ideal solution with the minimum
value equal to -21.2 kJ/mol for XLi = 0.5421. The analysis of experi-
mental data suggests, that the integral mixing enthalpy of Ga-Li liquid
solutions is independent of temperature. Moreover, the direct reaction
calorimetric method was used for the determination of the formation
enthalpy of alloys, which concentrations correspond to the Ga7Li2,
Ga9Li5, GaLi, Ga4Li5, Ga2Li3, and GaLi2 intermetallic phases. The ob-
tained experimental values of the standard formation enthalpy were:
-18.1 ±0.8 kJ/mol at., -26.5 ±0.3 kJ/mol at., -34.7 ±0.3 kJ/mol at.,
-33.5 ±0.5 kJ/mol at., -32.8 ±0.3 kJ/mol at., and -24.6 ±1.4 kJ/mol

This work was supported by the National Science Centre, Poland, for
funding Project No. 2014/13/D/ST8/03147 in the years 2015 - 2018.
PC6
Calorimetric measurements of Li-Zn system
W. Gąsior, A. Dębski, S. Terlicka Institute of Metallurgy and
Materials Science, Polish Academy of Sciences 30-059 Kraków, 25,
Reymonta Street, Poland
w.gasior@imim.pl
The solution calorimetric method was applied to determine the
standard formation enthalpy of the solid intermetallic phases: LiZn,
Li2Zn3, LiZn2, Li2Zn5, LiZn4 and the heat of solution of zinc in liquid Sn.
These alloys were prepared from pure, metallic Li and Zn, which were
melted in a glove-box filled with high purity argon with a very low
concentration of impurities. All experiments were measured with the
use of Setaram MHTC 96 Line evo calorimeter. The heat of solution of
zinc in Sn-bath at 723K-926K was equal on average 8.6 ±0.3 kJ/mol at.
The standard formation enthalpy of the solid alloys, which concentra-
tions corresponds to LiZn, Li2Zn3, LiZn2, Li2Zn5, LiZn4 intermetallics,
was measured at 723 K. The obtained values of the standard formation
enthalpy were: -15.2 ±0.2, -16.3 ±0.2, -15.5 ±0.2, -15.2 ±0.2, -12.1
±0.1 kJ/mol at, for the LiZn, Li2Zn3, LiZn2, Li2Zn5, LiZn4, respectively
and were compared with the data calculated by means of the Miedema
model.
PC7
On the phase equilibria and liquidus projection of the Mg-Ni-Y
system
Kai Xu1, 2, Shuhong Liu1, *, Yong Du1, Zhanpeng Jin2
1 PC9
State Key Lab of Powder Metallurgy, Central South University,
Changsha, Hunan 410083, P. R. China
2 during spreading test and after aging treatment
School of Materials Science and Engineering, Central South
University, Changsha, Hunan 410083, China
*E-mail: shhliu@csu.edu.cn
Mg-Ni-Y based magnesium alloys with LPSO structure recently at-
tract considerable attention as the simultaneous achievement of high
strength and good ductility [1]. Besides, Mg-Ni-Y system is also con-
sidered to be one of the promising candidates for the nickel-metal hy-
dride battery (MH) [2]. However, only partial phase equilibria of this
system at 300, 400 and 500 ˚C have been experimentally investigated
[3-5]. Further measurement on the phase equilibria are needed for the
system.
Based on the optical microscopy (OM), X-ray diffraction (XRD),
electron probe microanalysis (EPMA) and differential scanning calori-
metry (DSC), the present work determined the isothermal section at 400
˚C, several invariant reaction and the liquidus projection. 13 ternary
compounds have been confirmed. The presently obtained phase dia-
gram data and the data in literature will be used to perform the ther-
modynamic modeling of the Mg-Ni-Y.
Acknowledgments
The financial support from the National Science Foundation of
China (Grant No. 51101172, 51429101) and the National Basic
Research Program of China are greatly acknowledged.
References
[1] Y. Kawamura et al., Materials Transactions, 42 (2001) 1172.
[2] S. Yasuoka et al., J. Power Sources, 156 (2006) 662.
[3] Q. Yao et al., J. Alloys Compounds, 421 (2006) 117-119.
[4] M. Jiang et al., Intermetallics, 57 (2015) 127-132.
[5] Z. L. Wang et al., J. Alloys Compounds, 649 (2015) 1306-1314.
PC8
On the phase equilibria of the Mg-Mn-Zn system
Dandan Huang1, Shuhong Liu1, *, Honghui Xu1, Yong Du1
1
State Key Lab of Powder Metallurgy, Central South University,
Changsha, Hunan 410083, P. R. China
52
Calphad xxx (xxxx) xxx–xxx
*E-mail: shhliu@csu.edu.cn
Materials based on the ternary Mg-Mn-Zn system are promising
candidates for biomedical applications due to their good biocompat-
ibility, low density and elastic modulus which are close to human bone
and much higher mechanical strength than the biodegradable poly-
mers. However, the published information on the phase equilibria of
the Mg-Mn-Zn system is very limited.
In the present work, isothermal section of the Mg-Mn-Zn system at
320 ˚C was constructed by a combination of XRD (X-ray diffraction) and
EPMA (electron probe micro-analysis). DSC was carried out to check
the invariant reactions. The thermodynamic modeling of the Mg-Mn-Zn
system is performed by CALPHAD (calculations of phase diagrams)
based on the available thermodynamic and phase diagram data from
the present work and the literature. The descriptions of the Mg-Mn and
Mg-Zn binary systems were taken from the recent assessments [1, 2],
while the Mn-Zn system is re-assessed since there is no comprehensive
thermodynamic description for the Mn-Zn system. A set of self-con-
sistent thermodynamic description of the Mg-Mn-Zn system was finally
obtained. The comparisons between the calculations and the experi-
mental data were presented reasonably.
Acknowledgments
The financial support from State Key Lab of Powder Metallurgy,
Central South University, Changsha, Hunan, China is greatly acknowl-
edged.
References
[1] J. Gröbner et al., J.Phase Equilib., 26 (2005) 234.
[2] R. Agarwal et al., Z. Metallkd., 83 (1992) 216.
[3] Y. Yuan et al., CALPHAD, 44 (2014) 54.
The influence of Li addition to ZnAl alloys on Cu substrate,
Tomasz Gancarz1,#, Janusz Pstrus1, Katarzyna Berent2
1
Institute of Metallurgy and Materials Science, Polish Academy of
Sciences, 30-059 Krakow, Poland
2
AGH University of Science and Technology, Academic Centre for
Materials and Nanotechnology, 30-059 Krakow, Poland
# - corresponding author, t.gancarz@imim.pl
Abstract
The spreading of Cu substrate by ZnAl eutectic-based alloys with
0.05, 0.1 and 0.2 wt% of Li additions were studied using the sessile drop
method in the presence of QJ201 flux. Wetting tests were performed
after 1, 3, 8, 15, 30 and 60 min of contact, at temperatures of 475, 500,
525 and 550 ˚C. Samples after spreading at 500 ˚C for 1 min were
subjected to aging for 1, 10 and 30 days at 120, 170 and 250 ˚C. The
spreadability of eutectic Zn-5.3Al alloy with different content Li on Cu
substrate was determined in accordance with ISO 9455-10:2013-03.
Selected, solidified solder-substrate couples, after spreading and aging
test, were cross-sectioned and subjected to scanning electron micro-
scopy, energy dispersive spectroscopy (EDS) and x-ray diffraction
(XRD) study of the interfacial microstructure. An experiment was de-
signed to demonstrate the effect of Li addition on the kinetics of for-
mation and growth of intermetallic CuZn, Cu5Zn8, CuZn4 phases
(IMCs), during spreading and aging. The formed IMCs layer at interface
were identified using XRD and EDS analysis. The increasing addition of
Li to ZnAl alloys caused reducing thickness of IMC layer at interface
during spreading and increasing during aging. The calculated activation
energy increasing for Cu5Zn8 phases and reducing for CuZn, CuZn4
phases with increasing Li content in ZnAl-Li alloys and the highest
value 142 (kJ.mol-1) obtained for ZnAl with 1.0 Li during spreading and
69.2 (kJ.mol-1) for ZnAl with 0.05 Li during aging. The aging at 250 ˚C
caused increased only Cu5Zn8 layer which has lowest Gibbs free energy
in Cu-Zn system and connected with high diffusion of Cu from substrate
to solder.
Keywords: ZnAl-Li, Spreading test, Lead-free solder, IMCs, Aging

Acknowledgement
This work was financed by the Minister of Science and High
Education of Poland grant IP2014 011473, in the years 2015-2017.
PC10
Phase equilibria in the Mn-Al-C system at crystallization
Bazhenova I.1, Fartushna I.1, Khvan A.1, Dinsdale A.1, Hallstedt B.2
1
Thermochemistry of Materials Scientific Research Centre, NUST
MISIS,
Leninsky prosp. 4, 119049 Moscow, Russia
2
Institute for Materials Applications in Mechanical Engineering,
RWTH Aachen University, Augustinerbach 4, 52062 Aachen, Germany.
Recently the attention of modern car producers has been drawn to a
new class of advanced high-strength steels with additions of manganese
and aluminum. Development of these new materials requires a good
thermodynamic description of the basic system Fe-Mn-Al-C. According
to the contemporary literature data, there are still some uncertainties in
the thermodynamic description of κ-carbide (Fe,Mn)3AlC and the so-
lubility of carbon in ferrite, which arise from the poor description of the
boundary system Mn-Al-C.
The information on phase equilibria in the Mn-Al-C system is lim-
ited to isothermal sections at 700 and 1000 ˚C [1]. The ternary com-
pound Mn3AlC (κ) (antiperovskite structure type CaTiO3, сР5-Pm-3m, a
= 3.86 Å [2]) was reported earlier. No experimental data on crystal-
lization of the alloys is available. Therefore, the goal of the present
research is to study the phase equilibria in the Mn-Al-C system on
crystallization.
Phase equilibria in the Mn-Al-C system were studied by DTA, X-ray
diffraction, SEM and EPMA. The liquidus and solidus projections and
the melting diagram (liquidus + solidus) were constructed. It was
shown that the ternary compound Mn3AlC (κ) melts congruently and
coexists with most of the phases based on the binary compounds.
The liquidus surface is characterized by the fields of primary crys-
tallization of phases based on the components, binary compounds and
the ternary κ-carbide. The carbide Mn5C2, which in the binary Mn-C
system is formed in the solid state by peritectoid reaction, participates
in equilibrium with the liquid phase in the ternary Mn-Al-C system. The
solidus surface of the Mn-Al-C system in the region up to 50 at.% Al is
defined by the co-existence of the κ-carbide with almost all phases of
the boundary systems. The solidus surface in the region >50 at.% Al is
defined by the co-existence of the carbide (Al4C3) with all phases of the
boundary systems. The (γMn)-phase dissolves about 30 at.% Al and 10
at.% C forming an elongated narrow phase region γ-Mn. Solubility of C
in phase (εAlMn) was established to be not less than 10 at.%. The κ-
carbide shows significant changes in the lattice parameter а = 3.828-
3.866 Å depending on the composition, which indicates the presence of
a region of homogeneity of this phase. Therefore, the κ-carbide cannot
be modeled as a stoichiometric compound. It is interesting that the
thermal heating curves of all alloys, which are located close to the
homogeneity region of phase (εAlMn), exhibit an exothermic effect at
478-579°C. This exothermic effect corresponds to the formation of the
metastable τ-phase, which is formed by mechanism: ε → ε' (B19) → τ.
In the alloy 55Mn-40Al-5C after DTA i.e. after slow cooling (5°C / min)
the ordered metastable phase τ (AuCu, tP2-P4/mmm, a = 2.760, c =
3.600 Å) is clearly visible according to XRD.
Acknowledgement
The authors gratefully acknowledge the financial support of the
Ministry of Education and Science of the Russian Federation in the
framework of RFMEFI58715X0023.
References
[1] J.C. Schuster, H. Nowotny, Z. Metallkd. 72 (1981) 63–66.
[2] A.L. Ivanovskii, Russ. J. Inorg. Chem. 41 (1996) 628-635.
PC11
Thermodynamic properties of rare earth sesquioxides
Yumin Zhang1, Guoqiang Lan2, Jun Song3 and In-Ho Jung4
53
Calphad xxx (xxxx) xxx–xxx
McGill University, Mining and Materials Engineering, Montreal,
Canada
(1yumin.zhang@mail.mcgill.ca; 2
guoqiang.lan@mail.mcgill.ca;
3 4
jun.song2@mcgill.ca; inho.jung@mcgill.ca)
In order to develop the thermodynamic database containing rare
earth sesquioxides, RE2O3, accurate thermodynamic description of all
stable and metastable RE2O3 phase are required. Rare earth sesqui-
oxides have numerous polymorphs, which are (from low to high tem-
perature) the cubic phase (labelled C), the monoclinic phase (B), the
hexagonal phase (A), the high temperature hexagonal phase (H), and
the high temperature cubic phase (X). However, the thermodynamic
property data available for these different polymorphous are relatively
insufficient especially for the high temperature region and also for
metastable form.
In this study, all Δ??o298, ??o298, CP (or heat content) and phase
transition temperature (Ttr) data available in the literature were col-
lected and critically evaluated for each rare earth sesquioxide based on
the experimental procedures and techniques employed. Relationships
between Δ??o298, ??o298, and Ttr against the ionic radii of the whole rare
earth sesquioxide series were then established and missing thermo-
dynamic information was predicted. In general, the enthalpy (ΔHtr) and
entropy (ΔStr) changes of the C – B, B – A, A – H, and H – X transitions
are either scarce or nonexistent. For the C – B and B – A transitions,
experimental enthalpy data and entropies extracted using the Clausius –
Clapeyron relation were collected from the literature and employed
together with results obtained from Density Functional Theory (DFT)
calculations to estimate the ΔHtr and ΔStr. For the A – H and H – X
transitions, the ΔHtr were calculated using optimized crystal structures
of the H and X phases and DFT calculations, while the ΔStr were cal-
culated using these obtained ΔHtr and critically evaluated Ttr. In these
way, the Gibbs energies of all stable and metastable RE2O3 phases (RE
= Y, Sc, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu)
are prepared for the expansion to binary and multicomponent system.
PC12
Effect of Ni content on the ferrite-to-austenite transformation
during austenitizing in spheroidal graphite cast iron
Tatsuya Tokunaga1, Tatsuki Furukawa2, Hidenori Era1
1
Department of Materials Science and Engineering, Kyushu
Institute of Technology, Kitakyushu 804-8550, Japan
2
Graduate School of Engineering, Kyushu Institute of Technology,
Now at Saveway Japan Co., Ltd., Kitakyushu 805-0012, Japan
The effect of Ni content on the ferrite-to-austenite transformation
during austenitization in spheroidal graphite cast iron with a ferrite
matrix was investigated. In this study, ferritic Si-solution strerngthend
ductile cast irons (SSFDI) with different Ni contents, namely, 0, 0.1, 0.5
and 1.0 mass%Ni, were used. The samples were immersed in molten Al
alloy baths heated at temperatures between 850 ˚C and 900 ˚C and held
at these temperatures for various periods, after which the samples were
quenched in water to interrupt the ferrite-to-austenite transformation.
Microstructural observation was carried out using optical microscopy
and the fraction of martensite obtained after quenching was evaluated
as the fraction transformed to austenite during austenitization. The
distribution of constituent elements was investigated by means of
electron probe micro analysis (EPMA). Microstructural observation re-
vealed that the rate of the ferrite-to-austenite transformation increased
with increasing Ni content. EPMA showed that Si and Ni segregated
near the graphite nodules while Mn segregated at the eutectic cell
boundary in the as-cast SSFDI samples. In addition to the experiments, a
simulation of the austenitization was performed for SSFDI with dif-
ferent Ni contents using the DICTRA software package [1] employing
kinetic and thermodynamic databases. The calculated progress of the
isothermal austenite transformation for SSFDIs at various temperatures
was found to reproduce the observed results well.

Reference
[1] J.-O. Andersson, L. Höglund, B. Jönsson and J. Ågren:
Fundamentals and Applications of Ternary Diffusion, Ed. by G. R. Purdy,
Pergamon Press, New York, 1990, pp. 153–163.
PC13
Experimental determination and thermodynamic calculation of
isothermal sections at B2O3-rich corner in the BaO-In2O3-B2O3
system
Xing Fan, Liumei Su, Gemei Cai*, Zhanpeng Jin*
School of Materials Science and Engineering, Central South
University, Changsha, 410083, China
*E-mail addresses: caigemei@csu.edu.cn (Gemei Cai), jin@csu.e-
du.cn (Zhanpeng Jin).
Scintillators are materials which can efficiently absorb high energy
radiation and convert it into radiation with a wavelength in or around
the visible spectral region. In the BaO-In2O3-B2O3 system, the com-
pound Ba3InB9O18 possesses an excellent scintillation property which
makes it a good candidate for high energy detection[1]. In practice,
scintillators are usually single crystals, so it is necessary to grow single
crystal of Ba3InB9O18. Technological process of single crystal growth
needs to refer to phase diagrams, but in BaO-In2O3-B2O3 system only
the subsolidus phase relations[2] have been studied. Under this cir-
cumstance, the melting type of Ba3InB9O18 was examined, and iso-
thermal sections atBO1.5-rich corner were measured.
The thermal stability of Ba3InB9O18 was studied through melting
and quenching method. Results showed that Ba3InB9O18 melts incon-
gruently into InBO3 and liquid at ～1025 ˚C. Isothermal sections of 900,
950, 1000, 1025, 1050 ˚C at B2O3-rich corner were measured with
EPMA and XRD. Two constraint conditions (tie-line and Ba/In mole
ratio) were adopted to determine the composition of liquid phase.
Based on the established isothermal sections, primary crystal region of
Ba3InB9O18 was determined, which will be benefit to designing com-
position and process for crystal growth.
Based on the existingexperimental data, thermodynamic parameters
can be calcutaled by the means of CALPHAD method using the Thermo-
calc software package[3]. The two-sublattice ionic liquid model
(In3+,Ba2+)p(O2-, BO33-,B4O72-, B3O4.5)Q[4] was adopted todescribe
theliquidphase,and solid phases were treated as stoichiometric com-
pounds whose Gibbs energy was modeled following Neumann–Kopp's
rule [5]. A set of self-consistent thermodynamic parameters are ob-
tained. Due to the short of experiments, these parameters may only be
valid in limited temperature and composition range. Present in-
vestigations may be useful for the whole ceramic community working
with BaO-In2O3-B2O3 systemas well as for the development of func-
tional materials.
Acknowledgments
Financial supports by grants from the Major State Basic Research
Development Program of China (No. 2014CB6644002), the National
Natural Science Foundation of China (No. 51472273), the Hunan
Provincial Science and Technology Department (No. 2014FJ4099) and
the Project of Innovation-driven Planin Central South University
(2015CX004).
References
[1] G. Cai, et al., A new promising scintillator Ba3InB9O18, Journal
of Solid State Chemistry, 181 (2008)646-651.
[2] G.M. Cai, et al., Crystal structure and photoluminescence of
Tb3+-activated Ba3InB9O18, Materials ChemistryandPhysics,
129(2011)761-768.
[3] B. Sundman, etal., The Thermo-Calc databank system,
Calphad,9(1985)153-190.
[4] H. Yu, et al., Thermodynamic reassessment of the BaO-B2O3
system, Joural of Phase Equilibria, 20(1999)479-484.
[5] H. Kopp, Investigations of the Specific Heat of Solid Bodies,
Philosophical Transactions of the RoyalSocietyofLondon, 155(1865)71-202.
54
Calphad xxx (xxxx) xxx–xxx
PC14
Thermodynamic assessment of the Fe-Mn-H system
Evgeny Syutkin1, Alexandra V Khvan1, Alan T Dinsdale1
1
Thermochemistry of Materials Scientific Research Centre, NUST
MISIS,
Leninsky prosp. 4, 119049 Moscow, Russia
TWinning Induced Plasticity (TWIP) steels have become of great
interest over the last few years because of their excellent combination
of mechanical properties. However, some of these types of steels are
susceptible to hydrogen embrittlement.
As a part of a thermodynamic analysis of the effect of hydrogen on
the embrittlement of steels, a CALPHAD-type assessment of the Fe-Mn-
H system has been carried out. In order to improve the thermodynamic
description of ternary system it has been necessary to revise the ther-
modynamic descriptions of the Mn-H and Fe-H systems by in-
corporating pressure dependence. In this work the Gibbs energies of the
individual phases were modeled, and the model parameters were ob-
tained from best fit optimizations to available experimental and first-
principles calculation data.
A very satisfactory description of the system has finally been ob-
tained and this will be discussed in this paper.
PC15
Phase Diagram of the Fe-Pd-Y Ternary system at 773K
Y.S. Du1, 2, G. Cheng1, 2, X.F. Wu1, 2, X.L. Xu1, L.Y. Cheng1, Z.F.Gu,
G.H.Rao
1
. School of Materials Science and Engineering, Guilin University of
Electronic Technology, Guilin 541004, China e-mail: Cheng59@gue-
t.edu.cn
2
. Guangxi Key Laboratory of Information Materials, Guilin 541004,
China)
Abstract: The solid-state phase equilibrium in the Fe-Pd-Y ternary
system at 773K was investigated by X-ray diffraction (XRD), scanning
electron microscopy (SEM) and energy dispersion spectroscopy (EDS)
techniques. The existence of 14 binary compounds, Fe17Y2 (Ni17Th2
structure), Fe23Y6 (Mn23Th6 structure), Fe3Y (PuNi3 structure), Fe2Y
(Cu2Mg structure), FePd (AuCu structure), FePd3 (AuCu3 structure),
Pd3Y (Cu3Au structure), Pd2Y, Pd3Y2, Pd4Y3 (Pd4Pu3 structure), PdY
(CrB structure), Pd2Y3 (Er3Ni2 structure), Pd2Y5 (Dy5Pd2 structure) and
PdY3 (Fe3C structure) was confirmed. The 773K isothermal section
consists of 17 single-phase regions, 32 two-phase regions, and 16 three-
phase regions. At 773 K, it is confirmed that the maximum solid solu-
bility of Y in γ-(Fe, Pd), FePd and FePd3 are roughly 1 at.% Y. There are
almost no solid solubility of Fe in the compounds Pd3Y, Pd2Y, Pd3Y2,
Pd4Y3, PdY, Pd2Y3, Pd2Y5 and PdY3. No ternary compounds were ob-
served.
Acknowledgements
This study was supported by the National Nature Science
Foundation of China (Grant No: 51261004, 51161005) and the
National Basic Research Program of China (Grant No: 2014CB643703).
References
[1]. W. Zhang , G. Liu, , K. Han, in: "Phase Diagrams of Binary Iron
Alloys", H. Okamoto (ed.), Materials Information Soc., Materials Park,
Ohio (1993)
[2]. O. Loebich, Jr. and E. Raub, J. Less-Common Met. 30 (1973) 47
[3]. H. Okamoto, in: "Phase Diagrams of Binary Iron Alloys",
Materials Information Soc. Materials Park, Ohio (1993).
PC16
Experimental investigation of Phase relations in the Gd-Mn-As
system at 773K
Z. F. Gu*, K. Hu, G.Cheng, L.Ma, Ch.F.Xu, L.J.Hong, R.S.Lin
Faculty of Material Science and Engineering, Guilin University of
Electronic and Technology, Guilin 541004, PR China
*e-mail:gzfwzi88@163.com

Abstract
Phase relations in the ternary Gd-Mn-As system at 773K were in-
vestigated experimentally by X-ray diffraction (XRD), scanning electron
microscopy (SEM) and Energy Dispersive Spectroscopy (EDS) techni-
ques. The isothermal section consists of 12 single-phase regions, 21
two-phase regions and 10 three-phase regions. The presence of 9 binary
compounds Mn3As，Mn2As，αMn3As2，Mn4As3，γMnAs，GdAs，
Mn2Gd，Mn23Gd6and Mn12Gdwasconfirmed. No compounds exist in
the region of more than 50at%As. The maximum solubility of Mn in
GdAs compound is about 0.824at. % Mn and Gd in γMnAs compound is
about 0.58 at. % Gd.No new compound was found.
References
[1] H. Okamoto, The As-Mn (arsenic-Manganese) system, Bulletin of
alloy phase diagrams 10(5) (1989) 549
[2] K.A. Gschneidner et.al., The As-Gd (arsenic-Gadolinium) system,
Bulletin of alloy phase diagrams 7(4) (1986) 340 [3]J. Grobner, A.
Pisch, R. Schmid-Fetzer J.Alloys Compds 317-318(2001)433 .
Acknowledgments
This workwas supported by the National Nature Science Foundation
of China (GrantNo: 51161005, 51261004) and the National Basic
Research Program of China (Grant No: 2014CB643703)
PC17
Thermodynamic Calculation of phase equilibria in the Nb-Ni-Zr
ternary Amorphous Alloy
Dhanesh Chanra
University of Nevada Reno, Reno, Nevada, USA
As an excellent candidate of metallic glasses with high corrosion
resistance and high thermal stability, the Ni-Nb-Zr metal alloy (Ni-
based composite materials) has attracted much attention. In order to
better understand the amorphous behavior for Ni-Nb-Zr metal alloy, it
is necessary to explore the polymorphism of phase equilibria in Ni-Nb-
Zr ternary system. Therefore, a thermodynamic study of phase equili-
bria in the Ni-Nb-Zr ternary system has been carried out by using the
CALPHAD method with a simple ternary extrapolation of constituent
binary systems, ternary parameters were optimized and procured de-
pending on experimental information such as in-situ X-ray diffraction
(XRD) and Differential scanning calorimetry (DSC) for these ternary
systems. To enable the thermodynamic description of the constituent
binary systems, the results from a previous evaluation were adopted for
the Nb-Ni, Nb-Zr, and Ni-Zr binary systems. In this study, the ternary
isothermal sections at 25 ˚C, 200 ˚C, 250 ˚C, 300 ˚C, 350 ˚C, 400 ˚C and
pseudobinary isopleth sections with various compositional combination
were calculated for Ni-Nb-Zr ternary systems. Furthermore, the liquidus
surface projection of Ni-Nb-Zr ternary system was studied and 9 types
of ternary invariant reactions in the Ni-Nb-Zr system were presented in
this work.
PC18
L21/C1b order-disorder transformation and phase decomposi-
tion in NiMn1-xTixSb alloys
Ryosuke Umino, Xiao Xu, Ryosuke Kainuma
Department of Materials Science, Tohoku University, Aobayama 6-
6-02, Sendai 980-8579, JAPAN
Half metals are widely used in the field of spintronics due to its high
degree of spin polarization. NiMnSb is well known as one of the first
reported half-metallic ferromagnetic alloy [1]. However, it is difficult to
obtain high spin polarizations experimentally [2]. This is because of the
occurrence of disordering. Comparing the two Heusler structures, if the
C1b structure is considered as the result of ordering of Ni and vacancies,
the L21 structure is the result of disordering of them. NiMnSb trans-
forms from C1b to L21 structure at about 850 ˚C with the C1b structure
55
Calphad xxx (xxxx) xxx–xxx
being stable at low temperatures [2, 3]. In this study, increasing the
L21/C1b order-disorder transformation temperature was attempted and
the phase diagram of Ni-Mn-Ti-Sb system including order-disorder
transformation temperature and Curie temperature was experimentally
investigated.
Ni-Mn-Ti-Sb alloys made by arc melting were heat-treated at around
1050 ˚C. The phase diagram was determined by composition mea-
surements by EPMA, thermal analysis by DSC and thermal magnetic
analysis by VSM.
Figure 1 shows the NiMnSb-NiTiSb pseudobinary phase diagram. It
was found that the two-phase region of L21 and C1b exists from com-
position substituted by 3% Ti for Mn. The two-phase region expands
with increasing temperature and transformation temperature from C1b
to L21 increases due to the addition of Ti. The magnetic properties were
also evaluated at low temperatures. The magnetization well obeys the
Generated Slater-Pauling rule (GSP) [4] for half-Heusler alloys until
30% substitution of Ti for Mn. Therefore there is a possibility that the
alloys show half-metallic property up to this composition.
References
[1] R. A. de Groot et al., Phys. Rev. Lett., 50 (1983) 2024.
[2] D. Orgassa et al., Phys. Rev. B, 60 (1999) 13237-13240.
[3] M. Nagasako et al., Intermetallics, 61 (2015) 38-41.
[4] I. Galanakis and P. H. Dederichs, Phys. Rev. B, 66 (2002)
134428.
PC19
Numerical simulation for diffusion couple including stoichio-
metric compound phase by using non-equilibrium multi-phase-
field model coupled with CALPHAD database
Sukeharu Nomoto1, Shigeyuki Tamura1, Yuki Matsuzaki1, Masaki
Kurata2
1
Science & Engineering Systems Division, ITOCHU Techno-
Solutions Corporation, Kasumigaseki Bldg., 3-2-5, kasumigaseki,
Chiyoda-ku, Tokyo 100-6080, Japan
2
High Temperature Fuel Science R&D group, Nuclear Science and
Engineering Directorate, Japan Atomic Energy Agency,
Shirakatashirane 2-4, Tokai-mura, Ibaraki-ken 319-1195, Japan
The multi-phase-field (MPF) method coupled with CALPHAD data-
base is applied to simulate reaction of the diffusion couple that consists
of stainless steel and B4C. In this reaction, the interface region of
stainless steel and B4C melts in high temperature with strong non-
equilibrium interfacial condition in the early stage. We introduce a MPF
model with finite interface dissipation proposed by Steinbach et al.,
which is based on non-equal diffusion potential assumption. We de-
velop the MPF code in order to estimate the liquid phase growth rate by
developing numerical model of the stoichiometric compound of B4C

phase. The numerical simulations are performed by onedimensional
model in the uniform holding temperature from 1450K to 1700K. The
stainless steel phase is assumed as FCC of composition, Fe(bul.)-18%Cr-
8%Ni-0.01%C. CALPHAD database developed in JAEA is applied to
these calculations. Diffusivity values of FCC phase are estimated from
DICTRA diffusion database. The experimentally measured parabolic
rule of liquid phase growth is confirmed after initial transitional stage
in the condition of uniform holding temperature. We find this system is
controlled by liquid phase diffusivity. Next, we calibrate Arrhenius-type
diffusion coefficient values of liquid phase to obtain the same experi-
mentally measured parabolic rate constant from 1450K to 1700K.
Finally, This MPF code is applied to simulation in the realistic tem-
perature profile condition obtained by macroscopic numerical analysis
of the nuclear reactor model.
Acknowlegement
A part of this study was performed in “Advanced Multi-scale
Modeling and Experimental Tests for Fuel Degradation in Severe
Accident Conditions in JFY2014”, which was supported by METI
(Ministry of Economy, Trade, and Industry) in Japan.
PC20
Thermochemical Measurements for the Yellow Phases Formed
in Nuclear Fuel Waste Glasses: The OECD/NEA Mo TDB Project
Masao Morishita1, Hiroki Houshiyama2, Motohiro Fukushima2 and
Yoshiki Kinoshita2
1
Dept. Chem. Eng. and Mater. Sci., Univ. Hyogo, 2167 Shosha,
Himeji, Hyogo 671-2280, JAPAN
2
Graduate Students of Univ. Hyogo, 2167 Shosha, Himeji, Hyogo
671-2280, JAPAN
The OECD/NEA Thermochemical Database (TDB) Project
(www.oecd-nea.org/dbtdb/) provides a database of chemical thermo-
dynamic values treating the most significant elements related to nuclear
waste management [1]. The present investigation was carried out as a
part of the Mo TDB project. Molybdenum is generated as fission product
from uranium in the operating nuclear reactor. It is a harmful element
as it forms hygroscopic crystals, known as "yellow phases" in bor-
osilicate nuclear waste glasses. The host crystals of the yellow phases
are Na2Moa4 and CaMoO4 depending on the composition and process
for making nuclear waste glasses. In order to understand the phase
stability of the yellow phases, thermodynamic properties for the end
members should be inevitably necessary. In the present study, the C°p,m
data for CaMoO4, SrMo04[2], BaMoO4 [3] and Ag2MoO4 were mea-
sured from 2 K for the first time.
Figure 1 shows the C°p,m data for BaMoO4 at 2-400 K by relaxation
method [3] and at 500-1250 K by DSC, compared with ones by drop
carolimetry by Singh et al.[4]. The third law entropy, S°m(TK), as a
function of the tempearature,T, were determined from the the present
obtained C°p, m via Debye-Einstein function below 298.15 K and Haas
-Fisher polynomal over 298.15 K. Its ΔfG°m (TK) from low to high
tempearature were determined by combining S°m (TK) obtained with
ΔfH°m (298.15K) re-evaluated by Gamjager and Morishita [5].
As in the same way, the ΔfG°m (TK) data for CaMoO4, SrMoO4 and
Ag2MoO4 were determined. The end members of the yellow phases are
found to be very stable, indicating that enough cooling rate should be
kept for depressing crystallization of the yellow phases during waste
glass making.
56
Calphad xxx (xxxx) xxx–xxx
References
[1] M.E. Ragoussi and S. Brassinnes, Radiochim. Acta.,103 (2015)
679-685.
[2] M. Morishita and H. Houshiyama, Mater. Trans., 56 (2015) 545-
549.
[3] M. Morishita, et al. Mater. Trans., 57 (2016) 46-51.
[4] Z. Singh, et al., J. Alloys and Compd., 279. (1998) 287-294.
[5] H. Gamsjager and M.Morishita, Pure and Appl. Chem., 87(2015)
461-47
PC21
Thermodynamic analysis of BCC/FCC martensitic transforma-
tion in the Fe-Mn-Al system
Toshihiro Omori1, Ikuo Ohnuma2, Kiyohito Ishida1, Ryosuke
Kainuma1
1
Department of Materials Science, Graduate School of Engineering,
Tohoku University, Aoba-yama 6-6-02, Sendai 980-8579, Japan
2
Computational Materials Science Unit, National Institute for
Materials Science (NIMS), 1-2-1 Sengen, Tsukuba 305-0047, Japan
It is known that the γ phase (FCC) in many Fe-based alloys under-
goes martensitic transformation to the α’ phase (BCC, BCT) or ε phase
(HCP). On the other hand, although being rare in Fe-based alloys, the α
phase (BCC) martensitically transforms to the γ phase in Fe-Mn-Al al-
loys. In the present study, thermodynamic analysis of the α/γ trans-
formation in Fe-Mn-Al alloys was carried out by the CALPHAD method,
and the transformation was experimentally investigated.
Figures 1(a) and 1(b) show the calculated differences in Gibbs en-
ergy ΔGα/γ and that in entropy ΔSα/γ between the α and γ phases in Fe-
20Mn-10Al and Fe-36Mn-16.5Al alloys (at%), respectively, where the
magnetic term (Hillert and Jarl model) is included or excluded. In Fe-
20Mn-10Al alloy, ΔSα/γ with magnetic term abruptly increases with
decreasing temperature although ΔSα/γ without magnetic term is ne-
gative. As a result, ΔGα/γ increases with decreasing temperature due to
the magnetic contribution of the α phase, meaning the occurrence of γ/
α transformation. Decrease of the Curie temperature reduces the effect
of magnetic contribution and ΔSα/γ becomes negative in Fe36Mn-
16.5Al alloy. Therefore, the γ/α transformation does not occur, but the
α/γ transformation is predicted from the calculation of ΔGα/γ. The
calculated equilibrium temperature T0 lines and Curie temperature of
Fe-Mn-Al are shown in Fig. 1(c). The γ loop diminishes in 36Mn alloy,
suggesting the α/γ martensitic transformation. It was experimentally
found that Fe-36Mn-15Al alloy exhibits the martensitic transformation
from α to γ[1]. Furthermore, Fe-34Mn-15Al-7.5Ni alloy shows super-
elasticity with low dependence of critical stress for transformation due
to low ΔSα/γ[2].

References
[1] K. Ando et al., Appl. Phys. Lett., 95 (2009) 212504.
[2] T. Omori et al., Science, 333 (2011) 68.
[3] R. Umino et al., J. Phase Equil. Diff., 27 (2006) 54.
PC22
Microstructure and magnetic properties of amorphous/crys-
talline composite ribbons in Fe-Zr-Si-B-Cu immiscible alloys
J.H.Zhu, C.P.Wang, S.Y.Yang, J.J.Han, Y.H.Guo, Y.Lu,X.J.Liu*
Department of Materials Science and Engineering, College of
Materials, Xiamen University, Xiamen361005, P.R.China
E-mail:lxj@xmu.edu.cn
ABSTRACT: Based on the CALPHAD (Calculated of Phase Diagrams)
approach, a series novel micro-scale amorphous/crystalline composite rib-
bons of (Fe0.75Zr0.2Si0.8B0.15)100-xCux (x = 5, 15, 25, 35, 45, 60, at.%) alloys
were designed and successfully fabricated by using melt-spinning method in
this study. The designed compositions of Fe-Zr-Si-B-Cu exhibit an obvious
two-liquid miscibility phase equilibrium in the liquid-temperature region
(see in Fig. 1). The prepared ribbons show a Fe-Zr-Si-B rich amorphous/Cu-
rich crystalline composite microstructure. The microstructure of the prepared
ribbons changedfrom droplet-type to double layer type and sandwich type
microstructures with the increasing of the copper content (see in Fig. 2).
Meanwhile, the effect of cooling rate on the microstructure was also in-
vestigated. The coercive force of the composite ribbons almost the same as
Fe75Zr2Si8B15 amorphous ribbon, but their saturation magnetization de-
creases with increasing Cu content. The formation mechanism of the pre-
pared composite ribbon is originated from the occurrence of liquid phase
separation at high temperature and the different glass-forming ability (GFA)
of the two separated liquids during the rapid solidificationprocess.
57
Calphad xxx (xxxx) xxx–xxx
Acknowledgments
This work was supported by the National Natural Science
Foundation of China (Grant No. 51471138) and the Ministry of
Education of China (GrantNo.20120121130004).
PC23
Experimental investigation of phase equilibria in the Nb-Si-V
system
J.Li1, S.Y.Yang1,2, Z.Shi1,2, C.P.Wang1,2, X.J.Liu1,2,*
1
. Department of Materials Science and Engineering, College of
Materials, XiamenUniversity, Xiamen 361005, P.R.China
2
. Research Center of Materials Design and Applications, Xiamen
University, Xiamen 361005, P.R.China
*Correspondingauthor:lxj@xmu.edu.cn
Abstract
Alloying Vanadium can bring some visible microstructural change
and improvement of mechanical properties of Nb-Si based alloys. In
order to well understand the effects of V on the microstructures and
properties of Nb-Si based alloys, the knowledge of phaseequilibria in
theNb-Si-V system is prerequisite. However, the phase equilibria about
Nb-Si-Vsystem were rare. In this study, the phase equilibria in the Nb-
Si-Vternary system at 1373 K , 1473 K and 1573 K (Fig. 1) were in-
vestigated by means of back-scattered electron (BSE), electron probe
microanalysis (EPMA) and X-ray diffraction (XRD).The (Nb,V)2Si
compound is found in all these three isothermal sections for the first
time. The compounds NbSi2 and VSi2 form a complete solid solution
phase (Nb, V)Si2. The solubilities of Nb in V6Si5 phase and V5Si3 phase,
as well as the solubility of V in the αNb5Si3 phase, are very large.
Whereas the solubility of Nb in the V3Si phase and the solubility of Si in

the β(Nb,V) phase are relatively small.
Acknowledgments
This work is supported by the National Natural Science Foundation
of China (Grant No. 51471138), the Ministry of Education of China
(Grant Nos. 20120120130004) .The supports from the China Aviation
Industry Group are also acknowledged.
PC24
Thermodynamic evaluation of molten-core concrete interac-
tion
Toru Kitagaki1, Hirotomo Ikeuchi1, Kimihiko Yano1, Hideki Ogino1,
Tadahiro Washiya1
1 [2] C. Journeau et al., Materials Science and Engineering, A299
Japan Atomic Energy Agency, 4-33 Muramatsu, Tokai-mura,
Ibaraki, 319-1194 Japan
In a severe accident at light water reactors, molten-core may pe-
netrate the reactor vessel and react with concrete in the containment
vessel. The interaction between molten-core and concrete is compli-
cated phenomena because of high temperature reaction of multiple
components. Various kinds of simulation codes on molten-core concrete
interaction (MCCI) have been developed to predict concrete ablation
and vessel penetration. Although solidification phenomena effect MCCI
progression such as crust growth which is the reaction between the
concrete and the molten pool and thermal properties such as viscosity
of molten pool, only some simulation codes install thermodynamic
database to decide the liquidus and solidus temperature of oxide molten
pool [1]. The simplification of solidification phenomena increases un-
certainty about the calculation results. In this study, solidification
phenomena on the mixture of molten-core and concrete in assumable
conditions are discussed based on thermodynamic equilibrium calcu-
lation. The composition of molten-core and concrete was determined
from typical BWR core component and basalt concrete, respectively.
The mixture ratio of concrete in molten-core, solidification model and
oxidation potential were set as main parameter. Phase equilibria during
solidification from melting temperature were calculated by thermo-
dynamic calculation tool: FactSage 6.2 and NUCLEA database.
In the equilibrium and low oxygen condition, (U,Zr)O2, (Zr,U)SiO4
and CaAl2Si2O8 are formed in sequence from liquidus temperature. On
the other hands, in the quench condition such as crust formation esti-
mated by scheil cooling model, the amount of (Zr,U)SiO4 is limited.
58
Calphad xxx (xxxx) xxx–xxx
This indicates that ZrO2 is separated from (U,Zr)O2 produced in molten
pool, it reacts with SiO2 and (Zr,U)SiO4 is produced. This tendency is
confirmed in experimental results [2]. Moreover, in the high oxygen
potential condition, thermodynamic calculation shows that (Zr,U)SiO4
is immediately formed just below liquidus temperature. CaAl2Si2O8 is
composed of CaO, Al2O3 and SiO2. The formation behavior of (Zr,U)
SiO4 and CaAl2Si2O8 is the key factor on solidification phenomena and
effects to the estimation of MCCI phenomena and MCCI products. It will
be discussed from the view point of the critical cooling rate and oxygen
potential. The formarion behavior of them in actual condition shoud be
considered in the MCCI calculation.
References
[1] M. Cranga et al., Progress in Nuclear Energy, 52 (2010) 76–83.
(2001) 249-266.
PC25
Evaluation of nano-sized internal oxidation in a Fe-13Cr alloy
exposed to water vapor atmosphere
Fernando Rizzo1, Leonardo Agudo Jácome2, María Mosquera
Feijoo2, Gert Nolze2, Axel Kranzmann2, André Costa e Silva3
1
Department of Chemical and Materials Engineering, PUC-Rio and
Instituto Nacional de Tecnologia (INT), Rio de Janeiro, RJ, Brazil
2
Department 5.1, Federal Institute for Materials Research and
Testing (BAM); Unter den Eichen 87, 12205 Berlin, Germany
3
EEIMVR-UFF, Av Trabalhadores 420, Volta Redonda, RJ, Brazil
The topotactic formation of nano-sized precipitates immediately
under the internal oxide layer in a Fe-13Cr alloy exposed to oxidizing
water vapor atmosphere was recently reported [1]. The precipitates
were identified as lath-shaped Fe-Cr spinel exhibiting a crystallographic
orientation relationship with the ferritic matrix. The authors proposed
that these precipitates could act as a precursor to the formation of the
spinel layer observed in the adjacent part of the oxide scale. The oc-
currence of internal oxidation in Fe–Cr alloys subjected to similar
conditions had been previously identified [2-5] and directly correlated
to the presence of water vapor. In the present work, we attempt to
rationalize the processes occurring during the oxidation of this alloy
through thermodynamic and kinetic analysis based on the CALPHAD
approach, using the geometrical representation of phase equilibria [6]
and concepts developed to describe internal oxidation [7-10]. The

influence of water vapor on the mechanism and kinetics of formation of
the nano-sized precipitates and its role in the overall oxidation process
is also considered.
References
[1] LA Jácome, MM Feijoo, G Nolze, F Rizzo. Nano-sized pre-
cipitates in an Fe-13Cr alloy formed under oxidizing water atmosphere,
In: International Conference on Solid-Solid Phase Transformations in
Inorganic Materials (PTM 2015), Whistler, BC, Canada; 2015: 379-386.
[2] E Essumana, GH Meier, J Żurek, M Hänsel, WJ Quadakkers. The
Effect of Water Vapor on Selective Oxidation of Fe–Cr Alloys. Oxidation
of Metals. 2008 Apr; 69(3-4):143–62.
[3] N. K. Othman, N. Othman, J. Zhang and D. J. Young, Corrosion
Science 51, 3039 (2009)
[4] D. Hünert, W. Schulz, and A. Kranzmann. Corrosion,
66(12):126001 (p.7), 2010.
[5] T. Jonsson, B. Pujilaksono, H. Heidari, F. Liu, J. E. Svensson, M.
Halvarsson and L. G. Johansson, Corrosion Science 75, 326 (2013).
[6] AD Pelton, H Schmalzried, On the geometrical representation of
phase equilibria. Metallurgical Transactions. 1973;4(May):1395–404.
[7] GR. Laflamme, JE. Morral, Limiting Cases of Subscale
Formation, Acta Metallurgica. 1978; 26: 1791-1794.
[8] Y Li, JE Morral. A local equilibrium model for internal oxida-
tion. Acta materialia. 2002;50(14):3683–91.
[9] JE Morral, Y Li. Internal oxidation and local equilibrium.
Materials at High Temperatures. 2003;20(3):273–5.
[10] J Agren, H Larsson, L Höglund. Thermodynamic and kinetic
modelling of internal oxidation. In: CALPHAD 2014. 2014.
PC26
Phase Equilibria of the Cu-Co-Zn System at 450 and 600 ˚C
Manxiu Zhao*, Bihong Chen, Fucheng Yin, Huixin Liu, Yongxiong
Liu
Key Laboratory of Materials Design and Preparation Technology of
Hunan Province, School of Materials Science and Engineering, Xiangtan
University, 411105, Hunan, P.R. China
*E-mail: zhaomanxiu@xtu.edu.cn
The 450 and 600˚C isothermal sections of the Cu-Co-Zn ternary
system have been investigated experimentally by means of scanning
electron microscopy coupled with energy dispersive x-ray spectroscopy,
and x-ray diffraction. Six three-phase regions exist in the isothermal
section at 450 ˚C, and five three-phase regions at 600 ˚C. The γ-Co5Zn21
and Γ-Cu5Zn8 form a continuous solid solution, which is designated as
the γ/Γ phase. No ternary compound is found. The maximum solubility
of Co in ε, and β’is 8.5 and 6.7 at.%, and the solubility of Cu in γ2, γ1
and β1 is up to 12.9, 14.4 and 11.2 at.% at 450 ˚C. The solubility of Co
in δ and β is up to 1.8 and 8.8 at.%, and the maximum solubility of Cu
in γ1 and β1 is 14.7 and 7.9 at.% at 600 ˚C
59
Calphad xxx (xxxx) xxx–xxx
Acknowledgments
This investigation was supported by National Natural Science
Foundation of China (No. 51471141) and (No. 51471140), Scientific
Research Fund of Hunan Provincial Science and Technology
Department (No. 2014FJ2010).
References
[1] G.P. Vassilevet al., J. Phase Equilib. Diff. 25(2004) 259-268.
[2] M.X. Zhaoet al.,J. Phase Equilib. Diff. 32 (2011) 183-192.
[3]W. Gierlotka. J. Mater, Res. 23(2008) 258-263.
[4]M. Palumboet al., Calphad. 30(2006) 171-178.
PC27
Phase Equilibria in the Fe-B-W system: Experiment and
Thermodynamic Modeling
Xuemei Ou Yang, Fucheng Yin*, Yongxiong Liu, Manxiu Zhao
Key Laboratory of Materials Design and Preparation Technology of
Hunan Province, School of Materials Science and Engineering, Xiangtan
University, 411105, Hunan, P.R. China
*Corresponding author.E-mail address: fuchengyin@xtu.edu.cn
The present work investigates the effect of the alloying element W
on the solidification process of the Fe-B alloy. The liquidus projection of
the Fe-B-W system in the Fe-rich corner was determined by identifying
primary crystallization phases in the as-cast alloys and from the li-
quidus temperatures obtained from the DSC analyses. The isothermal
section of the Fe-B-W system at 1323K has been investigated experi-
mentally using SEM-WDS, EPMA and X-ray. The formation enthalpy of
two ternary compound τ1-WFeB (-55.746kJ/mol), τ2-W2FeB2(-
62.262kJ/mol) were calculated using the first principle calculation.
Based on the available data from the literature [1-2] and the present
work, thermodynamic modeling of the Fe-B-W ternary system was
performed using the Calculation of Phase Diagram (Calphad) approach.
A set of self-consistent thermodynamic parameters of the Fe-B-W
ternary system was obtainedwith a good agreement between experi-
mental and calculated results.
Acknowledgments
This work was supported by national Natural Science Foundation of
china (No. 51471141), Scientific Research Fund of Hunan Provincial
Science and Technology Department (No. 2014FJ2010).
References
[1] Haschke, H et al., Monatsh. Chem., 97 (1966) 1459–1468
[2] A. Leithe-Jasper et al., J. Jpn. Inst. Met., 64 (2000) 154-162.

PC28
Phase diagrams of Ag-Sb-Ni and Ag-Ge-Ni ternary systems
Sinn-wen Chen, Ling-chieh Chen, Jen-chieh Wang and Po-han Lin
Department of Chemical Engineering, National Tsing Hua
University No. 101, Sec. 1, Kuang-fuh Road, Hsinchu 30013, Taiwan
Thermoelectric modules have attracted intensive research interests
because they can convert waste heat directly into electricity and en-
hance energy usage efficiencies. A thermoelectric module is usually
composed of arrays of thermoelectric P-N junctions. There are thus
numerous joints in a thermoelectric module. Ag-Sb eutectic and Ag-Ge
eutectic alloys are promising candidates as the joining materials for the
mid-temperature thermoelectric modules. In order to avoid interfacial
reactions between joining materials and thermoelectric materials,
nickel is commonly used as the barrier layer. The interfacial reactions
between Ni and the eutectic Ag-Sb and Ag-Ge alloys are crucial for the
properties and reliabilities of the thermoelectric modules using Ag-Sb
and Ag-Ge as joining alloys. Phase diagrams contain phase equilibria
information and are fundamentally important for understanding and
illustration of interfacial reactions. This study thus determines the
phase diagrams of the Ag-Sb-Ni and Ag-Ge-Ni ternary systems. Ternary
Ag-Sb-Ni and Ag-Ge-Ni alloys were prepared with pure constituent
elements. Proper amounts of constituent elements were melted together
by arc melting. The arc-melted samples were equilibrated at 350 ˚C and
550 ˚C for the Ag-Sb-Ni system, and were at 400 ˚C and 750 ˚C for the
Ag-Ge-Ni system. Figure 1 is the BEI micrograph of Ag-60at.%Sb- 30at.
%Ni heat-treated at 550 ˚C for six weeks, and Figure 2 is its powder X-
ray diffraction results. The dark phase is the NiSb phase and its com-
position is Ag-52.3at.%Sb-47.6at.%Ni. The gray phase is the NiSb2
phase and its composition is Ag-66.4at.%Sb-32.5at.%Ni. The brightest
region is a phase mixture region, and was the liquid phase at 550 ˚C.
60
Calphad xxx (xxxx) xxx–xxx
When the sample was removed from the furnace, the liquid phase so-
lidified, Sb and Ag3Sb phases were formed. The alloy Ag-60at.%Sb-
30at.%Ni at 550 ˚C is in the liquid+NiSb+ NiSb2 three-phase region.
Based on the ternary experimental results, phase diagrams of the con-
stituent binary systems and calculated ternary phase diagrams with
preliminary thermodynamic models using the Calphad method, the
isothermal sections of Ag-Sb-Ni at 350 ˚C and 550 ˚C are then de-
termined. There are seven tie-triangles at 350 ˚C and nine tie-triangles
at 550˚C. Following similar procedures, the isothermal sections of the
Ag-Ge-Ni ternary system are also determined and there are six tie-tri-
angles at 400 ˚C and seven tie-triangles at 750 ˚C.
PC29
Experimental investigation of the Ti-Fe-Ta ternary system
F. Yang, J.B. Zhang, H.Y. Zhang, Z. Shi, X.J. Liu, C.P. Wang*
College of Materials, Xiamen University, Xiamen 361005, P.R.
China
* Corresponding author. E-mail: wangcp@xmu.edu.cn
Abstract:
It is well known that titanium and titanium alloys have a lot of
practical desirable properties, i.e. high strength, specific modulus, good
corrosion resistance and biocompatibility, etc., which make them at-
tract more and more attentions. As conventional alloying elements for
titanium alloys, tantalum and iron are important additions in multi-
component biomedical application titanium alloys, offering improve-
ment in both absence of toxic element and the low Young`s modulus. As
a result, it is of theoretical importance to investigate the phase re-
lationship of the Ti-Fe-Ta system.
The phase equilibria of the Ti-Fe-Ta ternary system were in-
vestigated using a combined methods of electron probe microanalyzer
(EPMA), back scattered electron (BSE) and X-ray diffraction (XRD). A
ternary compound was found, and temporally designated as
τ(Ti54Fe32Ta14) (as seen in Fig. 1). And also found (Ti,Ta)Fe2 form a
mutually soluble single-phase compound: (Ti,Ta)Fe2. The following
four three-phase equilibria at 1000 oC were well determined: (1)
(Ti,Ta)Fe2+TaFe+TiFe, (2) TiFe+TaFe+τ, (3) β(Ti,Ta)+TiFe+τ, (4)
β(Ti,Ta)+TaFe+τ. Two isothermal sections of the Ti-Fe-Ta ternary
system at 1000 ˚C (as seen in Fig. 2) and 1200 ˚C were experimentally
established.

Acknowledgments
This work was supported by National Natural Science Foundation of
China (Grant No. 51471138) and the Ministry of Education of China
(Grant No. 20120121130004).
PC30
Experimental investigation of the Ag-Ge-Zn system
S. Delsante1,2, D. Li3; R. Novakovic2, G. Borzone1,2
1
Department of Chemistry and Industrial Chemistry, Genoa
University & Genoa Research Unit of INSTM, Via Dodecaneso 31, I-
16146, Genoa, Italy
2
Institute for Energetics and Interphases - National Research
Council (IENI-CNR), Via de Marini 6, I-16149, Genoa, Italy
3
Karlsruhe Institute of Technology (KIT), 76021 Karlsruhe,
Germany
Phase diagram
Ag-based alloys have industrial importance also in relation to their
use as high temperature solders in jewellery [1]. Silver solders usually
are based on the Ag−Cu binary system, nevertheless Zn can be con-
sidered a candidate for replacing copper; it reduces the melting point of
solder increases the fluidity of the alloys and deoxidizes the melt.
Furthermore, the very good tarnish-resistance of Ag−Ge and
Ag−Ge−Zn alloys [2] make them good candidates for bonding sterling
silver (Ag92.5 Cu7.5, wt %) which are commonly used in jewellery due to
their very special lustre and very good mechanical properties.
Moreover, the addition of Ge to sterling silver alloys can greatly reduce
the oxidation during melting and casting.
Concerning Ag−Ge−Zn alloys, neither literature data on their
phase diagram nor on thermodynamic properties are available. The
experimental investigation of the Ag−Ge−Zn phase diagram was
performed by using combined microstructural, XRD and Differential
Scanning Calorimeter (DSC) analyses. The samples were subjected to
thermal analysis by a heat-flux DSC apparatus with heating and cooling
rate of 0.5 or 0.3 ˚C /min.
The microstructure of the samples, both after annealing and after
DSC analysis, was studied by optical and scanning electron microscopy.
Considering the slow heating and cooling rate, the isothermal section at
room temperature was established. No ternary compounds were ob-
served. On the basis of the experimental investigations the invariant
reactions were identified.
61
Calphad xxx (xxxx) xxx–xxx
References
[1] Welding, Brazing and Soldering, ASM Handbook, Vol.6, eds. J.R.
Davis, K. Ferjutz, N.D. Wheaton, M.S. Woods, ASM International, 1993.
[2] M.R. Pinasco, G. Pellati, A. Saccone, G. Borzone, E. Ricci, R.
Novakovic, A. Passerone, "Leghe a base di argento e procedimenti per la
loro realizzazione, particolarmente per la fabbricazione di gioielli".
Patent (2006). N. GE2006A000118.
PC31
Predictions of local structure of chromium ion with high-va-
cancies in dicalcium silicate by first-principles calculation and
XANES spectroscopies
Toshihiro Okajima1,2, Masanori Suzuki3, Norimasa Umesaki3, ahd
Toshihiro Tanaka3
1
Kyushu Synchrotron Light Research Center, 8-7 Yayoigaoka, Tosu,
Saga 841-0005, Japan
2
RCSLA, Kyushu Univ., 6-1 Kasugakohen, Kasuga, Fukuoka 816-
8505, Japan
3
Graduate School of Engineering, Osaka Univ., 2-1 Yamadaoka,
Suita, Osaka 565-0871, Japan
Dicalcium silicate (2CaO·SiO2, C2S) is a typical silicate compound
that is typically found in cement, sludge, concrete materials, and me-
tallurgical slags produced during metal production. C2S consists of
regular edge-linkes trigonal prisms of calcium ions with SiO4 tetrahedra
in the ceter, showing five polymorphs, α-, α'H-,α'L-, β- and γ-phase, on
C2S with temperature [1,2]. Different types of elements can be dis-
persed in C2S to form a solid solution phase. However, the dispersion
behavor of transition elements in stable form in terms of chemical va-
lences and local arrangements in C2S is not well understood. Chromium
(Cr) ion can exhibit various chemical valencies, including 2+, 3+, 4+,
5+ and 6+, in existing oxide compounds. Cr3+ ion is normally re-
garded as the most stable among those formed in air atmosphese, and it
is often octahedrally coordinated with neighboring oxygen anions.
Conversely, high-valence Cr ions (Cr4+, Cr5+, Cr6+) can associate with
several oxygen anions via tetrahedral coordination [3]. In this study,
we investigated the environments, such as local structure and electro-
valence of Cr ion with high-valences in γ- and β-C2Ss, which exist at
room temperature, by first-principles calculations and X-ray absorption
near edge structure (XANES) spectroscopies.

Figure 1 shows the Cr K-edge XANES spectrum of Cr dispersed β-
C2S (β-C2S:Cr) and theoretically obtained Cr K-edge XANES spectra
with the high-valence with from Cr4+ to Cr6+ ions occupying the tet-
rahedral Si4+ sites inβ-C2S. The results of K2CrO4 as a reference sample
are also shown together. A broad peak is obserbed at pre-edge region
ofβ-C2S:Cr and the peak energy is lower by about 1.2 eV from that of
K2CrO4 in which Cr ion has 6+. All the calculated spectra of Cr dis-
persed β-C2S show a sharp pre-edge peak corresponding to the CrO4
tetrahedral structure, and the pre-edge peak energy monotonically shift
to higher values with increasing Cr ion electrovalence states. These
results indicate that several types of Cr ions with different electro-
valence coexist in Cr-doped β-C2S. The contributions of Cr ions with
4+ and 6+ electrovalence to the distribution of pre-edge peak are
relatively smaller than that of the Cr5+ ion. In contrast, we revealed
that the Cr ions in γ- C2S occupied the tetrahedral Si4+ sites with
electrovalence of 6+.
62
Calphad xxx (xxxx) xxx–xxx
References
[1]I. Nettleship, et. al., J. Am. Ceram. Soc., 75 (1992) 2400-2406.
[2] Y.J. Kim, et. al., J. Am. Ceram. Soc., 75 (1992) 2407-2419.
[3] F. Xiuji and L. Shizong, Cem. Concr. Res., 16 (1986) 587-601.
PC33
Giant dimension changes induced by complex phase transfor-
mation behaviors in Ni-Mn based alloys
Shuiyuan Yang1,*, Yuding Liu1, Cuiping Wang1, Hengxing Jiang1,
Jiahua Zhu1, Yong Lu1, Rongpei Shi3, Xingjun Liu1
1
Department of Materials Science and Engineering, College of
Materials, Xiamen University, Xiamen 361005, China
3
Department of Materials Science and Engineering, Ohio State
University, 2041 College Road, 477 Watts Hall, Columbus, OH 43210,
USA
* Corresponding author: yangshuiyuan@xmu.edu.cn
Unusual giant dimension changes induced only by one thermal cycle
(i.e. heating and cooling) are observed in Ni50Mn50, Ni50-xCuxMn50 (x
= 8, 10, 12) and Ni40Co10Mn50 alloys (at.%), with the largest dimen-
sion expansion up to 2.2% in Ni40Cu10Mn50 alloy upon heating.
Complex phase transformation behaviors during the cycle and the
corresponding microstructural evolutions are found to be responsible
for this unique phenomenon. The difference in transformation sequence
is the occurrence of a temperature-induced irreversible martensite
structural transformation from the non-modulated L10 martensite to the
modulated 14M martensite upon heating in Ni50-xCuxMn50 alloys. As
such, there are not only different microstructures in these alloys
quenched from different annealing temperatures ranging from 500 ˚C to
900 ˚C, but also different amounts of dimension changes upon heating
and cooling. The pre-deformation on the samples is also found to have a
significant influence on the behaviors of dimension change during
thermal tests according to different microstructures. For example, the
largest high-temperature shape recovery strain of about 1.8% is ob-
tained in Ni38Cu12Mn50 alloy quenched from 600 ˚C and pre-deformed.
Acknowledgements
This work supported by the Fundamental Research Funds for the
Central Universities (No. 20720160078) and the National Science
Foundation of China (No. 51201145, 51571168).