CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry #vol# (xxxx) xxxx–xxxx

Contents lists available at ScienceDirect

CALPHAD: Computer Coupling of Phase Diagrams and

Thermochemistry
journal homepage: www.elsevier.com/locate/calphad

Using the PARROT module of Thermo-Calc with the Cr–Ni system as

example
⁎
Florian Tang , Bengt Hallstedt
Institute for Materials Applications in Mechanical Engineering, Augustinerbach 4, 52064 Aachen, Germany

A R T I C L E I N F O A BS T RAC T

Keywords: The Cr–Ni system is a relatively simple system with high technological importance. The system has been
Calphad modeled thermodynamically previously, but there is no detailed description of its assessment available. In
Cr–Ni addition the enthalpy of mixing of the liquid has been measured a few times with quite different results since the
Parrot previous assessments.
Modeling
In this paper a detailed thermodynamic assessment of the Cr–Ni system is presented. The system is
Thermo-Calc
described very satisfactorily with a small number of parameters. In contrast to most assessment papers also the
assessment procedure is described in detail, including the optimization of the parameters using the PARROT
module in Thermo-Calc. Extensive material is provided as supplementary material. The hope is that this can be
of some use for young researchers just starting with Calphad type modeling.

1. Introduction implies that it is not just a matter of optimizing a number of

The Calphad method is a powerful tool for of modeling modern
materials and especially suitable for complex multi-component and
multi-phase systems. The ability to reliably and accurately describe
multi-component systems depends on a detailed modeling of low-order
(in particular binary and ternary) systems combined with thermody-
namic extrapolation to higher-order systems. In order to reach this goal
it is particularly important that the modeling of the binary systems is of
the highest possible quality. Not only should the stable phase diagram
be correctly reproduced, but also the thermodynamic properties and
extrapolations into metastable regions. For reasonable extrapolations
to higher-order systems, the latter is more important. Extrapolations
within the binary system to regions where there are no experimental
data should be reasonable. All thermodynamic parameters should be
reasonable and ill-determined parameters should be avoided, or, at
least, be identified. Metastable phases should be reasonably described.
When this is accomplished, the complete experimental and theoretical
knowledge about the phase equilibria and thermodynamic properties of
a system is described by a small number of thermodynamic parameters
(or coefficients). It is the task of the assessor to make the best possible
use of the available information.
The complete procedure of collecting and evaluating experimental
and, increasingly, theoretical data, setting up thermodynamic models,
optimizing the thermodynamic parameters and comprehensibly pre-
sent the results is usually termed a thermodynamic assessment. This
parameters, but an intellectual effort to evaluate and valuate the
available knowledge of a system. Although there is a large number of
thermodynamic assessments published, there is a rather small number
of publications discussing the actual process. The most important
source is the book by Lukas et al. [1], which also includes chapters on
the use of the PARROT module and the BINGSS program. The latter is
also described by Lukas and Fries [2]. A more general discussion of the
assessment procedure and database development is given by Schmid-
Fetzer et al. [3]. In the present paper we will discuss the assessment
procedure and describe how to use the PARROT module in Thermo-
Calc [4] to optimize thermodynamic parameters, in the hope that this
can be of some help to researchers who are just starting with Calphad
modelingrev1. For this purpose we have selected the Cr–Ni system. The
system is of considerable practical importance, is relatively simple,
experimentally reasonably well-determined and there is a reasonable
amount of experimental data on both the phase diagram and various
thermodynamic properties available. A relatively simple system is
selected in order not to obscure the basic ideas too much by complex
modeling-related issues.
2. The Cr–Ni system
Known for the generally very high resistance against oxidation and
corrosion, Ni–Cr alloys are widely used in high-temperature and high-
pressure applications such as turbo chargers and exhaust systems, and

⁎
Corresponding author.
E-mail address: f.tang@iwm.rwth-aachen.de (F. Tang).

http://dx.doi.org/10.1016/j.calphad.2016.10.003
Received 29 March 2016; Received in revised form 7 October 2016; Accepted 14 October 2016
Available online xxxx
0364-5916/ © 2016 Elsevier Ltd. All rights reserved.

Please cite this article as: Tang, F., CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry (2016),
http://dx.doi.org/10.1016/j.calphad.2016.10.003
F. Tang, B. Hallstedt
good creep resistance enables the use in turbine blades and heating
chambers. These alloys (e.g. the Inconel family) are Ni-based (>50 wt
%), with Cr as the main alloying component (5 –25 wt%). Typically Fe,
Mo, Nb and Mn are also used in small amounts in these alloys. Almost
pure mixtures of Ni and Cr are used as resistance heating wire and in
thermo elements for high temperatures due to the high melting
temperature. Furthermore, the Cr–Ni system is an important subsys-
tem for stainless steels and a large number of high-temperature alloys.
The Cr–Ni phase diagram is characterized by a single eutectic
invariant at about 54 at% Cr and 1618 K and the ordered CrNi2 phase,
which is stable below 863 K [5–8]. The Ni- rich fcc phase has a very
high (up to 50 at% at 1618 K) solubility of Cr, which still remains
comparatively high at 863 K with about 32 at%. For the full composi-
tion range the liquidus and solidus temperature of the fcc phase are
almost indistinguishably close. The solubility of Ni in the bcc-Cr phase
at the eutectic temperature is about 35 at%, but rapidly decreases to
less than 5 at% at about 1250 K and is below 1 at% under 1000 K. In
contrast to the fcc phase, the bcc phase has a maximum difference of
about 200 K between the liquidus and solidus temperatures.
The system was reviewed by Nash [9], taking into account
essentially all data published up to 1983. The most widely used
thermodynamic description is from Lee [10]. There are further
descriptions from Udovsky and Kozodaeva [11] and Tomiska et al.
[12]. Since then there have been new calorimetric measurements of the
enthalpy of mixing of the liquid phase [13–15]. None of the thermo-
dynamic descriptions mentioned include the CrNi2 phase. This has
been included later by e.g. Turchi et al. [16] and Xiong [17].
The recent progress in first-principles calculations are especially
useful to model the lower-temperature ordered phase CrNi2 [16–18].
There is general agreement on the disordering or decomposition
temperature of 863 K, but the scatter is large concerning its solid
solution range at lower temperature. The modeling of the CrNi2 phase
as well as the magnetic transitions (discussed in some detail by Xiong
[17]) are somewhat outside the scope of this paper and will only be
briefly mentioned.
3. Experimental data
3.1. Types of data
Experimental data can generally be divided in two groups; phase
diagram (or constitutional) data and thermodynamic (or thermoche-
mical) data. Phase diagram data include all data regarding the phase
diagram, such as liquidus and solidus temperatures, solid solubilities,
stability, crystal structure, composition range and temperature range of
intermetallic phases, and invariant reactions. Measurements can be in
situ, using differential thermal analysis (DTA) or high- temperature X-
ray diffraction (HTXRD) or ex situ, using e.g. X-ray diffraction (XRD),
metallography or electron probe micro-analysis (EPMA) on annealed
and quenched samples. Analyzing as cast samples can give valuable
information about the solidification path, although the samples do not
represent an equilibrium state. Thermodynamic data include chemical
potentials, activities, enthalpies of mixing, enthalpies of formation,
enthalpies of melting, and heat capacities. There is a wide range of
calorimetric methods which have their specialized uses. Activities and
chemical potentials can be measured using Knudsen effusion mass
spectroscopy (KEMS), electromotive force (EMF) and various equili-
bration methods. To some extent the two groups overlap. Sometimes
phase boundaries can be derived from activity or chemical potential
data. Differential scanning calorimetry (DSC) give information on both
enthalpies and temperatures of invariant reactions. Measurements of
the phase boundaries of miscibility gaps give detailed information
about the thermodynamic properties of the demixing phase. For more
details the book by Zhao [19] can be recommended for phase diagram
data and the classic book by Kubaschewski et al. [20] can be
recommended for an overview on thermochemical measurements.
CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry xx (xxxx) xxxx–xxxx
There is an increasing amount of increasingly accurate ab initio
data using density functional theory (DFT) calculations becoming
available. Most of them concern calculations at 0 K and can often be
directly used as enthalpy of formation or enthalpy of mixing data. They
are particularly valuable for compositions or phases that cannot be
measured experimentally, because the phase is not stable or its
formation is too slow. In many cases these data can be handled just
as experimental calorimetric data. The accuracy is often similar to (or
even better than) good calorimetric data, but not always, and it can be
very difficult to judge the accuracy of ab initio data. There is also an
increasing amount of ab initio calculations for non-zero temperatures
using e.g. quasi-harmonic based approaches or ab initio molecular
dynamics. However, the computational cost so far prohibit their use for
other than elements and simple compounds.
In order to reach an accurate and reliable thermodynamic descrip-
tion it is necessary to have access to good data from both groups (phase
diagram and thermodynamic). Phase diagram data are very sensitive to
the relative Gibbs energies of different phases, but give very little
information on their absolute values. There is also no information how
the Gibbs energy varies within a single-phase region. On the other
hand, thermodynamic data are rarely accurate enough to reproduce the
phase diagram. A phase diagram calculation based purely on thermo-
dynamic data would in most cases lead to a phase diagram very far
away from the measured one. Thus, it is important to have access to
both kinds of data. This is actually one of the essential ideas behind the
Calphad method.
3.2. Primary data
As a general rule only primary data from original publications
should be used in a serious assessment. There are many reasons for
this, but sometimes exceptions are unavoidable; e.g. when the original
publication is unavailable or the primary data are not reported in the
publication. The actual source of the data points must always be stated.
It may be tempting to use data directly from a review paper where
all the data points are nicely plotted and tabulated. This should be
avoided as much as possible. It is impossible to judge the quality of the
data if the original publication is not consulted. Sometimes it is not
clear if the data have been measured, derived from other data,
estimated or calculated. For some types of data (e.g. enthalpies of
formation) “chain citation” is common and when following the chain
back one often finds that the data are very old, with high uncertainty or
have been estimated. It is disturbingly common that data have been
incorrectly transferred in some way. This includes misprints, incorrect
interpretations, wrong units or references. The original publication
may, of course, also contain mistakes and it may not always be clear if
data points have been measured or derived in some way. In short: One
should never take anything for granted.
During an optimization it may often be necessary to use derived or
estimated data to have a stable optimization. These should be removed
as much as possible during the final optimization. It is e.g. often helpful
to include data for all invariant reactions, at least during initial
optimization runs, even if they have not been directly measured.
3.3. Finding data
Experimental data have been published in a wide range of publica-
tions from all over the world and during a long period of time. Much is
published in internationally available journals, but there is also much
published in hard-to-get “gray” literature, such as local non-english
journals with limited circulation, conference proceedings, PhD theses
and technical reports. Fortunately, thermodynamic data and phase
diagram data have been collected and reviewed in a structured manner
and there are sources of data collections and references to literature.
Binary phase diagrams have been evaluated by ASM and published in
the Bulletin of Alloy Phase Diagrams (now Journal of Phase Equilibria
2
F. Tang, B. Hallstedt CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry xx (xxxx) xxxx–xxxx

and Diffusion). These phase diagrams are also collected in the Phase
Diagrams for Binary Alloys [21]. In addition Predel has evaluated a
large number of binary phase diagrams published in the Landolt-
Börnstein series [22]. Ternary phase diagrams have been evaluated by
the Materials Science International (MSI) group around Effenberg,
published first by VCH [23] and later by Springer in the Landolt-
Börnstein series [24]. MSI also runs its own web-based databank [25]
where evaluated phase diagrams and literature can be searched on a
per system basis. The Scientific Group Thermodata Europe (SGTE)
offers a literature database (Papyrus/Thermdoc [26]) which also can be
searched on a per system basis. Currently the most extensive collection
of data searchable on a per system basis is at Springer Materials [27].
Crystallographic data, in particular for binary compounds, are exten-
sive and can be considered reliable. For phase diagrams there are often
many different versions offered, but no advice which one might be
more correct. It often happens, even in “well known” systems, that
some information is missing. It can then be useful to check with related
ternary systems, which may have been in more recent focus of
attention. Oftentimes investigations on ternary systems also contain
information which is relevant for the binary subsystems. Although
magnetic properties are not discussed in this paper, as they are already
adequately modeled [28], it should be emphasized that the modeling of
the magnetic properties is part of the assessment. For the modeling one
needs information on transition temperatures and magnetic moments.
For the former, data from experimental measurements is needed,
whereas the latter can be reliably calculated with ab initio methods.
There are many recent publications on magnetic properties, frequently
in physics journals such as Phys Rev B. When searching literature one
should also consult the major literature citation sources such as Web-
of-Science [29], SciFinder [30], Scopus [31] and Engineering Village
[32]. However, it can be very difficult to find literature for a specific
system such as Cr–Ni since anything including Cr and Ni is considered
a hit.
A number of phase diagram review sources have been mentioned in
this section. In this context it must be pointed out that one should
always make an effort to find the primary source and extract the
primary data (see Section 3.2).
3.4. Judging data
The most essential, but also most interesting and difficult, part of a
thermodynamic assessment is to interpret, evaluate and judge the
available data. There is no standard procedure for this and more often
than not some detective work is involved. Some criteria that can be
used for evaluating data are:
0.01 or less (in atomic fraction). A calorimetric enthalpy of formation
or enthalpy of mixing measurement rarely has an error estimate of less
than 500 J/mol.
4. Review of experimental data in the Cr–Ni system
4.1. Phase stability information
Experiments in the Cr–Ni system date back to the 1930s, when
Jette et al. [7] investigated solubility ranges of the Cr phase, followed
by liquidus temperature measurements done by Jenkins et al. in 1937
[33]. Jenkins determined the eutectic composition and temperature to
be 6 at% Ni and 1618 K, results still valid today. Determining the
liquidus and solidus lines of the chromium rich side of the binary
system was not achieved until Svechnikov and Pan [34] used differ-
ential thermal analysis in 1962.
For the solubility limit of chromium in the fcc phase, the most
reliable results stem from works of Taylor and Floyd [35], Baer [5],
Pugliese and Fitterer [36], Karmazin [6]. Similarly, the combined
works of Dench [37], Collins [38], Jette et al. [7] completely describe
the solubility of Ni in Cr in the bcc phase.
A single data point for the CrNi2 phase at 863 K by Jette et al. [39]
is used to find the peritectic temperature. Little experimental results on
solubility of either chromium or nickel are available, and a detailed
description remains outside of the scope of this work.
All constitutive data included in the evaluation are shown in Fig. 1
along with the optimized phase diagram.
4.2. Enthalpy of mixing
Works of Dench [37], Watson and Hayes [40] were used to fit the
enthalpy of mixing in the solid phases at 1550 K and are shown
alongside the fitted curve in Fig. 2. Results from Kubaschewski [41]
were neglected because they were derived from measured activity data.
In the liquid phase, enthalpy data is available for the nickel-rich
side from Thiedemann et al. [13], Saltykov et al. [15]. The only
available data for the chromium-rich side is from Sudavtsova [14] at
2200 K. The oldest and for long time only available data from Batalin
et al. [42] differs widely from the more recent data. Predating these
experiments, the previous assessment by Lee [10] subsequently has a
very different enthalpy curve in the liquid phase (Fig. 3).

• Are the purities of the materials used given and are they sufficient?
• Is the experimental procedure reasonably described and appropri-
ate?
• Could contamination from crucibles or the atmosphere be an issue?
• Is the annealing time sufficient to reach equilibrium and has this
been verified in some way?
• Are the results contradicted or supported by other data?
• Is the scatter among the data points high or low?
• Is there a discussion of the results (experimental problems, relations
to other data) ?
• What is the reputation of the group? Have they done similar
measurements in other systems?

These criteria should be used to determine the error estimate to be

used in the optimization in the pop-file. Additionally, the criteria can be
used as guidance to set the weights during the optimization (see
Section 6.5). An accurately determined temperature would have an
error estimate of 1 or 2 K, whereas a not so well determined
temperature should have an error estimate of 10 K or more. An
accurately determined composition would have an error estimate of Fig. 1. Optimized version of the Ni–Cr phase diagram.

3
F. Tang, B. Hallstedt
Fig. 2. Enthalpy of mixing at 1550 K including data from Dench [37], Watson and Hayes
[40] with equal weights of 1.0. Experimental error was set to be 500 kJ/mol for each data
point.
Fig. 3. Enthalpy of mixing in the liquid phase above 1850 K. Old experimental data from
Batalin et al. [42] was used for a previous assessment by Lee [10], but subsequently
contradicted by Thiedemann et al. [13, Saltykov et al. [15].
4.3. Activity
In Fig. 4, optimized activity of chromium in the solid state is shown
at 1300 K alongside data from Mazandarany and Pehlke [43] and Rao
and Flores- Magon [44] with large deviation between the two data sets.
The measurements from [44] do not reach unity for pure Cr and are
therefore dismissed. Experiments conducted by Panish et al. [45] at
1023 K and Kubaschewski [41] at 1600 K were mostly dismissed
because of large uncertainties in the measurements.
Gilby and Pierre [46] first investigated the chromium activity in the
liquid phase, with the results generally supported by later works of
Katayama et al. [47], Pei and Wijk [48], Sudavtsova [14] although no
clear trend emerges for Cr contents above 20%, as shown in Fig. 5.
CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry xx (xxxx) xxxx–xxxx
Fig. 4. Activity at 1300 K. Experimental data from Rao and Flores-Magon [44] is
weighted with 0.1, whereas data from Mazandarany and Pehlke [43] is weighted 1.0.
Fig. 5. Activity at 1873 K. Experimental data from [14,46,48] all weighted 1.0.
Katayama et al. [47] is weighted 0.5 due to the large scatter of results.
5. Thermodynamic models
5.1. Solution phases
The Gibbs energy functions for the unary phases are taken from the
SGTE unary database by Dinsdale [49,50] and are not subject to
θ ∘ θ
optimization. These ( ∘GCr , GNi) are included in the description for the
Gibbs energy of the solution phases (liquid, fcc, bcc):
θ
Gmθ = x Cr · ∘GCr + xNi · ∘ GθNi + RT ·(x Cr ·ln x Cr + xNi ·ln xNi ) + x Cr xNi · L Cr , Niθ
(1)
in this equation, the ideal substitutional solution terms
RT ·(x Cr ·ln x Cr + xNi ·ln xNi ) is considered, and L Cr , Niθ is the interaction
parameter which is expressed as a Redlich-Kister (RK) series for the
excess energy of the solution of chromium and nickel of the following
4
F. Tang, B. Hallstedt
structure:
k changed by PARROT until the minimum is found. Finding the true
Lijθ = ∑ν=0 (xi − xj )ν ·νLijθ
ν θ
Lij = νaijθ + νbijθ ·T + νCijθ ·T ln T + νdijθ ·T 2
with ν denoting the order of the RK series element, θ the phase, and i
and j the components of interaction. Typically (including this assess-
ment), if no experimental data for the heat capacity is available, only
the fixed and the linear temperature-dependent part are used. In the
case of Cr–Ni, the RK polynomial would look like:
θ
L Cr,Ni =
k
∑ν=0 (xCr − xNi)ν (νaCr,Ni
θ
+ ν bCr,Ni
θ
·T)
The order of the polynomial needed (and which terms should be
temperature dependent) must be tested during the optimization.
Higher order than k = 3 is rarely needed. When information for a
phase is available only at low or high concentration one should
consider using only even terms. Odd terms can lead to severe
distortions of the mixing properties in the part of the system where
there are no data.
5.2. Intermetallic phase CrNi2
The Cr–Ni system has one intermetallic phase CrNi2, which is
modeled as a stoichiometric compound using a simple linear expres-
sion for its Gibbs energy of formation:
GmCrNi2 = ∘GCr
bcc
+ 2∘ Gfcc
Ni + a
CrNi2 + b CrNi2 · T
5.3. Magnetic contributions
The magnetic contributions for the fcc and bcc phases are taken
from Kajihara and Hillert [51]. They originate from an unpublished
work by Dinsdale [28].A Nishizawa horn is present in the fcc phase
with a critical point at 573 K and x Cr = 0.011. No further optimization is
done here. A very good overview on modeling of magnetic properties is
given by Xiong [17], which also includes a more detailed treatment for
the Cr–Ni system.
5.4. Adjustable parameters
The thermodynamic optimization process is like an upside-down
pyramid - based on unary thermodynamic descriptions for the ele-
ments, higher-order systems are subsequently built from lower-order
assessments. Changes to the most fundamental - the unary descriptions
- would influence every assessment including these elements.
Therefore, only the parameters of the mixing-terms (νLijθ , e.g
0 θ 0 θ 1 θ 1 θ
aij , bij , aij , bij , …) are optimized. Additionally, the Gibbs energy of
formation of the CrNi2 phase (aCrNi2 , bCrNi2 ) must be assigned.
6. Optimization procedure
6.1. Introduction to PARROT
In this Section, the general usage of Thermo-Calc for a from-
scratch assessment of a binary system is illustrated using the Cr–Ni
system. The proper handling of the thermodynamic functions as well as
the experimental data will be explained, with a focus on how to
understand and use the output given by the optimization for a
reasonable and reliable modeling of the system.
The PARROT module is used for the actual optimization of the
thermodynamic parameters. PARROT works by minimizing the sum of
squared errors, where the error is the difference between the value
calculated using the current parameter values and the experimental
CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry xx (xxxx) xxxx–xxxx
value, multiplied by some weight. The parameter values are then
(2) global minimum usually requires several reruns of PARROT. It is clear
that this procedure is purely statistical in nature. To reach an optimal
(3) result experimental data should be evenly distributed throughout the
system and the individual data points should show a Gaussian
distribution around their true values. The situation in real systems is
very far from this ideal state. Therefore, it is the assessor who must
determine what is an acceptable outcome of the optimization. This
outcome is reached by selecting the set of parameters to optimize and
setting the weights of the experimental data points. There is usually
some tradeoff between the number of parameters and the fit to the
(4)
experimental data. In most cases there are some data points that
cannot quite be reproduced, no matter what. Using excessive force
(weight) or too many parameters will then lead to bad parameter values
and bad extrapolations.
The general procedure for an optimization is first to write the setup-
file which defines the phases, their models and the parameters (called
variables in PARROT) that are possible to optimize. Then the experi-
mental data are coded in the POP file and both files are compiled with
Thermo-Calc. After the files have been successfully compiled all
equilibria in the POP file should be calculated once in the EDIT-
EXPERIMENTS (ED-EX) submodule of PARROT using COMPUTE-ALL-
EQUILIBRIA. The commands in ED-EX are similar to POLY-3 with
some extra commands. Most of the equilibria in the POP file can only
be calculated if the optimizing parameters have reasonable start values.
If the system has been previously modeled, these values can be used as
(5) start values. If not there are different ways of finding reasonable start
parameters such as estimating them, using driving force (DGM)
conditions (see Section 6.4) or using the alternate mode in PARROT
(not described here). If the system is complex it can be useful to start
with only a few phases or start with a simple model for a phase before
changing to a more complex model. If some equilibria in the POP file
cannot be calculated with the current set of parameters they can be
temporarily removed by setting their weights to 0. The first optimiza-
tion run in PARROT should be done with 0 iterations and the result
listed. This listing should be carefully checked. If some equilibrium is
incorrectly calculated (e.g. on the wrong side of an intermetallic phase)
it must be corrected in ED-EX. If some equilibrium is causing a very
large error its weight should be reduced. If this is not done further
optimization is likely to fail. When all this has been accomplished the
actual optimization can begin. This will require repeated optimization
runs. Now and then the variables should be rescaled so that the various
statistical measures, in particular the relative standard deviation, are
meaningful. By changing weights on the experiments and changing the
parameters (variables) to optimize one tries to reach the best possible
description of the system. This means that all parameters have
reasonable values and most of the experimental data are described
within their expected error limits. This is almost always a compromise
and one will have to use some judgement when determining what
actually is the best possible description.
All files and information given in this section are also supplied as
complete datasets in the supplementary material of this paper.
6.2. The setup-file
Starting off a blank setup in the GES module (GIBBS-ENERGY-
SYSTEM) of Thermo-Calc, elements and unary description functions
are added with the description taken from Dinsdale [49,50]. The
interaction parameters are entered as depending on variables, which
are indicated by Vxx with xx being numbers from 01 to 99.
Every phase of the system has to be defined as a function of
composition for each constituent, in this case chromium and nickel.
There are 4 phases: Liquid, FCC_A1, BCC_A2 and CRNI2_C11B, with
their respective functions entered as described in Section 5. For the
liquid, fcc and bcc phases, substitutional solution models are used.
5
F. Tang, B. Hallstedt
Since no information about the heat capacity for CrNi2 is available it is
modeled with a linear Gibbs energy of formation.
If a database (TDB) from an older description of the system is
available, the setup file does not have to be written from scratch. Using
LIST-DATAwith option P in the GES module a file with the correct
syntax for a setup file can be created. The values of the parameters to be
optimized then need to be replaced with the optimizing variables Vxx
and the old parameter values can be defined as start values for the
optimization using the commands SET-OPTIMIZING-VARIABLE or
SET-FIX-VARIABLE. In this case we use the parameter values from
Lee [10] as start values. It is recommended to include all possible
parameters (i.e. more than actually expected) from the start in order to
avoid having to recompile the setup file. The setup file should end with
CREATE-NEW-STORE-FILE.
6.3. The POP-File
The so called POP file contains all the experimental data points that
are going to be used during the optimization. The experimental data
points are coded in the form of commands to the ED-EX module, which
has most of the commands from the POLY-3 module and some
additional commands to handle the experimental data points.
Fig. 6 shows how the eutectic reaction is coded. The first line
CREATE-NEW initiates the equilibrium, with the first number being a
sequential number (within the file) to identify the equilibrium. It is
useful to leave some gaps in the sequence to be able to add data found
later. The second number is an initiation code. Code 2 means that all
elements and phases are entered. This is the standard when doing
Fig. 6. Excerpt from the pop file showing the eutectic data point as two separate
experiments, giving the opportunity to separately set the weight of either temperature
(first equilibrium) or composition (second equilibrium).
CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry xx (xxxx) xxxx–xxxx
calculations in POLY-3. Code1 means the all elements are entered and
all phases are suspended. This is the standard in POP files since
experimental data always concern a defined set of phases. Code 0
means that all elements and phases are suspended. This is useful when
optimizing e.g. a binary and a ternary system at the same time. The
following two lines CHANGE-STATUS and SET-CONDITION define the
equilibrium state. In this case we require liquid, fcc and bcc to
participate (eutectic invariant) in the equilibrium and the total pressure
is set to 1 bar. It is necessary to set a start value at least for the
temperature. This can be done either by SET-START-VALUE T=xxxx
or SET-ALL-START-VALUES xxxx Y. The latter also sets automatic
start values for all site fractions (compositions). Setting start values can
be tricky and is discussed more in detail later on. The last line is the
experimentally measured temperature with an estimated error. The
error should reflect the expected accuracy of the measurement. Since
changes in the errors and in the weights are handled in the same way
during the optimization, it is sufficient that the errors are reasonable.
The fine tuning during the optimization is done by changing the
weights. It would be possible to include experiments also for the
compositions of the phases here, but it turns out to be useful to have
the compositions in a separate equilibrium. In this way it is possible to
set different weights for the temperature and the compositions.
Often there are several data points of the same type, e.g. points
along a liquidus curve or solvus. These can be conveniently collected in
tables, see Fig. 7. The table head between the TABLE-HEAD and the
TABLE-VALUES sets all conditions for each equilibrium following in
the tabulated part. By using @1 and @2, it refers to either the first or the
second column of the following block of data. This feature is not limited
to two variables, but can be used for more columns, e.g. the error or a
phase name. Each line between TABLE-VALUES and TABLE-END
represents one data point. These lines can also contain text such as
phase names.
The POP file must end with the command SAVE-WORKSPACE.
Setting start values in the POP file so that all the equilibria can be
calculated without manual intervention can be very tricky. The global
minimization which is used by default for calculations in POLY-3 is
very efficient in finding the true equilibrium, but cannot be used in ED-
EX. The reason is that the global minimization automatically creates
new composition sets, which are needed to describe miscibility gaps
and ordered states. However, if they are created during an optimization
the PARROT workspace is destroyed. If extra composition
sets are actually needed they have to be created in the setup file.
This means that start values have to be set manually when needed.
Unfortunately, commands that work reliably in POLY-3 do not
seem to do so in ED-EX. What does seem to work is to set
start values for site fractions, either using SET-START-VALUE
Y(PHASE,ELEMENT#SUBLATTICE=FRACTION or by using SET-
ALL-START-VALUES and entering all site fractions. The latter can
also be used interactively to transfer start values from a working
equilibrium to a non-working. Setting start values for overall composi-
tions (i.e. X(PHASE,ELEMENT)) or using ADVANCED-OPTIONS SET-
MAJOR do not seem to work reliably or not at all. When intermetallic
phases are present it is quite common that an equilibrium on the wrong
side of the compound is found. This must be corrected before starting
the optimization. Otherwise the optimization may go badly wrong. In
the present system start values are not a major issue. Only the invariant
equilibria (eutectic and peritectoid formation of CrNi2) sometimes need
manual intervention to converge correctly.
6.4. Start values for parameters
Since the optimization works by calculating the difference between
the calculated and experimental value it is necessary that the equilibria
in the pop file can be calculated. This is only possible when the
parameter values are such that these equilibria exist. If one tries to
start with all optimizing variables equal to 0 most equilibria in the pop
6
F. Tang, B. Hallstedt
Fig. 7. Excerpt from the pop file showing experimental data for solidus temperatures.
Uncertainty of the experiment is expressed via a fixed error bar of 10 K in each
experiment.
file will probably not exist. Thus, it is usually necessary to estimate
reasonable start values for some parameters so that most equilibria can
be calculated. If the system has been assessed previously one can use
those parameters as start values. The starting parameters for this
assessment were set to those from Lee [10], complemented by the
values of Hirabayashi et al. [39] for the CrNi2 phase.
If there is no previous assessment and the system is complex it can
be useful to start with only a few phases, e.g. the liquid and the
elemental solution phases, and then add the other phases one by one.
When there are phases that do not appear where they should be stable
a temporary stability condition to force the phase to become stable can
be added to the pop file. This would look like EXPERIMENT
DGM(PHASE) > 0.1:0.1. This condition (with the opposite sign) can
also be used to suppress phases that appear where they should not be
stable. It is possible to start with all optimizing variables equal to 0 if
CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry xx (xxxx) xxxx–xxxx
the ALTERNATE-MODE is used in PARROT, but the present authors
have not used it.
6.5. Setting weights
Setting the weights on the different experimental data points is (in
addition to selecting the optimizing variables) the only way to influence
the optimization. There is always some degree of arbitrariness in this
and it is the task of the assessor to use his or her judgement to find a
good balance between the different pieces of information. Some general
advice can be given, though. If there are many data points of one type
e.g. activities in the liquid their weight should be decreased. If there are
several measurements of the same quantity, e.g. invariant temperature
or enthalpy of formation, or if there is an obvious contradiction only
one should be used. If it is not clear which one is the better different
alternatives can be tested. It is quite frequent that a definite statement
is not possible.
Due to the nature of the least-square method, if an integer multiple
of relevance to the fitted curve (e.g. “this experimental data is twice as
relevant as the other”) is desired, the square root of the according
multiple should be chosen.
Most likely, the experimental information is not evenly spread
throughout all composition or temperature ranges, this has numerous
considerable implications for setting weights. An example for a low-
density range of experimental data is found in the 50–80 at% of the
chromium bcc solubility line, where only the data from Dench [37] is of
appropriate quality. In the 95–100 at% range of solubility, a large
amount of experiments [7,37,38] is available (Fig. 1). Therefore, the
optimized functions might deviate further than expected from the
experimental data in the low-density ranges, since the functions are
more determined by the high-density range data. In addition, the
reliability of experiments does not correlate with the number of
measurements. The data from Dench [37] was therefore weighted
higher to balance the scarceness of results in this range.
Even the most detailed parameters can and should not accurately fit
every experimental value, which can also be thought of as an advantage
of smoothing typical for polynomial functions. The residual error of the
optimization will naturally converge to some higher value for more
scattered experimental data.
The leading cause for the re-evaluation and new assessment of the
chromium-nickel system done in this paper was the unreasonable
mixing enthalpy in the liquid phase. Considerable attention was paid to
the appropriate optimization, since these experiments in a way added
stability to the optimization parameters for enthalpies in the full
temperature range.
Since experimental data remains scarce for high-temperature
liquids as aggressive as chromium, special care has to be taken with
assessing the few experiments available. Data from Batalin et al. [42]
seems completely unlikely, despite the paper not revealing obvious
mistakes. Experiments from Thiedemann et al. [13], Sudavtsova [14]
are much closer to a regular mixture.
The activities of chromium–nickel mixtures have been investigated
by numerous researchers [14,36,41,43–48,52,53]. Natural to this
amount of data, quite some contradictory data have to be discarded.
Fitterer [36] found an increasing deviation from the ideal behavior with
increasing temperature, which deflates the reliability of these experi-
ments. Data from Mazandarany and Pehlke [43] and Pei and Wijk [48]
are found to be the most recent and complete data sets, whereas
Wagner et al. [52] and Ichise et al. [53] are not included since they do
not present data in a form that can be used. The older data from Gilby
and Pierre [46], Kubaschewski [41] only covers up to 40 at% chro-
mium, with acceptable deviation from ideal behavior. Panish et al. [45],
Rao and Flores-Magon [44] have unreasonable values for high
chromium content and their weights is set at 0.1 leaving them without
leverage to affect the optimization while still calculating the equilibria.
Even though different levels of confidence can be assigned to each
7
F. Tang, B. Hallstedt
Fig. 8. Examples for output lines of a list-result command in the PARROT module with
the columns being: identification number of the experiment, experiment and experi-
mental value, current calculated value, the uncertainty divided by the square of the
weight, the difference between the calculated and experimental values and in the last
column the quotient between the latter two.
experiment, all activity data was assumed to have a fixed experimental
error of 0.05. Further tuning was done by changing the weights.
6.6. Running and ending the optimization
Every optimization will follow a similar procedure. Once the setup
file and the pop file have been successfully compiled all equilibria have
to be calculated using COMPUTE-ALL-EQUILIBRIA in the ED-EX
module. This has to be repeated each time the setup file or the pop file
is recompiled. If some equilibria do not converge they can be removed
temporarily by setting their weights to 0. Then all equilibria should be
calculated in PARROT using OPTIMIZE-VARIABLES with 0 iterations
and the result listed with LIST-RESULT. This list (Fig. 8) should be
inspected carefully to make sure that all equilibria are calculated
correctly and there are no excessively large errors (marked with * or
# in the last column). Errors should be corrected and weights for
equilibria producing large errors should be reduced in ED-EX. If this is
not done the following optimization is likely to go wrong.
It is useful to start with a relatively small number of optimizing
variables and use repeated OPTIMIZE-VARIABLES runs to adjust the
weights so that different types of data have a balanced influence and
invariant equilibira are reasonably reproduced. Convergence is some-
times slow so that a large number of iterations and repeated
OPTIMIZE-VARIABLES runs are needed. Once convergence has been
reached the optimizing variables should be rescaled (RESCALE-
VARIABLES) and the optimization run once more. If something goes
wrong the previous parameter values can be recovered with RECOVER-
VARIABLES. The parameter values and their relative standard devia-
tions (RSD) should be inspected (Fig. 8). A temperature dependent
parameter with a value larger than about 10 J/(K mol-atoms) should
be viewed with suspicion. If this is a parameter for the liquid
interaction it can cause an inverted miscibility gap. An RSD larger
than about 1 suggests that the parameter is statistically not well
determined and one should consider not using it or setting it to a fixed
value.
Looking at the list of results is not sufficient to determine if the
outcome of an optimization is acceptable or not. The phase diagram
and all other property diagrams where experimental data exist should
be calculated and plotted together with the experimental data. Since
this will have to be done more than once it is useful to have macros to
do all plots automatically. It is not uncommon that the calculated phase
diagram has some interesting surprises in store when the list of results
suggests that the optimization converged nicely. This will suggest
changes in the weights and additional equilibria to put into the pop
file. It is very useful to also calculate metastable extrapolations of two-
phase equilibria (Fig. 9) and the Gibbs energies of all phases across the
whole composition range at some intermediate temperature to make
sure that there are no strange features. A common problem, which can
be very difficult to get rid of, is an inverted miscibility gap in the liquid.
This should be suppressed as much as possible (preferably to above
6000 K) using stability conditions (EXPERIMENT QF(LIQUID) > 1:1).
In Cr–Ni this is not a problem, though.
Towards the end of the optimization the weights should be fine-
tuned and different combinations of optimizing variables tested to see
if some further improvement can be achieved. It will usually be found
CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry xx (xxxx) xxxx–xxxx
Fig. 9. Metastable extrapolations of the Ni–Cr phase diagram.
that not all experimental data can be as closely reproduced as expected.
There will always be a compromise between the number of parameters
used, reasonable parameter values and how closely the experimental
data can be reproduced. One should keep in mind that good extra-
polations to higher order systems (and outside stable ranges of the
phases) can only be achieved when the parameter values are reason-
able. It is up to the judgement of the assessor to decide when the best
compromise has been reached.
As the very last step all parameter values should be rounded. Lukas
and Fries [2] suggest rounding the parameters to the nearest 1 J/mol at
1000 K, i.e. temperature dependent parameters to the third decimal,
whereas Schmid-Fetzer et al. [3] suggests rounding to the nearest
0.1 J/mol at 1000 K. Rounding to 1 J/mol will be sufficient in almost
all cases, but when two compounds are very close in composition even
0.1 J/mol might not be sufficient. A more robust way is to successively
fix the parameters in PARROT (starting with those with the highest
RSD) and reoptimize until all parameters except one has been fixed.
The sum of squares should not increase significantly in this process. If
it does a significant digit has to be added to one or two parameters.
In general the final optimization (before rounding) should be done
with all (used) optimizing variables. However, there are some excep-
tions to this rule. Parameters for the heat capacity for compounds and
magnetic parameters should be optimized before other parameters are
optimized and kept fixed during the rest of the optimization.
If thermodynamic data (enthalpies of formation, enthalpies of
mixing, chemical potentials, activities) are completely missing in a
(binary) system it is still possible to optimize the system, but the result
will be extremely unreliable. Fortunately, this situation is becoming
quite rare as data from ab initio DFT calculations are available for a
large number of systems or can be produced at low cost. In any case
one should then at least test the result in ternary extrapolations.
7. Results and discussion of the present optimization
All parameters assessed in this work are presented in Table 1.
Notably no higher order than 2 is needed for the RK series. All
parameters are fairly tightly constrained by the experimental data.
The phase diagram generally fits the experimental data quite well
with very few deviations, Fig. 1. The solubility of nickel in the fcc phase
is very close to experimental results at temperatures below 1200 K. The
calculated line is very close to results of Taylor and Floyd [35], whereas
8
F. Tang, B. Hallstedt
Table 1
Thermodynamic parameters for the Ni–Cr system determined in the present work.
GmCrNi2 = ○GCr
bcc fee
+ 2○G Ni −6000 −6.8·T
0 bcc
L Cr,Ni = 14,500–9·T
1 bcc
L Cr,Ni = 27,500–7.6·T
0 fee
L Cr,Ni =4300–8.9·T
1 fee
L Cr,Ni = 27,000–13.8·T
0 liq
L Cr,Ni =− 13,300+2.7·T
1 liq
L Cr,Ni =2900+1·T
All parameter values are given in SI units (J, mol).
experimental results from Pugliese and Fitterer [36] have been derived
from activity measurements and are probably less accurate. The shape
of the bcc solvus is very sensitively dependent on the bcc (and to some
extent fcc) interaction parameters and also very sensitive to the
weighting of the individual data points. Crucially, the selected experi-
ments show little scatter. Liquidus and solidus temperature ranges for
the nickel-rich side are easily assessed and fit the experimental data by
Jenkins et al. [33] quite well. On the chromium-rich side, the fit of
liquidus temperatures reproduces the experimental results quite well,
whereas the solidus temperatures determined by Svechnikov and Pan
[34] deviate by up to 20 K. A large solidification interval such as this
leads to strong segregation, making determination of the equilibrium
solidus very difficult, as the results from Jenkins et al. [33] in the 60–
70 at% range suggest.
The metastable phase diagram, Fig. 6, shows that the assessment is
well suited for extrapolation to higher order systems, since no
miscibility gap or other unreasonable deviation is observable.
Activity measurements at low temperatures are shown in Fig. 4.
While the alignment of the calculated activity of chromium with the
data from Mazandarany and Pehlke [43] is excellent, a gap to the
results of Rao and Flores-Magon [44] is apparent. Data points from
Rao and Flores-Magon [44] seem to have a systematic error which
could be caused by an incorrect reference state and thus are not
included in the actual optimization. At high temperatures, an increas-
ing scatter of chromium activity results is observed with increasing
chromium content, Fig. 5. No general trend of temperature dependency
or obvious erroneous methodology warranted to omit any of the shown
data sets [14,46–48] and consequentially the optimized activity curve
averages the scattered points quite well.
Exhibiting the biggest change compared to previous assessments,
the enthalpy of mixing in the liquid phase fits the new experimental
data sets from Thiedemann et al. [13] and Saltykov et al. [15] quite well
(Fig. 3). Sudavtsova [14] is the only experimental source for liquid
phase results in chromium-rich alloys but shows a considerable gap to
the data from Thiedemann et al. [13] and Saltykov et al. [15]. However,
the results from Sudavtsova [14] strongly suggest that the enthalpy of
mixing in the liquid phase is nearly symmetric (i.e. regular). In the
solid state, mutually consistent results have been found for the
enthalpy of mixing by Watson and Hayes [40], Dench [37] which the
optimization reproduces to an acceptable degree (Fig. 2). Enthalpies of
mixing of fcc and bcc have been investigated with ab-initio methods
recently by Breidi et al. [54], Wróbel et al. [55] and are in good
agreement with experimental data shown in Fig. 2. In Breidi et al. [54]
the agreement is only qualitative since the scatter in the calculated data
is large, in particular for bcc. The ab initio data from Wróbel et al. [55]
cannot be applied directly since the formation energy of fcc-Cr is much
larger than that used for Calphad calculations [49]. This is caused by
the massive dynamic instability of fcc-Cr (Grimvall et al. [56]). The
added constraint of high temperature experimental results and phase
diagram data limited the fitting. However, the formation enthalpy of
CrNi2 calculated by Wróbel et al. [55] to be ΔHCrNi2 = −4.6 kj mol−1 is
reasonably close to the ΔHCrNi2 = −6 kj mol−1 used in this assessment.
CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry xx (xxxx) xxxx–xxxx
8. Conclusions
A consistent thermodynamic description of the entire Cr–Ni binary
system well fitted for extrapolation in higher order systems was
obtained, including previously not included enthalpy of mixing experi-
ments. The process of the assessment has been described in detail in
the hope of being of help for young Calphadians.
Acknowledgement
The authors gratefully acknowledge the financial support of the
Deutsche Forschungsgemeinschaft (DFG) within the Collaborative
Research Centre (SFB) 761 “Steel-ab initio: Quantum mechanically
guided design of new ferrous materials”.
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