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A CALPHAD thermodynamic model for multicomponent alloys under pressure and its
application in pressurized solidified Al–Si–Mg alloys

Wang Yi, Jianbao Gao, Lijun Zhang

PII: S2772-834X(24)00013-7
DOI: https://doi.org/10.1016/j.apmate.2024.100182
Reference: APMATE 100182

To appear in: Advanced Powder Materials

Received Date: 29 November 2023

Revised Date: 1 February 2024
Accepted Date: 11 February 2024

Please cite this article as: W. Yi, J. Gao, L. Zhang, A CALPHAD thermodynamic model for
multicomponent alloys under pressure and its application in pressurized solidified Al–Si–Mg alloys,
Advanced Powder Materials (2024), doi: https://doi.org/10.1016/j.apmate.2024.100182.

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 A CALPHAD thermodynamic model for multicomponent alloys under pressure
and its application in pressurized solidified Al-Si-Mg alloys

Wang Yi1, Jianbao Gao1,2, Lijun Zhang1,*

1
State Key Laboratory of Powder Metallurgy, Central South University, Changsha,
410083 Hunan, P.R. China
2
State Key Laboratory of Materials Processing and Die & Mould Technology, School
of Materials Science and Engineering, Huazhong University of Science and
Technology, Wuhan 430074, China

*
Corresponding author. Email: lijun.zhang@csu.edu.cn

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Author profiles
Wang Yi (1994-) is now a doctor candidate supervised by Prof.

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Lijun Zhang at Central South University, China. Currently, he has
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published 3 papers in J. Mater. Sci. Technol., J. Mater. Inf., and
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CALPHAD. His research interest lies in alloys design driven by an
integration of computational thermodynamics, computational
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kinetics, machine learning, and key experiments.

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Jianbao Gao (1993-) received his Dr. degree from Central South
University, China (Supervisor: Prof. Lijun Zhang) in 2023. He is
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now a postdoctoral researcher at Huazhong University of Science

and Technology in China. He is interested in materials design
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driven experiments and calculation methods, including

thermodynamics, phase-field method, and machine learning. Up to
now, he has published more than 25 SCI papers, including Acta
Mater., Sci. Technol. Adv. Mater., J. Mater. Sci. Technol. And Addit.
Manuf. He is presiding 1 China Postdoctoral Science Foundation.

Lijun Zhang (1983-), professor and doctoral supervisor of Central

South University, China. His research interests lie in design,
preparation, and applications of advanced metallic structural
materials. He has published more than 200 papers as the
first/corresponding author in journals such as Acta Materialia,
Nature Communications, npj Computational Materials, Advanced
Powder Materials, etc. He concurrently serves as a
member/associate Secretary general at the Computational
Materials Branch of the Chinese Society of Material Research, and
 associate editor of the international journal Frontier in Materials.
Moreover, he also serves as the (youth) editorial board member of
“Materials”, “Advanced Powder Materials”, “Journal of
Magnesium and Alloys”, etc. He has been selected as a young
scholar in the "Changjiang Scholars Award Program" of the
Ministry of Education, Hunan Provincial Science Fund for
Outstanding Youth, Hunan Young Talents, Global Scholars
Database 2021/2022 Top 100,000 Scientists in the World. Lijun
has also won the first prize of Hunan Provincial Natural Science
Award (ranked 3rd), the Outstanding doctoral thesis Award of
Hunan Province, the Best Paper Award of the Year of the
International CALPHAD journal, and the Top Ten Progress of
China’s Nonferrous Metals (ranked 3rd).

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Acknowledgements -p
This work was supported by the Science and Technology Program of Guangxi
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province, China (Grant No. AB21220028), the Natural Science Foundation of Hunan
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Province for Distinguished Young Scholars (Grant No. 2021JJ10062), and the
Lvyangjinfeng Talent program of Yangzhou. Yi Wang acknowledges the financial
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support from the Fundamental Research Funds for the Central Universities of Central
South University (Grant No. 2021zzts0094) and the Hunan Provincial Innovation
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Foundation for Postgraduate (Grant No. CX20210094). Jianbao Gao acknowledges

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the financial support from China Postdoctoral Science Foundation (Grant No.
2023M741244).
 Graphical Abstract

This work developed a CALPHAD thermodynamic model for multicomponent alloys

under pressure and achieved its integration into the CALPHAD design framework for
pressurized solidified Al-Si-Mg alloys.

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A CALPHAD thermodynamic model for multicomponent alloys

under pressure and its application in pressurized solidified

Al–Si–Mg alloys

Abstract
High pressure technology has been utilized as an important means to regulate phase
structure and improve the properties/performance of alloys. The CALPHAD approach
based on accurate databases has great advantages in efficient alloy design. However,
the application of CALPHAD in high pressure field is hindered by the lack of reliable
thermodynamic model/database for multicomponent alloys under pressure. In this

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paper, a phenomenologically thermodynamic model for multicomponent alloys under
pressure is first developed by separating the contribution into two parts, one is at

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atmosphere pressure and the other is caused by an increase in pressure, and then
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successfully applied to establish the pressure-dependent thermodynamic database of
ternary Al–Si–Mg system. The calculated phase equilibria/thermodynamic properties
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of pressure dependence in related alloys are in good agreement with the limited
experimental data in the literature, validating the reliability of the obtained
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thermodynamic database. After that, a CALPHAD design framework for pressurized

solidified alloys is proposed by integrating the present pressure-dependent
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thermodynamic model/database, CALPHAD-type calculations/simulations, and

previously developed high-throughput calculation platform Malac-Distmas. Such a
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framework is finally applied to predict the pressurized solidification and high pressure
heat treatment behaviors in different Al-Si-Mg alloys. The predicted microstructure,
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phase transitions and phase equilibria after pressurized solidification and high
pressure heat treatment are consistent with the experimental data. Furthermore, the
insights into effect of pressure on the thermodynamic essence of alloys are gained,
which may definitely facilitate the advancement of alloy design under high pressure
technology.

Keywords: Pressure; Thermodynamics; Al–Si–Mg alloys; CALPHAD; Pressurized

solidification.

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1. Introduction
In the thermodynamics of materials, pressure is an important variable that is as
important as temperature and composition [1–3]. In recent years, high pressure
technology has been utilized as an auxiliary means to regulate phase structure and
even improve properties of different alloys, including Al- [4–8] and Mg-based [9–11]
alloys. Especially in the automotive industry, as the invention of Model Y developed
by Tesla, the high pressure die casting technique has been utilizing to produce super
large aluminum castings for replacing a huge number of traditional parts, greatly
reducing energy consumption [12,13]. To control the microstructure and properties of
alloys under pressure, it is the prerequisite to comprehensively understand the

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influence of pressure on the thermodynamics of target alloys. However, one cannot

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get a full view based on the sole experimental investigations, which are also very
time- and labor-consuming. Fortunately, to date, many computational approaches are

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(FP) calculation [14],
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available for investigating the thermodynamics of alloys, including the first-principles
molecular dynamic (MD) simulation [15], CALculation of
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PHAse Diagram (CALPHAD) technique [16–18], and phase-field (PF) modeling
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[19–21].

Among the above computational approaches, the CALPHAD technique has great
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advantages in efficient and accurate prediction of the thermodynamic properties of

target material and has been widely used to guide the composition screening and
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process optimization of alloys during the past fifty years [22–25]. The key to
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performing reliable thermodynamics calculations/analysis through the CALPHAD

technique lies in the accurate database(s) [22]. While the first step in obtaining an
accurate database is to select/develop the appropriate model. Over the past century,
some efforts have been made to derive the Gibbs energy expression related to the
pressure. Such efforts can be divided into two different forms. One is based on lattice
vibrations [26–28] and the other is empirical [29–31]. Among all the proposed
pressured-dependent thermodynamic models, the one proposed by Lu et al. [31] is
relatively easy to handle and can deal with a variety of pure substances. However, it
has been criticized for giving unphysical extrapolation to high pressure regions
(i.e., >10 GPa). In this context, Joubert et al. [32,33] introduced two exponential
terms into Lu’s model to avoid the wrong extrapolations of the Cp and entropy to high
pressure and temperature regimes. Liu and Oikawa [34] tried to extend Lu’s model to
binary Al–Si system, and the calculated pressure-dependent phase diagram can
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reproduce partial experimental data [35,36]. Unfortunately, the effect of pressure on
the binary interaction parameters was not considered in their work, resulting in a large
deviation between the predicted eutectic temperature and the experimental data [37].
Recently, Oh et al. [38] employed the atomistic simulations to investigate the
influence of pressure on the interaction parameters of fcc and bcc binary solid
solution phases at 0K, and proposed an approach to evaluate the pressure-dependent
excess volume of the solution phase. However, there is still a lack of systematic study
on the pressure-dependent interaction parameters of a real binary alloy, not to mention
the higher-order alloys.

Under this situation, it is urgent to upgrade the thermodynamic model for

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multicomponent alloys to be a pressure-dependent one by deriving the relationships

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between Gibbs energy and pressure. Then, the pressure-dependent thermodynamic

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database of multicomponent alloys can be obtained by assessing the original
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experimental data of phase equilibria under pressure. After that, the pressurized
solidification and high pressure heat treatment behaviors of alloys can be studied to
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provide guidance for the discovery of novel alloys with excellent properties.
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Consequently, the aims of this paper are to develop a phenomenologically

thermodynamic model for multicomponent alloys under pressure, and realize its
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application in pressurized solidification alloys. Moreover, the ternary Al–Si–Mg

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alloys, commonly used in high pressure die casting technology, are selected as the
target. The major research objectives of this paper are: (i) to develop a
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pressure-dependent thermodynamic model for multicomponent system by separating

the contribution at atmosphere pressure and the other caused by an increase in
pressure; (ii) to establish a pressure-dependent thermodynamic database of the
Al–Si–Mg system, and validate its reliability by comparing various model-predicted
phase diagrams with the corresponding experimental data available in the literature;
(iii) to propose a CALPHAD design framework for pressurized solidification and
apply it in the technologically important Al–-Si–Mg alloys.

2. Results and discussion

2.1. Pressure-dependent thermodynamic database of Al–Si–Mg system

In the present work, the molar Gibbs energy of pure element i (i.e., Al, Si, and Mg)
in Al–Si–Mg system at 0.1 MPa was directly taken from the compilation by Dinsdale
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[39]. The pressure and temperature dependence molar volumes of Al, Si, and Mg were
taken from Liu and Oikawa [34], and Huang et al. [40]. Fig. S1-S3 in the
Supplementary Material file show the calculated thermo-physical properties (i.e.,
molar volume, isothermal compressibility, and temperature-pressure diagram) of pure
Al, Si, and Mg by using the thermodynamic parameters from Refs. [34, 40]. The
binary and ternary interaction parameters of Al–Si–Mg system at 0.1 MPa were taken
from Tang et al. [41]. The pressured-related interaction parameters for Al–Si–Mg
system were optimized by using the PARROT module incorporated in the
Thermo-Calc software package [42] in this work. In the first step, all the
pressure-dependent parameters of three binary systems (i.e., Al–Si, Al–Mg, and
Mg–Si) were assessed. In those binaries, the assessment began with the intermetallic

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phase. The pressure-related thermodynamic parameters of β-Al140Mg89, ε-Al30Mg23,
γ-Al12Mg17, and Mg2Si were first obtained to reproduce the thermo-physical

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properties data. Next, the solubilities of elements in the solid solution phase (i.e., (Al)
or (Mg)) were considered. The pressured-related thermodynamic parameters of solid
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solution phases were acquired to reproduce the solvus data. After that, the
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pressure-related thermodynamic parameters of liquid phase were accordingly adjusted

to fit the phase equilibria (i.e., liquidus, solidus, and eutectic reaction) related to liquid
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phase. Furthermore, all the selected experimental data were used simultaneously to
obtain a self-consistent set of pressured-related thermodynamic parameters. In the
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second step, based on the assessed thermodynamic descriptions of three boundary

binaries, the pressure-dependent thermodynamic database of Al–Si–Mg ternary
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system was established. The finally obtained pressure-related thermodynamic

parameters in Al–Si–Mg system are listed in Table S1.

Fig. 1 presents the phase diagrams of ternary Al–Si–Mg system at different

pressures based on the present pressure-dependent thermodynamic database. The
experimental data from literature were also superimposed as scattered symbols in the
figure for comparison. The lines indicate the calculation results in the present work.
Fig. 1(a) displays the calculated phase diagram of binary Al–Si system at 2.1 GPa
along with the experimental data from [43]. As can be seen in the figure, most of the
experimental data can be well reproduced by the present calculations. Moreover, the
calculated maximum solubility of Si in (Al) phase is 5.1 at.%, which well reproduces
the experimental one (4.9 at.%). Fig. S4 gives the calculated binary phase diagrams of
Al-Si system at 2.8 GPa and 5.4 GPa, compared with the experimental data by

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[35,36,44]. The presently calculated results are in general agreement with most of the
reported experimental data. Moreover, the calculated Si solubility in the (Al) phase in
the present work is 15.5 at.% at 560 oC and 5.4 GPa, which is consistent with the fact
pointed out by Matsumuro et al. [44] that the Si solubility in (Al) phase at 560 oC and
5.4 GPa should be larger than 15 at.%. However, the calculated Al-rich solvus at 5.4
GPa shows a certain deviation from the experimental data [36]. One possible reason is
that the pressure effect on the electromotive force (EMF) of thermocouples was not
considered by Mii et al. [36] owing to the difficulty in making exact corrections. The
authors [36] claimed that their measured values were lower than the true ones by 5%
at such pressure. A comprehensive comparison between the model-predicted eutectic
temperatures of pressure dependence and the experimental data available in the

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literature [35,37,43] is displayed in Fig. 1(b). It is encouraging to see that the
experimental eutectic temperatures of pressure dependence are well reproduced by the

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Fig. S5 shows the calculated thermo-physical properties (include molar volume
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and bulk modulus) of β-Al140Mg89, ε-Al30Mg23, and γ-Al12Mg17 phase by using the
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thermodynamic parameters in the present work. Fig. 1(c) presents the calculated
phase diagrams of Al-Mg system at 2.2 GPa. Fig. S6 shows the calculated binary
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phase diagrams of Al-Mg system at 3.3 GPa and 5.4 GPa, in comparison to the
experimental data from the literature [45–48]. It can be seen from Fig. 1(c) and Fig.
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S6 that the currently calculated phase diagrams at 2.2 GPa, 3.3 GPa, and 5.4 GPa are
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in good agreement with most of the reported experimental data [45,46]. Particularly,
the calculated Al solubility in (Mg) solid solution phase at 773K and 5.4 GPa in this
work is 20.5 at.%, which is consistent with the fact pointed out by Matsumuro et al.
[46] that the Al solubility in (Mg) solid solution phase at 773 K and 5.4 GPa should
be larger than 20 at.%. Fig. 1(d) shows the calculated liquidus projection of binary
Al-Mg system versus Mg content and pressure together with the reported
experimental data [47,48]. There are four primary phase regions in the figure,
including (Al), β-Al140Mg89, γ-Al12Mg17, and (Mg). When the pressure is lower than
0.5 GPa, the primary phases of the alloy with Mg content are in order of (Al),
Al140Mg89, Al12Mg17, and (Mg). When the pressure is between 0.5 GPa and 4.0 GPa,
no Al140Mg89 exists in the primary crystallization fields. The primary crystallization
fields consist of the (Al) phase in Al-rich side and the (Mg) phase in the Mg-rich side
when the pressure is above 4.0 GPa. It can be seen from Fig. 1(d) that the

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model-predicted pressure-dependent primary phases of Al-Mg system are
considerably consistent with the corresponding experimental results [47,48].

In the Mg-Si system, there is a need to evaluate the pressure-dependent

thermodynamic parameters of Mg2Si compound since it acts as the important
strengthening phase in the Al-Si-Mg casting alloys. Fig. S7 shows the calculated
thermo-physical properties of Mg2Si phase, compared with the corresponding
experimental/calculated results [49–58]. The temperature-dependent bulk modulus of
Mg2Si phase at 0.1 MPa is shown in Fig. S7(a). It is noted that the present
calculations are in good agreement with the experimental data [49,50], but show large
deviations from the bulk modulus calculated by Yu et al. [51], Ganeshan et al. [52],

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and Guezlane et al. [53]. The temperature-dependent molar volume for Mg2Si phase

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at 0.1 MPa is plotted in Fig. S7(b), while the pressure-dependent molar volume at

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room temperature is presented in Fig. S7(c). It can be seen that the presently
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calculated results fit well with the most experimental/calculated data [51,54–58]. Fig.
1(e) demonstrates the calculated phase diagrams of Mg-Si system at different
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pressures. Unfortunately, there are no reports on the pressure-dependent phase
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equilibria of the Mg-Si system in the literature for comparison. From Fig. 1(e), it can
be seen that the melting temperature of Mg2Si phase continues to increase along with
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pressure.
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To have clear and detailed information about the effect of pressure on the phase
equilibria of the Al–Si–Mg system, a comprehensive comparison of vertical sections
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along Al-0.4Mg-xSi (in at.%) system at different pressures is demonstrated in Fig.

1(f). Again, there are no pressure-dependent phase equilibria in the Al-Si-Mg system
available in the literature for direct comparison. As shown in Fig. 1(f), there are four
phases, including liquid, (Al), (Si), and Mg2Si, in this figure, and the increase of
pressure can expand the phase regions of (Al), liquid+(Al), liquid+(Al)+(Si), and
(Al)+(Si). Moreover, increase in pressure leads to an increase in the liquidus and
solidus temperatures. As indicated by the black arrow, the maximum solubility of Si
in (Al) increases continuously from 1.64 at.% at 0.1 MPa to 14.46 at.% at 5.0 GPa.
Therefore, on the basis of solid solution strengthening, it is expected that
high-performance Al-Si-Mg with high Si content in (Al) matrix can be prepared.
Furthermore, the triple point of liquid+(Al)+(Si) moves towards higher Si
concentration as the pressure increases. In other words, a fully eutectic Al-Si-Mg alloy
with high Si content can be prepared using the high pressure solidification technique,
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and such alloy is anticipated to own excellent comprehensive properties.

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Fig. 1 (a) Calculated phase diagram of Al–-Si system at 2.1GPa, compared with the corresponding
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experimental data [43]; (b) Model-predicted pressured-dependent eutectic temperature of the
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invariant reaction, Liquid→(Al)+(Si), compared with the experimental data [35,37,43]; (c)
Calculated phase diagram of Al–Mg system at 2.2GPa, compared with the corresponding
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experimental data [45]; (d) Model-predicted liquidus projection of Al–Mg system versus Mg
content and pressure, compared with the experimental data [47,48]; (e) Calculated phase diagrams
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of Mg–Si system at 0-5GPa; (f) Calculated vertical sections along Al-0.4Mg-xSi (in at.%) system
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at 0-5 GPa.

2.2. CALPHAD design framework for pressurized solidification and its application in

Al–Si–Mg alloys
With the pressurized solidification technique, different pressures may result in
different solidified microstructures of target alloys, and then affect their
mechanical/functional properties and performance. Based on the presently developed
thermodynamic model and database of pressure dependence, the thermodynamic
essences of pressurized solidification and high pressure heat treatment for
multicomponent alloys can be clarified by coupling with the high-throughput
computations platform Malac-Distmas [59] developed in our previous work.
Accordingly, a CALPHAD design framework for pressurized solidified alloys is
proposed, as schematically displayed in Fig. S8.
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 Following the idea in Fig. S8, on one hand, with the accurate pressure-dependent
thermodynamic database, the non-equilibrium solidification simulations can be
performed using the Scheil–Gulliver mode, resulting in reliable prediction of
pressurized solidification behaviors, including the solidification sequences, phase
transition temperatures, phase fractions, solubility, microsegregation, and so on. From
the well-predicted pressurized solidification behaviors, one can design the alloy
composition and/or the loaded pressure by establishing either a qualitive relation
between solidified microstructure and the properties based on the expert experience
[16] or a quantitative one based on e.g., machine learning technique [23]. On the other
hand, with the reliable pressure-dependent thermodynamic database, the equilibrium
property diagram under different pressures calculations can be conducted to obtain the

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phase-related information, like phase status, phase fractions, solubility, etc., with
which insights into the underlying mechanisms of heat treatment under pressure can

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be gained. Thus, one may perform design of the solution/aging temperature and/or the
loaded pressure for the heat treatment of the target alloy.
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2.2.1. Pressurized solidification
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Fig. 2 depicts the solidification behaviors of Al-Si alloys simulated with the
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Malac-Distmas platform [59] based on the current pressure-dependent thermodynamic

database. The solidification curves of Al-20Si (in wt.%) alloy under pressure are
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shown in Fig. 2(a). Each color denotes one type of phase reaction. The
two-dimensional (2-D) solidification diagram of Al-20Si alloy with different
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pressures can be then synthesized, as displayed in Fig. 2(b). Such a solidification

diagram is actually a side projection of Fig. 2(a). The corresponding fractions of
different structures in Al-20Si alloy, including primary (Si), primary (Al), and binary
eutectic (Al)+(Si), are illustrated in Fig. 2(c). As clearly indicated in Fig. 2(a)-(c),
there is a critical pressure of 1.62 GPa in Al-20Si alloy, at which only the
Liquid→(Al)+(Si) binary eutectic reaction occurs without the formation of any
primary phase. When the pressure is lower than 1.62 GPa, the primary phase is (Si).
Increasing the solidification pressure, the content of primary (Si) decreases while that
of (Al)+(Si) eutectic structure increases. When the pressure is at the critical point of
1.62 GPa, the primary (Si) exactly vanishes, and the fraction of binary eutectic
structure just achieves 100%. Further increase in the solidified pressure results in the
appearance of primary (Al), and its content continues to increase along with pressure,
while that of the binary eutectic decreases. Moreover, it should be noted that the
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simulated solidification sequences and phase fractions in Al-20Si alloy at 0.1 MPa, 1
GPa, 2 GPa, and 3 GPa are consistent with the experimental results reported by Ma et
al. [7]. Such a fact further validates the reliability of the presently assessed
pressure-dependent thermodynamic database.

By adding one more axis of Si concentration, a three-dimensional (3-D)

solidification diagram of Al-Si system was further constructed and displayed in Fig.
2(d). From such a 3-D diagram, the solidification sequences of the Al-Si alloys with
arbitrary composition under different pressures can be efficiently obtained. The
critical point in Fig. 2(b) and (c) extends into a black dashed line in Fig. 2(d). Along
this line, the (Al)+(Si) binary eutectic structure directly forms from the melt. On the

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left side of this line, the solidification microstructure consists of primary (Al) and

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(Al)+(Si) binary eutectic structure, while on the right side of this line, the

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solidification microstructure consists of primary (Si) and (Al)+(Si) binary eutectic
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structure. Besides, the critical eutectic line moves towards the Si-rich side as the
pressure increases. Therefore, it is expected to prepare a completely eutectic Al-Si
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alloy with higher content of Si under higher pressure.
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Fig. 2 (a) Simulated solidification curves of Al–20Si (in wt.%) alloy under different pressures; (b)
Constructed 2-D solidification diagram for Al–20Si alloy under different pressures; (c) Calculated
phase fraction diagram of Al–20Si alloy under different pressures, compared with the

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experimental data [7]; (d) Constructed 3-D solidification diagram of binary Al–Si system under
different pressures.

Fig. 3 presents the solute solubility in different Al-Mg alloys after

non-equilibrium solidification under different pressures. Fig. 3(a), (b), (c) and (d)
display the solubility of Mg in (Al) matrix phase versus pressures for Al–9.6Mg,
Al–20Mg, Al–30Mg, and Al–40Mg (in wt.%) alloys, respectively. The experimental
solubilities from the literature [47,48,60–62] are also superimposed in the figure for
direct comparison. It can be seen that the model-predicted solubilities agree well with
most of the reported experimental data. Moreover, the value and microsegregation of
Mg solubilities in the (Al) matrix phase increase as the pressure increases. Fig. 3(e)

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and (f) present the solubility of Al in (Mg) matrix phase versus Al content at 0.1 MPa
and 4.0 GPa, respectively. It can be seen in the figures that the predicted results are

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considerably consistent with the measured ones [9–11]. Besides, the solubility of Al in
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(Mg) matrix phase increases and the segregation decreases with the increase of Al
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content at both 0.1 MPa and 4.0 GPa pressures.
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Fig. 3 Model-predicted solubility of solute in matrix phase of different Al–Mg alloys after
solidification at different pressures [9–11,47,48,60–62]. (a) Mg in (Al) of Al–9.6Mg (in wt.%)
alloy; (b) Mg in (Al) of Al–20Mg alloy; (c) Mg in (Al) of Al–30Mg alloy; (d) Mg in (Al) of
Al–40Mg alloy; (e) Al in (Mg) at 0.1 MPa; (f) Al in (Mg) at 4.0 GPa. Max., Ave., and Min. in the
figure represent the calculated maximum, average, and minimum solute solubility in different
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Al–Mg alloys after non-equilibrium solidification under different pressures.

As for the Al–Si–Mg ternary system, Al–20Mg2Si (in wt.%) alloy was chosen as
the target to demonstrate an in-depth understanding of the impact of pressure on
solidification. Fig. 4(a) and (b) show the experimental microstructures of Al-20Mg2Si
alloy solidified at 0.1 MPa and 3 GPa reported in [5]. It can be seen that the primary
phase is Mg2Si at 0.1 MPa (Fig. 4(a)); when the solidification pressure is 3 GPa, the
primary Mg2Si phase disappears, and the primary (Al) phase appears (Fig. 4(b)). The
simulated solidification behaviors of Al-20Mg2Si alloy were presented in Fig. 4(c)-(f)
to provide insights into the impact of pressure on the non-equilibrium solidification
behaviors of alloy. Fig. 4(c) shows the solidification curves of alloys at different

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pressures. Fig. 4(d) and (e) display the solidification diagram and phase fractions of
Al-20Mg2Si alloys versus pressure obtained from Fig. 4(c), respectively. There is a

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critical pressure of 1.05 GPa in Al-20Mg2Si alloy where no primary phase is formed
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and only the Liquid→(Al)+Mg2Si binary eutectic reaction occurs. When the pressure
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is lower than 1.05 GPa, the primary phase is Mg2Si, and its formation temperature
decreases with pressure. Besides, the amount of primary Mg2Si phase decreases while
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that of (Al)+Mg2Si binary eutectic structure increases as the solidification pressure

increases. The primary Mg2Si phase completely vanishes, and the fraction of binary
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eutectic structure just achieves the maximum value of 95.63% when the pressure is at
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the critical point. Further increase in the pressure results in the formation of primary
(Al). Its formation temperature increases with pressure, and the amount continues to
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increase along with pressures, while that of the binary eutectic structure (Al)+Mg2Si
decreases. It is worth noting that the simulated solidification sequences and the
primary phase fraction agree well with the experimental results [5]. Besides, Fig. 4(f)
illustrates the solubility of Si and Mg in the (Al) matrix phase when the pressure is
higher than 1.05 GPa. It can be seen that the predicted solubility agrees well with the
origin data from [5]. Moreover, it can be found that the solubilities of Si and Mg
increase with pressure both in value and segregation.

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Fig. 4 (a-b) Experimental microstructrus of Al-20Mg2Si (in wt.%) alloy after solidification at 0.1
-p
MPa (a) and 3 GPa (b) [5]; (c) Simulated solidification curves of Al-20Mg2Si alloy under different
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pessures; (d) Solidification diagram of Al-20Mg2Si alloy versus pressure; (e) Solidification phase
fraction of Al-20Mg2Si alloy versus pressure; (f) Solubility of Mg and Si in primary (Al) phase of
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Al-20Mg2Si alloy after solidifiation at different pressures.

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2.2.2. Heat treatment under pressure

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Fig. 5 illustrates the calculated equilibrium property diagram of Al–7Si (in wt.%)
alloys at different pressures. As shown in Fig. 5(a), the temperature and pressure of
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phase transition and phase equilibrium can be obtained for Al–7Si alloy. When the
pressure is lower than 2.7 GPa, as the temperature decreases from 1200 oC to 0 oC, the
(Al) phase firstly forms from liquid phase, and then the binary eutectic reaction
(liquid→(Al)+(Si)) occurs until all the liquid completely transforms into (Al)+(Si)
eutectic structure. When the pressure is higher than 2.7 GPa, as the temperature
decreases, the (Al) phase forms from liquid phase until all the liquid completely
transforms into (Al) phase. The (Si) phase may precipitate from the (Al) with the
further decrease in temperature. In other words, the (Si) phase can be fully dissolved
only when the pressure is above 2.7 GPa. The higher the pressure is, the lower the
precipitation temperature of (Si) is. Fig. 5(b), (c) and (d) display the 2-D property
diagrams of Al-7Si alloy at 0.1 MPa, 2.7 GPa, and 6.0 GPa, respectively. The (Si)
phase can never be fully dissolved in the (Al) solid solution phase in the alloy with

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solution treatment at 0.1 MPa (see Fig. 5(b)). As the temperature is above 617 oC, the
solution treatment at 2.7 GPa can promote the full dissolution of the (Si) phase, but it
cannot avoid the re-melting of (Al) phase (see Fig. 5(c)). When the pressure is 6.0
GPa, the (Si) phase is completely dissolved, and there is a single (Al) phase existing
in the alloy in the solution temperature range of 355~911 oC (Fig. 5(d)). The
experimental microstructures of Al–7Si alloy after solution treatment at 0.1 MPa and
550 oC, as well as at 6 GPa and 700 oC observed by Liu et al. [8] is also inserted in the
figure for a direct comparison. Fig. 5(b) and (d) show that the predicted phase status
is in good agreement with the observed by Liu et al. [8].

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Fig. 5 Calculated property diagram of Al–7Si (in wt.%) alloy at different pressures: (a) 3-D
property diagram over the pressure range of 0.0001~6 GPa; (b-d) 2-D property diagrams at 0.1
MPa (b), 2.7GPa (c), and 6.0 GPa (d). Experimental microstructures of Al–7Si alloy solution
treatment at 0.1 MPa and 550 oC, as well as at 6.0 GPa and 700 oC [8] were also inserted in the
figure for comparison.

As for the Al–Mg system, Fig. 6(a) plots the predicted property diagram of
Al–20Mg (in wt.%) alloy versus temperature at 2 GPa. It can be seen that the phase
fraction of β-Al140Mg89 decreases with the temperature increases. When the
temperature is above 393 oC, the β-Al140Mg89 phase is completely dissolved in the (Al)
13 / 23
matrix phase. Fig. 6(b), (c) and (d) present the experimental microstructure of
Al–20Mg alloy solution treatment at 2GPa and 20, 300, and 400 oC, respectively [6].
The alloy microstructure consists of (Al) and β-Al140Mg89 phases after solution
treatment at 200 and 300 oC, while only a single (Al) phase exists in the alloy after
solution treatment at 400 oC. This indicates that the predicted microstructure agrees
well with the corresponding experimental one.

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Fig. 6 (a) Calculated property diagram of Al–20Mg (in wt.%) alloy at 2 GPa, compared with the
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experimental microstructures solution treatment at 200 oC (b), 300 oC (c), and 400 oC (d) [6].
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As a brief summary, with the pressure-dependent thermodynamic model and

database one can successfully capture the thermodynamic essence of pressure,
temperature, and composition dependence. That is, the predicted properties, i.e., phase
transition temperature, phase region, phase fraction, solubility, and microsegregation,
are consistent with the reported experimental results. It is anticipated that the
presently proposed CALPHAD design framework together with the present
thermodynamic model/database for multicomponent alloys under pressure can be
applied in the advancement of alloy design under high pressure technology.

3. Conclusions

⚫ Following the CALPHAD methodology, a phenomenologically thermodynamic

model for multicomponent alloys under pressure is first developed by separating

14 / 23
 the contribution into two parts, one is at atmosphere pressure and the other is
caused by an increase in pressure.

⚫ The pressure-dependent thermodynamic database of ternary Al–Si–Mg system is

established based on the developed model together with the pressure-dependent
phase equilibria/thermodynamic properties in the literature. The model-predicted
phase equilibria/thermodynamic properties of pressure dependence in Al–Si–Mg
ternary system and its boundary binaries are in good agreement with the limited
experimental data in the literature, validating the reliability of the obtained
thermodynamic database.

⚫ A CALPHAD design framework for pressurized solidified alloys is proposed by

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integrating the present pressure-dependent thermodynamic model/database,
CALPHAD-type calculations/simulations, and the Malac-Distmas platform. Such

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a framework is applied to predict the pressurized solidification and high pressure
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heat treatment behaviors in different Al–Si–Mg alloys. The predicted
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microstructure, phase transitions, and phase equilibria after pressurized
solidification and high pressure heat treatment are consistent with the
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experimental data.
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⚫ The insights into effect of pressure on the thermodynamic essence of alloys are
gained, which are anticipated to facilitate the advancement of alloy design under
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high pressure technology.

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4. Phenomenologically thermodynamic model for multicomponent alloys under

pressure

Here, we proposed to divide the molar Gibbs energy of arbitrary phase θ under
pressure in multicomponent systems into two parts,

GP = GP0 + GP , (1)

P
The first contibution G 0 represents the contribution at atmosphere pressure (i.e.,

P0=0.1 MPa), and its expression for different types of phases in multicomponent
system can be referred to numbers of publications in the literature [63]. While the
P
second contribution G is caused by a change in pressure from P0 to P

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 , (2)

V represents the molar volume of phase θ that is of pressure, temperature, and

composition dependence. Taking a general substituional solution phase in a
multicomponent system for an example, V can be expanded according to the
Redlich-Kister polynomial [64]
V =  xiVi +  xi x j  Vi ,nj ( xi − x j ) +  xi x j xk  Vi , j ,k +    ,
n
(3)
i i j i n =0 i j i k  j n=0

here, Vi is the pressure and temperature dependent molar volume of pure element i. All

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the related data in this work are limited in the region of < 10 GPa. Thus, we prefer to
adopt Lu’s phenomenological model in the present work, which can be written as [31]

r
-p , (4)
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−1
where is the exponential integral function and E1 represents its
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inverse function. V0 is the molar volume at 0 K and 0.1 MPa, VA is the integrated
volumetric thermal expansion, VC is the parameter to fit the high pressure data, and
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VK is the isothermal compressibility at 0.1 MPa.

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The Vi ,nj and Vi , j ,k in Eq. (3) are the pressure-, temperature-, and

composition-dependent binary and ternary interaction parameters for excess molar

volume. Following the suggestion from Gheribi et al. [65] that the variation of the
excess molar volume in alloy systems with temperature and pressure is weak, and

the interaction parameters, Vi ,nj and Vi ,nj ,k , can be given as

, (5)

, (6)

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where the interaction coefficients, ain, j , bin, j , cin, j n, din, j , Vi , V j , and Vk are

to be optimized based on the available experimental/calculated molar volume

and/or phase equilibria at different pressures.

Declaration of Competing Interests

The authors declare that they have no known competing financial interests or personal
relationships that could have appeared to influence the work reported in this paper.

Data Availability

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All data needed to evaluate the conclusions in the paper are present in the paper.

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Additional data are available from authors upon request.

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 Highlights

⚫ A pressure-dependent thermodynamic model for multicomponent alloys was

developed.

⚫ The pressure-dependent thermodynamic database of Al-Si-Mg system was

established.

⚫ A CALPHAD design framework for pressurized solidified alloys was proposed.

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 Declaration of competing interest

The authors declare that they have no known competing financial interests or personal
relationships that could have appeared to influence the work reported in this paper.

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