CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 43 (2013) 94104

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CALPHAD: Computer Coupling of Phase Diagrams and

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

CALPHAD modeling of metastable phases in the AlMgSi system

Erwin Povoden-Karadeniz a,n, Peter Lang b, Piotr Warczok c, Ahmad Falahati c,
Wu Jun c, Ernst Kozeschnik a,c
a
Christian Doppler Laboratory for Early Stages of Precipitation, Institute of Materials Science and Technology, Vienna University of Technology,
Favoritenstrae 9-11, 1040 Vienna, Austria
b
Materials Center Leoben Forschung GmbH, Roseggerstrae 12, 8700 Leoben, Austria
c
Institute of Materials Science and Technology, Vienna University of Technology, Favoritenstrae 9-11, 1040 Vienna, Austria

art ic l e i nf o

a b s t r a c t

Article history:
Received 28 September 2012
Received in revised form
11 March 2013
Accepted 16 March 2013
Available online 10 May 2013

In the framework of the CALPHAD approach, a thermodynamic assessment of the metastable phases in
AlMgSi alloys is presented. The early MgSi co-clusters are described as a regular solid solution phase.
A split model of fcc-based ordering is used for GuinierPreston (GP)-zones as suggested by the
assessment of microstructural data. The model parameters are optimized based on new thermodynamic
rst-principles data of the binary subsystems. CALPHAD parameters of Mg5Si6 and Mg1.8Si are rened for
application in thermo-kinetic simulations. Mg5Si4Al2 is modeled as an Al-containing form of . B, U1
and U2 are described as line compounds, with parameters derived from rst-principles molar enthalpies.
Vibrational entropies are determined by combination of rst-principles calculations, experimental solvus
and heat ux data of continuous-heating DSC. Decreasing entropies of formation of intermetallic MgSi
and AlMgSi phases correlate with decreasing enthalpies of formation, as predicted from the modeling.
First-principles heat capacities are included in the optimization. Application of the assessed thermodynamic parameters in precipitation kinetics simulations is demonstrated in the computational
evaluation of continuous-heating experiments of a quenched AlMgSi alloy. The simulations show
good accordance with the experimentally known evolution of metastable phases.
& 2013 Elsevier Ltd. All rights reserved.

Keywords:
Co-clusters
GP-zones
Ordering
B-phase
U-phase
AlMgSi

1. Introduction
The scientic interest for metastable phases in the AlMgSi
system dates back to the mid of the last century, when their huge
potential for precipitation hardening was discovered [1]. Later,
with the application of density functional theory, it became
possible to access their thermodynamics by rst-principles analyses, the results of which can be found in a number of publications [29]. Nowadays, there is general agreement about the
following principle sequence of metastable phases from the
quenched supersaturated solid solution (SSSS) at room temperature up to the formation of thermodynamically stable Mg2Si ()
and Si:
SSSS-Clusters-Coclusters; GPzones--; B; Uphases
In the analysis of the early metastable phases in the AlMgSi
system, high-resolution transmission electron microscopy (HRTEM)
revealed the existence of disordered MgSi co-clusters [10], which
have been predicted decades ago [11], in addition to ordered GPzones [12] at low temperatures. Changes of heat ow in continuousn

Corresponding author. Tel.: +43 1 58801 308 46; fax: +43 1 58801 308 95.
E-mail address: erwin.povoden-karadeniz@tuwien.ac.at
(E. Povoden-Karadeniz).
0364-5916/$ - see front matter & 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.calphad.2013.03.004

heating differential scanning calorimetry (DSC) experiments of

solution-treated and quenched alloy AA6016 was related to the
formation and dissolution of these metastable phases [13]. Recent
rst-principles phonon calculations for monoclinic Mg5Si6 (), hexagonally close-packed Mg1.8Si () [7,14] and U-phases [14] have
delivered theoretical thermodynamic solvus temperatures as a function of alloy composition, as well as heat capacities of , and Uphases [14].
In the present study, we present a thermodynamic assessment
of metastable MgSi co-clusters and ordered GP-zones, an Alcontaining form of , Mg5Si4Al2 (Al-), as well as other Alcontaining phases, which are, in terms of their thermal stabilities,
closely related to . These are B, U1 and U2, and we denote this
group of phases as Al-pre-. The thermodynamic description of
stable Mg2Si is taken from a previous assessment [15]. Kozeschnik
et al. [16] analyzed the potential of thermo-kinetic simulations for
improving thermodynamic model parameters even in nonequilibrium regions: Predictive models for nucleation and growth
of precipitates are, along with thermodynamic, mobility and
physical properties databases, embedded in the comprehensive
software package MatCalc [17]. Utilizing kinetic simulation results
obtained from these models, thermodynamic parameters of metastable phases can be rened in order to reproduce experimental
ndings on the metastable states that occur. In classical CALPHAD

E. Povoden-Karadeniz et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 43 (2013) 94104

assessment, the optimization process of thermodynamic model

parameters minimizes a sum of errors over all the available input
data, rst-principles energetics and experimental thermodynamics. In the present study, non-equilibrium experiments are
utilized for the optimization of thermodynamic model parameters,
in addition to classical CALPHAD assessment. In this context, the
following strategy is used: The heat ux due to evolving precipitates during continuous heating DSC experiments [13] is rst
simulated with tentative thermodynamic parameters based on
rst-principles analysis and experimental solvus data. If necessary
for the best reproduction of experimental heat ux data in the
thermokinetic precipitation simulation, the thermodynamic
model parameters of metastable phases are rened inside the
error range of rst-principles and solvus data. In the last part of
this paper, the thermo-kinetic simulation results using optimized
model parameters are compared with experiments.

95

Al
Si
Mg

(0

1)

[001] stacking direction

of ordered subunits
[010]

[100] direction of
modulation

Fig. 1. Structure of ordered GP-zones, Matsuda-phase including Al, schematic.

4 Al2MgSi unit cells are shown. The (0 1 1) lattice plane is indicated by dashed lines.

2. Literature survey
2.2. Microstructure and ordering of GP-zones
2.1. The concept of co-clusters
In quenched AlMg alloys, Mg has a tendency to form clusters
inside the coherent fcc Al-matrix. The size of clusters depends on
the binding energy between solute atoms. The binding energy of
MgMg clusters is too low to support cluster formation other than
doublets or triples of solute atoms [18]. In AlSi alloys, the
occurrence of initial SiSi clusters after quenching has been
discussed controversially. An early study suggested that the initial
stage of precipitation would involve Si clustering [19], while DSC
analysis did not indicate cluster formation prior to Si precipitation
[20]. On the other hand, streak regions observed with TEM were
interpreted as coherent Si-clusters [21]. Recently, clusters in Al
MgSi alloys have been further distinguished by their different
effect on resistivity and heat ow [2225]. It seems that vacancy
kinetics, e.g. the rate of vacancy migration, plays an important role
for these differences between several cluster types [25]. However,
these effects are not considered in the present study, and the
thermodynamics of pure Mg- and Si-clusters are not treated here.
The term co-cluster is used to denote clusters involving two
alloying elements such as MgSi in AlMgSi alloy. The simplest
form of a co-cluster is a dimer, a chemical structure formed from
two subunits. Dimer clusters are too small to be detected experimentally [26]. However, nowadays co-clusters involving 10 or
more atoms can be explored by atom probe tomography (APT).
In AlMgSi alloys, the concept of cluster and co-cluster formation
was suggested by Edwards et al. [11], describing the earliest
features of precipitation at the lowest aging temperatures. These
are distinguished from the Al-matrix by techniques such as
HRTEM, APFIM (atom probe eld ion microscopy) or 3D atom
probe. Edwards, by using APFIM, postulated the formation and
dissolution of Si- and Mg-clusters preceding the formation of coclusters. Later, Murayama et al. [27,28] suggested from 3D atom
probe results that the formation of MgSi co-clusters takes place
by aggregation of Mg- and Si-clusters, which exist in quenched
AA6016. According to those studies, MgSi co-clusters alter their
composition towards higher Mg contents, when the alloy composition is changed from Si-excess to Si-balance. Recently, aggregation of Mg and Si before formation of GP-zones has been
determined by HRTEM and quantied by atom probe tomography
[10]. Nearly all measured aggregates were MgSi co-clusters.
Co-cluster compositions cumulated around Mg:Si 1:1 for both
Si- and Mg-rich AA6016 alloys aged at 373 K for 16 h. After room
temperature aging for 7 days, clusters showed higher Si contents
in Si-rich alloys and vice versa for Mg.

HRTEM of solution-treated and quenched balanced-Si Al-1.6 wt

% Mg2Si specimens revealed a few nanometer wide monolayers
platelets after ageing at 343 and 423 K [12]. These monolayers
were composed of Mg and Si columns with Mg:Si 1:1, arranged
along crystallographic [1 0 0]-direction of the Al-matrix. Monolayers or bilayers of solute atoms in an Al-matrix seem to be a
rather common feature of GP-zones. They were also observed in
the AlMg [29], AlCu [30], AlMgZn [31], and AlCuMg [32]
systems. MgSi-planes coating Al layers are shown schematically
in Fig. 1. They constitute an fcc-based ordered phase, described by
the formula Al2MgSi. In contrast to Al-free MgSi Matsuda-phase,
Al2MgSi would be energetically, as well as in terms of its lattice
mismatch, favourable as coherent phase in the Al-matrix [5].
An earlier study by Thomas [33] suggests a different type of
ordering, with Mg2-rows and Si-rows on the (0 1 1) lattice planes
of the matrix growing along the [1 0 0]-direction and an atomic
ratio of Mg:Si 2:1. However, Ravi and Wolverton [4] concluded
from rst-principles calculations that this model is energetically
unfavourable.
In the binary AlMg subsystem of AlMgSi, ordered precipitates
were explored by Sato et al. [30], Bernole et al. [34] and Dauger et al.
[35]. Super-lattice spots detected by TEM of solution-treated and
water-quenched Al-10 wt% Mg alloy after ageing at room temperature implied that ordered precipitates form along crystallographic
[1 0 0], with the ordering type of L10 [34] or L12 [35].
2.3. Al-solubility in
The generally accepted stoichiometry for Al-free, monoclinic
with space group C2/m is Mg5Si6. This decision was based on a
comprehensive experimental high-resolution exploration in combination with rst-principles studies of energetically favorable
structures and compositions, which are found in a number of
earlier publications [25,3638]. New experiments indicate that, in
Mg5Si6, Si is partially substituted by Al [39,40]. At present, vital
uncertainty persists as to the extent of the Al solubility in Mg5Si6.
2.4. Al-pre- phases
Energy dispersive spectrometry measurements in AlMgSi
alloy revealed the existence of a structure of hexagonal Al3
4Mg89Cu2Si7 Q-phase without Cu, rst named B [41], then
denoted M [42] or type-C [43]. Cayron [44,45] further suggested
close structural correlation between trigonal type-A or U1-phase

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E. Povoden-Karadeniz et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 43 (2013) 94104

3. Thermodynamic modeling

added, based on rst-principles energies of the end member

compounds.
In the Gibbs energies of the ordered binary compounds (Eqs.
(4)(6)), interactions (Eq. (7)) and reciprocal interactions, representing a rst approximation to short range order (SRO) (Eq. (8)),
are dened analogously to Hallstedt and Kim [54] for the binary
AlLi system. The Gibbs energies of the ordered binary compounds
are written as

3.1. Co-clusters

4ssl
4ssl
G4ssl
A:A:A:B GA:A:B:A . . . GA3 B 3uAB GA3 B ;

4ssl
4ssl
G4ssl
A:A:B:B GA:B:A:B . . . GA2 B2 4uAB

and orthorhombic type-B or U2-phase [43,4648] with Cucontaining counterparts, QP and QC. Ravi and Wolverton [4]
calculated the molar enthalpies of these phases at 0 K in the
framework of the rst-principles plane wave pseudo-potential
method.

Starink and Wang [26] reproduced an extensive set of calorimetric data for CuMg co-clusters in AlMgCu, when treating the
co-clusters (co-cl) in a regular solution model. In analogy to their
work, we choose the following regular solution model for the
description of (Mg,Si) co-clusters in AlMgSi
Gcocl
m
E

xi Gcocl
i
i

cocl

RT xi lnxi G
i

xMg xSi LxMg xSi 

Gcocl
Mg

cocl

Gcocl
Si

and
are the molar Gibbs energies of fcc Mg and
cocl
fcc Si end members [49].E G
is an excess energy term representing the non-ideal mixing between Mg and Si, which is
expressed in terms of temperature-dependent interaction parameter 0 L. This is the simplest modeling approach for MgSi coclusters, which allows for a gradual change of chemical composition to evolve from high Si- to high Mg-contents.

and
4ssl
4ssl
G4ssl
A:B:B:B GB:A:B:B . . . GAB3 3uAB GAB3

with Al:Mg, Al:Si and Mg:Si as possible A:B combinations. uAB is an

expression for the bond exchange energy between A and B.
Due to the symmetry of the model, interactions are assumed to
be independent of the respective sublattice, as well as the
occupation of the other sublattices. This leads to the denition of
interaction parameters
4ssl
4ssl
L4ssl
A;B:n:n:n Ln:A;B:n:n . . . LAB ;

where the asterisk * stands for Al, Mg, or Si.

In a rst approximation, the reciprocal interactions are taken
identical and equal to the nearest neighbour energy bonds [50],
4ssl
4ssl
L4ssl
A;B:A;B:n:n LA;B:n:A;B:n . . . LABrec uAB

3.2. Ordered GP-zones

The following relations for the ternary model parameters (Eqs.

(9)(11)) are used in analogy to Kusoffsky et al. [50]

In the present study, GP-zones are considered as an ordered

Al2MgSi phase with fcc-based ordering of binary compounds. The
four substitutional sublattice model (4SLM), as proposed by
Kusoffsky et al. [50] and based on early studies of Gorsky [51]
and Bragg and Williams [52], is used.
Since the four sublattices are considered to be energetically
identical, this approach represents a symmetric model. In a binary
system, ordering is associated with the fractions of species on the
sublattices (site fractions) as follows: if all sublattices have the
same site-fractions of species, the phase is considered as being
disordered. If three of the four sublattices have identical site
fractions, the phase is considered to be an ordered structure of
L12 type [50]. With two identical pairs of sublattices, each
described by individual site fraction values, the phase is an
ordered structure of type L10. Thermodynamically, the molar
Gibbs energy of the disordered fcc-structure, as well as the
ordered structures, is described by two parts given as

G4ssl
Al2 MgSi 2uAlMg 2uAlSi uMgSi AAl2 MgSi ;

G4ssl
Mg2 AlSi 2uAlMg 2uMgSi uAlSi AMg2 AlSi ;

10

ord s
Gm Gdis
m xi Gm yi ;

where Gdis
m xi
s
and Gord
m yi

is the molar Gibbs energy of the disordered state

is the molar ordering energy. When the phase is
disordered, the ordering energy is zero. This is achieved by
expressing the ordering energy as
4ssl s
4ssl s
s
Gord
m yi Gm yi Gm yi xi

The two terms used in Eq. (3) to calculate the ordering energy
are represented by identical functions in the classical compound
energy formalism [53]. The difference between the two is that the
rst term is evaluated with the individual sublattice site fractions
yi and the second term using the mean value of site fractions,
which is achieved by replacing them with the mole fraction
variables xi.
The thermodynamic modeling of ordered GP-zones is started in
the AlMg subsystem. Then, descriptions of the purely hypothetical fcc-based ordering in the AlSi and MgSi subsystems are

and
G4ssl
Si2 AlMg 2uAlSi 2uMgSi uAlMg ASi2 AlMg

11

Eqs. (9)(11) relate the Gibbs energies of formation of the

ternary compounds to the nearest-neighbour energy bonds in the
constituting binary systems. Accordingly, the ternary reciprocal
parameter is related to the nearest-neighbour energy bonds as
LAl;Mg:Al;Si:n:n L4ssl
AlMgSirec 0:5uAlMg uAlSi uMgSi

12

Assessed interaction parameters are listed in Appendix A to this

article, where the complete set of model parameters of GP-zones is
summarized.
3.3. Al-containing Mg5Si4Al2
The binary end-member compound of is simply described as
(Mg)5(Si)6, in accordance with Zhang et al. [7].
When trying out a description for as hypothetical solid
solution ranging from high-Al Mg5(Si,Al)6 to Al-free Mg5Si6,
thermo-kinetic simulations could not reproduce the measured
calorimetric data obtained by Falahati et al. [13]. On the other
hand, the model (Mg)5(Si)4(Al)2 for stoichiometric Al- with the
lowest computed 0 K energy [39] appears to be well-suited for
thermo-kinetic simulations. This suggests that Al and Si are not
expected to appear together on the same crystallographic site, but
one of the (B)4-sites of Mg5Si6 can be either lled up by Si or Al.
3.4. Al-pre- phases
On basis of the reported stoichiometry in rst-principles
studies [4648], U1 is described as (Al)2(Mg)(Si)2 and U2 as (Al)

E. Povoden-Karadeniz et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 43 (2013) 94104

1.2

Mg/Si co-cl
1.1

Mg/Si GP
1

x(el) ; Mg:Si ratio

(Mg)(Si) in the present assessment. Originally, Matsuda et al. [43]

measured differing stoichiometry of type-A and type-B precipitates with the same structure and apparently similar stability as
U1 and U2, respectively. The composition of type-A and type-B
particles, having been extracted from the Al-matrix by the thermal
phenol method, compared well with the results from energydispersive X-ray spectroscopy. However, in contrast to U1 and U2, the
thermodynamics of these A-type and B-type phases have not yet
been determined by rst-principles calculations. (Al)3(Mg)9(Si)7
describes the compound with the lowest 0 K energy, whereas
(Al)4(Mg)8(Si)7 refers to the experimental composition of Q-phase.
Ravi et al. [4] thus suggested an increase of the Al/Mg ratio towards
higher temperatures. For the time being, experimental examination
of this observation is not available and, in the present study, a
tentative description of two stoichiometric B end-members,
(Al)3(Mg)9(Si)7 and (Al)4(Mg)8(Si)7 is proposed.

0.9
0.8

Edwards 1998

0.7
0.6
0.5

4. Model parameterization

Murayama 1999
Torster 2010
x (Mg) co-cl
x (Si) co-cl
323

In accordance to Falahati et al. [13], we accept that the DSC

curve from continuous heating experiments (symbols in Fig. 2) at
low temperatures reects the thermal stabilities of co-clusters and
GP-zones and the endothermal peak below the formation temperature of characterizes their kinetic solvi. In a heat ux DSC
with pure Al-reference, the heat ow is formulated as
sys

heat

T
dh hAl T


;

t
dT
t

13
sys

where csys
is
p is the specic heat capacity of the alloy in J/g K, h
the specic enthalpy of the alloy in J/g, and T/t is the heating
rate in K/s. csys
p and thus the simulated DSC curve is changing when
the matrix composition changes. During precipitation, composition changes of the matrix are related to amount and composition
of the precipitating phases, and in terms of thermodynamics their
Gibbs energy. In the present modeling of co-clusters, their Gibbs
energy is controlled by the value of the interaction parameter
0 cocl
LMg;Si

0 cocl
LMg;Si

in Eq. 1.
is optimized by using the reported MgSi
ratio of co-clusters [10,11,27] presented in Fig. 3 and the DSC curve

-0.005

exo

heat flow [W/g]

endo

0.01

0.005

373

423

Temperature, K

4.1. MgSi co-clusters

Al
flowW=g csys
p cp

97

experiment
simulation
-0.01
373

473

Temperature, K
Fig. 2. Comparison of low-temperature continuous heating DSC curve of quenched
AlMgSi alloy obtained in the present assessment with that from experimental
literature (symbols) [13].

Fig. 3. Simulated constitution of MgSi co-clusters (co-cl) and GP-zones in

quenched AA6016 alloy with excess Si, x(Si) 0.01 and x(Mg) 0.004 as obtained
in the thermo-kinetic simulations compared with experiments (symbols).

from Falahati et al. [13] shown in Fig. 2. Optimized A and BT terms

read
0 cocl
LMg;Si

75; 000 15 T

14

The high negative A-value of 0 Lcocl

Mg;Si stabilizes the co-cluster
phase at low temperatures. Without this adjustment, the phase is
13 kJ less stable and will not precipitate in AlMgSi alloys. The
positive, temperature-dependent B-term controls its dissolution
temperature and the associated endothermal DSC signal.
4.2. GP-zones
For the optimization of ordering parameters of GP-zones, 0 K
molar enthalpies are used in addition to DSC data and dissolution
temperatures. These data are computed for ordered, fcc-based
compounds of the binary subsystems using the plane wave
pseudo-potential method of the Vienna Ab initio Simulation
Package (VASP) [55,56] with the generalized gradient approximation (GGA). Projected augmented wave pseudo-potentials (PAWPBE) [57] and cells with 4 atomic sites (GP-zones) and 3 atomic
sites (Mg2Si) are used in the model. Energy and k-point convergence was asserted for all calculations with k-point meshes
20  20  20. k-point sampling using MonkhorstPack [58]
k-point meshes from 10  10  10 to 50  50  50 grids indicate
an uncertainty for the calculated total energy below 0.01 eV/atom.
The calculations are performed allowing all degrees of freedom
such as volume, shape, and ionic positions of the crystal structure
to relax. Total energies are then collected with respect to the fully
relaxed geometries. For cut-off energies the default values,
denoted ENMAX in the VASP-le POTCAR, are used. These are
ENMAX(Al)240.3 eV, ENMAX(Mg)126.143 eV and ENMAX(Si)
245.34 eV. For systems containing more than one element, the
maximum cut-offs are used for the calculations. The electronic
congurations of elements are for Al s2p1, for Mg s2p0 and for Si
s2p2. For the optimization of the binary AlMg ordering parameters, molar enthalpies from generalized gradient approximation
(GGA) calculations published in refs. [5,35] and new 0 K enthalpies
from the present work are taken together with experimental
dissolution temperatures of Al3Mg [5961]. The thermodynamic
data of the Al3Mg end-member was given a high weight in the

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E. Povoden-Karadeniz et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 43 (2013) 94104

optimization, since Al3Mg represents an experimentally observed

binary GP-zone, whereas all the other end-members of ordered Al
MgSi GP-zones represent hypothetical states. Care was taken that
the thermodynamic solvus of Al3Mg was higher than the experimentally determined dissolution temperature. This is shown in
Fig. 4. As discussed e.g. by Zhang et al. [7], both, interfacial and
strain energies, increase the Gibbs energy and decrease the
stability of metastable phases in the Al-matrix. Thus, the experimental phase boundaries are shifted towards lower temperatures
relative to the thermodynamic phase boundaries.
The calculated molar entropy and molar heat capacity of Al3Mg
at 300 K using the present description are 2.88 J/mol K and 0.74 J/
mol K higher than rst-principles data employing DFT and quasiharmonic approximation for the free energy [62]. The ordering
parameter uAlSi exerts strong control on the thermal stability of the
ternary GP-zones. With uAlSi being set to 8000 J/mol, a best t of
the available rst-principles data of ternary Al2MgSi GP-zones
[4,5,7] is obtained. A value of AMg2 AlSi +2800 J/mol in Eq. (10) is
used to stabilize ternary GP-zones in the thermo-kinetic simulation [13]. Other coefcients of model parameters (see Appendix A)
are essential for the reproduction of rst-principles molar enthalpies of ordered binary compounds. The quantitative comparison
between assessed and rst-principles data is given in Table 1.
Ravi and Wolverton [4] reported a more negative molar
enthalpy of Al3Mg L12, 1Hm(Al3Mg) 1400 J/mol by using rstprinciples with GGA. Van Huis [5] suggested 1Hm(Al3Mg)
900 J/mol, also with GGA. The only obvious differences of the
calculations among different groups that might inuence the

420

Osamura 1984
400

van Rooyen 1989

Starink 1997

Temperature, K

380
360

results, pertain cut-off energies (155 eV [4], 200 eV [5] and ENMAX
used in the present study) and pseudo-potentials (ultrasoft [4,5],
PAW-PBE used in the present study). If one adjusts thermodynamic model parameters such as to approximate further to the
more negative enthalpies of formation of Al3Mg from the literature, the reproduction of experimental solvus temperatures of
Al3Mg, shown in Fig. 4 becomes worse. The thermodynamics of
binary compounds also exert a strong effect on the thermal
stability of Al2MgSi GP-zones. The assessed CALPHAD enthalpies
given in Table 1 are thus resulting from a sensitive balance
between binary solvus data, rst-principles data, correct splitting
of site fractions due to the ordering, and the thermal stability of
GP-zones.
4.3. MgSi and
Molar enthalpies and entropies for and have recently
become available from rst-principles calculations including phonon contributions [7,14]. These data yield a good reproduction of
experimental solvus temperatures. Use of these thermodynamic
standard data for the thermo-kinetic simulation of precipitation
[13] in AlMgSi alloy AA6016 leads to qualitative agreement
between the predicted precipitate evolution and experiments. By
adjusting the suggested thermodynamics of and inside the
uncertainty limits given [7] in the present assessment, experimental exothermal (formation) and endothermal (dissolution)
DSC-peaks [13] are reproduced within 10 K for , and within
40 K for .
Heat capacities by NeumannKopp's rule differ from the rstprinciples results [14], by about 1 to 2 J/K mol for Mg5Si6. When
comparing relative heat capacities of metastable phases, one nds
that Neumann Kopp's rule suggests the lowest values for ,
whereas Zhao et al. [14] obtain the highest values, the difference
being 2.2 J/K mol at room temperature. Thus, excess terms (Gex
phase )
are used in order to correct this discrepancy, and the assessed
trend of heat capacity with temperature is shown in Fig. 5. The
following CALPHAD parameters are suggested, accordingly:
1 diamond
G 51 H hcp
500030 T Gex

Mg 6 H Si
7
2
Gex
T 3;
0:0096 T 1  10

340

15

and

320

G GMg2 Si 24; 25040:4 T Gex

2
1
Gex
;
5:9 TlnT0:0042 T 130; 000 T

300
280
0.05

0.1

0.15

0.2

x(Mg)
Fig. 4. Calculated thermodynamic solvus of ordered L12 Al3Mg. Symbols represent
experimentally determined dissolution data from the literature.

Table 1
Optimized formation enthalpies 1Hm (J/mol) of fcc-based ordered phases of the
binary subsystems AlMg and AlSi at 298.15 K and rst-principles data at 0 K,
referred to Al fcc, Mg hcp and Si diamond.
Compound

DFT (0 K)

CALPHAD 298.15 K

Al3Mg L12
AlMg L10
AlMg3 L12
Al3Si L12
AlSi L10
AlSi3 L12

780
146
+605
+10 652
+21 030
+35 578

669
487
+633
+9 727
+17 434
+36 092

16

GMg2 Si is adopted from Ansara et al. [15]. The heat capacity of

is based on the heat capacity of the face-centred cubic stable
Mg2Si phase [15] here. This assumption is made due to the
similarity between and regarding stoichiometry and thermal
stability. Gex
in Eq. (16) is added in order to obtain a atter slope of
the heat capacity curve towards high temperatures than by
NeumannKopp's rule, and in better agreement with the rstprinciples results [14] (see Fig. 5a).
4.4. Al-
With the assessed thermodynamics of Mg5Si6 at hand, the
A-parameter for Al-rich phase Mg5Si4Al2 is approximated to
rst-principles enthalpy data, 1Hm(Mg5Si4Al3)1Hm(Mg5Si6)
0.08 eV per mol of solute atoms [39]. In order to give a reasonable
value to the entropic contribution to the Gibbs energy, the inuence
of the B-term on the simulated DSC-curve is tted by trial and error.
Best results are obtained with the following description:
cc
5 Si4 Al2
GMg
5 H Mghcp
4 H Sidiamond
2 H Alf
30; 00018 T
m
m
m
m

17

E. Povoden-Karadeniz et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 43 (2013) 94104

29

29

b
c
a

28

c
b

25

24

27

a
26

28

Cp, J/mol K

Cp, J/mol K

27

26
25

U1

24

U2

23

23
22
300

99

400

500

600

700

800

22
300

Temperature, K

400

500

600

700

800

Temperature, K

Fig. 5. Heat capacities of some metastable phases. Comparison between optimized CALPHAD values (bold curves), rst-principles data [14] and heat capacities using
Neumann Kopp's rule. (a) and , (b) U1-phase and U2-phase.

obtained as

4.5. Al-pre- phases

4.5.1. Optimization of Cp-curves
With temperature-dependent excess terms, Gex
phase in Eq. (18)
and Eq. (19), Cp-slopes of U1 and U2 are adjusted in order to
approach the relative Cp data among metastable precipitates from
rst-principles analyses [14]. Cp-curves of U1 and U2 are shown in
Fig. 5b. Heat capacities of the other Al-pre- phases have not been
investigated, thus Neumann Kopp's rule is applied.

4.5.2. U-Phases
By accepting the older rst-principles molar enthalpies of Ravi
and Wolverton [4] for U1 and U2 in the model descriptions, these
phases become too prominent as precipitates. Consequently, and
B do not become stable in thermo-kinetic simulations, which is
not supported experimentally. This problem does not occur, if
most recent rst-principles results [14] are used instead. The
optimized Gibbs energy functions of of U1 and U2 read:
1 diamond
GU1 21 H fAlcc 1 H hcp
500010 T
Mg 2 H Si
ex
6
2
T 3 150; 000 T 1 ;
Gex
U1 GU1 0:0055 T 3  10

18

and
1 diamond
GU2 1 H fAlcc 1 H hcp
14; 0003:75 T
Mg H Si
ex
7
2
T 3 62; 500 T 1
Gex
U2 GU2 0:0015 T 7:5  10

19

4.5.3. B phase
Assuming a similar trend of 0 K molar enthalpies between B
compounds as rst-principles results of Cu-containing Q-phase
compounds [4], Al3Mg9Si7 is considered about 800 J/mol more
stable than Al4Mg8Si7 at room temperature. On the other hand, by
assigning higher entropy to Al4Mg8Si7, this compound is made the
preferred high-temperature modication. Besides 0 K molar
enthalpy of the Al3Mg9Si7 and entropies of formation being
estimated within the range of the other Al-pre- phases, the
optimization of model parameters of B also takes into account
the close microstructural correlation between and B revealed by
TEM [45]. Simultaneous renement of A and BT parameters leads
to the formation of B close to in the thermo-kinetic simulations.
The optimized Gibbs energy functions of B end members are

1 diamond
GAl3 Mg9 Si7 31 H fAlcc 91 H hcp
140; 00010 T;
Mg 7 H Si

20

and
1 diamond
115; 00020 T
GAl4 Mg8 Si7 41 H fAlcc 81 H hcp
Mg 7 H Si

21

The complete set of thermodynamic model parameters of the

AlMgSi database can be downloaded from Ref. [63].

5. Results and discussion

5.1. Thermodynamic data
In Fig. 6, molar enthalpies of hypothetic MgSi L10 GP-zones
resulting from density functional theory calculation are compared
with the optimized molar enthalpy of the disordered co-cluster
phase. The CALPHAD assessment suggests that co-clusters have
lower enthalpies of formation than ordered MgSi L10 and L12
phases.
In Table 2, the assessed standard molar enthalpies of metastable MgSi and AlMgSi phases at 298.15 K and rst-principles
results at 0 K are listed. Further, Hm of metastable phases referred
to Hm(Mg2Si) is given for the purpose of direct comparisons
between assessed CALPHAD and rst-principles data. The thermodynamic equilibrium phase is a suitable reference since its
thermodynamic properties are well-known from extensive experimental and rst-principles studies.
A clear tendency of increasing formation entropies from stable
to less stable compounds exists, which has also been reported
earlier for metastable phases in the AlCu system [64]. This trend
is shown in Fig. 7, where S of intermetallic MgSi and AlMgSi
phases is plotted as a function of formation enthalpies at 298.15 K.
Mg2Si shows the lowest value for the formation enthalpy, whereas
co-clusters exhibit the highest formation entropy. The assessed
thermodynamic data reproduce available literature data well.
Moreover, those formation entropies suggested in the present
work, which lack support by rst-principles calculations, lie well
inside the observed trend.
5.2. Solvi of metastable phases
Thermodynamic solvus temperatures of assessed metastable
phases and equilibrium phases are presented in Fig. 8.

100

E. Povoden-Karadeniz et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 43 (2013) 94104

The optimized metastable solvus of co-clusters is 30 to 40 K

higher than recent values by Starink et al. [65], using nearestneighbor interaction energies between co-cluster constituents,
coupled with experimental DSC data.
Interestingly, our predicted thermodynamic solvus of co-clusters
lies about 5 K higher than the solvus of ordered GP-zones. This implies
that a transformation from co-clusters to GP-zones does not necessarily happen, but these phases may rather be present simultaneously in

50

AA6016, with kinetic control of the predominance of one or the other.

By more elaborate modeling, one may bring the dissolution temperatures of co-clusters and GP-zones closer to each other, This, however is
not legitimated by the current experimental evidence.
Al-containing dissolves at lower temperatures than Mg5Si6. It
seems thus obvious that, in a sequence of metastable phase
formations in a continuous heating experiment of quenched
AA6016 alloy, Mg5Si4Al2 represents the low-temperature form.
This is conrmed by thermo-kinetic simulation results presented
in the following section.

Hm(pure) @ 0K, first princ.

Hm(pure) @ 298.15K, CALPHAD
Hm(GP) @ 0K, first princ.

Hm(phase), kJ/mol

40

co-cl

13

Hm(GP) @ 298.15K, CALPHAD

Hm(co-cl) @ 298.15K, CALPHAD

11
9

30

7
20

10

-25
0.2

0.6

0.4

0.8

Mg5Si 6
U1
U2
Al4Mg8Si7
Al3Mg9Si7

-15
-5

Al2MgSi GP
Mg5Si 6

Mg5Si4Al 2
U1
H,
5

J/mol

x(Si)

Mg2Si

Fig. 6. Enthalpies of formation of binary fcc-type ordered Mg-Si compounds from

Mg hcp and Si diamond, with L10 MgSi reecting hypothetic Al-free Matsuda-type
GP-zones: First-principles results at 0 K and CALPHAD optimization at 298.15 K, in
comparison with the modeling results of the MgSi co-cluster phase at 298.15 K are
shown. Also, computed 0 K enthalpies of formation of metastable Mg fcc and Si fcc
are given.

S , -3
J/Kmol

Fig. 7. Calculated entropies versus enthalpies of formation of assessed metastable

MgSi and AlMgSi phases (black diamonds) at 298.15 K and rst-principles data
(Ref. [14], white diamonds). Also, CALPHAD data for Mg2Si are given. References are
Al fcc, Mg hcp and Si diamond.

Table 2
Assessed CALPHAD (column 3) versus rst-principles standard molar enthalpies (column 4) of metastable phases and Hm of metastable phases referred to Hm(Mg2Si)
(column 5).
Formula

Phase description

1Hm, 298.15
K (J/mol)

1Hm, 0 K (J/mol)

1Hm(Phase)1Hm
(Mg2Si) (J/mol)a

Reference

Al2MgSi

GP-zones, Matsuda-phase
incl. Al-layers, L10

Mg5Si4Al2
Mg5Si6

l-, monoclinic
, monoclinic

+8
+7

+3
+4
+3

+25 800a
+25 514
+25 095
+19 018
+21 300
+21 800
+21 200

Al3Mg9Si7

B, hexagonal

Al4Mg8Si7
Al2MgSi2

B, hexagonal
U1, hexagonal

AlMgSi

U2, orthorhombic

Mg1.8Si

, hexagonal

van Huis [5], GGA

This work, GGA
This work, assessed
This work, assessed
Ravi and Wolverton [4],
van Huis et al. [5], GGA
Zhang et al. [7]b
Zhao et al. [14]
This work, assessed
Ravi and Wolverton [4],
This work, assessed
This work, assessed
Ravi and Wolverton [4],
Zhao et al. [14]
This work, assessed
Ravi and Wolverton [4],
Zhao et al. [14]
This work, assessed
van Huis et al. [5], GGA
Zhang et al. [7]b
Zhao et al. [14]
This work, assessed

+3 350
2 727

+3 312
376

7 368
6 056

753
733

4 506
4 496

15 500
15 677
15 444

000
633

300
000
500

6 900

3 100

+21 369
+11 100
14 377
+15 689
+14 900

5 800

+21 012
+12 200

12 700
12 600

+17 249
+5 100
+5 100

+6 301

GGA

GGA

GGA

GGA

a
The following 1Hm(Mg2Si) values in J/mol were reported and are used for respective calculations of 1Hm(Phase) 1Hm(Mg2Si): 17 800 [5], 17 700 [7], 18 000 [4],
17881 (for 0 K GGA data, this work), 21 745 (for 298.15 K CALPHAD data).
b
First-principles data scaled by CALPHAD standard data of Mg2Si.

E. Povoden-Karadeniz et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 43 (2013) 94104

liquid
900
M g 2 Si

800

Temperature,K

Si
Al4Mg8Si7

700

Al3Mg9Si7

U1

600

U2

Mg5Si6
co-cl

Mg5Si4Al2

500

GP-zones

400

co-cl [64]
[7 ]
[ 7]

300
0.002

0.006

-AlMg
-AlMg

0.01

-AlMg

0.014

x(Mg)
Fig. 8. Assessed solvi MgSi and AlMgSi phases as function of Mg-content in a
typical AA6016 alloy containing 0.76 at% Si and data from previous rst-principles
calculations including phonons (dotted curves), and modied by Mg2Si CALPHAD
parameters [7]. The suggested metastable solvus of co-clusters from Ref. [65] is also
shown. Solid lines are from present work. For completeness, solvi of AlMg phases
close to room temperature are included.

101

In Table 3, temperatures of experimentally observed precipitates (Tobs) after isothermal heat treatments of 6xxx Al-alloys with
typical Mg/Si ratios from various studies [11,12,28,3740,43,45,
47,48,6672] are related to their calculated metastable solvus
temperature, Tdis. Most of the listed examples contain small
amounts of Fe, Mn, Cr, Cu and/or Ti. However, no inuence on
the stabilities of phases presented in this study was found [73].
Thus, as rst approximation, these impurities are neglected in the
calculation of solvus temperatures. As discussed in Section 4.2, Tdis
will lie above the highest Tobs during isothermal aging, represented by bold values in Table 3. The modeling results obey this
rule, and TdisTobs in Table 3 is always positive, accordingly. For the
Al-pre- phases, the calculated TdisTobs is signicantly higher
than for the other phases. This is likely resulting from underestimation of their thermal metastability due to lack of experimental data.

5.3. Thermo-kinetic simulation

As described in Section 4 earlier in this paper, for the optimization of model parameters of metastable phases, we consider the
phase evolution during continuous heating, represented by DSC
signals (Fig. 9a), as key experiments in addition to thermodynamic
data. In order to show that this approach is successful and the

Table 3
Experimentally observed phases after quenching and isothermal ageing of Al-alloys and calculated metastable solvi.
Alloy type

at% Si

x(Mg)/x(Si)

Aging T (K)

Aging time (h)

Precipitate exp.

Exp. technique

Ref. exp.

TdisTobs (K)

6016
6016
6082
6061
6061
6016
6016
6061
6061
6016
6016
6016
6016
6016
6016
6016
6016
6016
6016
6016
6016
6016
6013
6082
6016
6016
6016
6061
6063
6063
6005
6005
6016
6082
6082
6082
6016
6016
6016
6016
6016
6016

0.33
0.33
0.51
0.55
0.58
0.6
0.6
0.63
0.63
0.7
0.7
0.7
0.72
0.72
0.72
0.72
0.72
0.73
0.73
0.73
0.73
0.73
0.74
0.74
0.75
0.75
0.75
0.76
0.79
0.79
0.79
0.79
0.84
0.84
0.86
0.86
0.88
0.88
0.88
1
1
1.1

2.12
2.12
1.08
1.93
1.59
1.67
1.67
1.75
1.75
0.93
0.93
0.50
0.81
0.81
0.81
0.81
0.81
0.96
0.96
0.96
0.96
0.96
1.46
0.80
0.69
0.69
0.69
1.17
0.76
0.76
0.77
0.77
0.48
0.83
0.78
0.78
0.41
0.41
0.41
1.00
1.00
0.18

343
343
458
453
443
553
588
458
458
343
343
523
448
448
448
448
493
343
523
523
523
523
453
573
448
448
448
343
458
458
458
663
373
573
423
533
448
448
448
553
588
448

16
16
5
5
333
0.5
0.5
600
600
16
16
3
36
208
208
208
45
1667
1
8
167
278
5
0.02
3
17
208
60
1
77
18000
0.003
16
0.02
48
8
3
208
208
0.5
0.5
3

GP-zones
co-clusters

Al-

B
GP-zones
co-clusters

Al-

U2-phase
Al-
GP-zones

TYPE-B (U2)
TYPE-A (U1)
TYPE-C (B)

GP-zones

co-clusters

Co-clusters

U1-phase
GP-zones
U2-phase

GP-zones

HREMa+TEM
HREM+TEM
TEM
TEM
APTb+TEM
SEMc+XRDd
SEM+XRD
HREM+TEM
HREM+TEM
HREM+TEM
HREM+TEM
HRTEM
APT+TEM
HRTEM
HRTEM
HRTEM
APT+TEM
HRTEM
HRTEM
HRTEM
HRTEM
HRTEM
TEM
TEM
TEM+HREM
TEM+HREM
TEM+HREM
TEM
TEM
TEM
TEM
TEM
HRTEM+ATP
TEM
TEM+HREM
EDe)+HRTEM
TEM+HREM
TEM+HREM
TEM+HREM
SEM+XRD
SEM+XRD
TEM+HREM

[28]
[28]
[37]
[66]
[40]
[67]
[67]
[45]
[45]
[28]
[28]
[43]
[39]
[68]
[68]
[68]
[39]
[12]
[43]
[43]
[43]
[43]
[66]
[69]
[47]
[47]
[47]
[11]
[70]
[70]
[71]
[71]
[10]
[71]
[38]
[48]
[47]
[47]
[47]
[67]
[67]
[47]

115
117
98
132
131
34
163
296
211
145
143
160
113
127
277
212
68
151
209
148
156
133
148
147
34
124
124
164
123
123
123
62
97
165
167
156
25
199
272
62
185
11

102

E. Povoden-Karadeniz et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 43 (2013) 94104

Table 3 (continued )
Alloy type

at% Si

x(Mg)/x(Si)

Aging T (K)

Aging time (h)

Precipitate exp.

Exp. technique

Ref. exp.

TdisTobs (K)

6016
6016
6016
6016
6016

1.1
1.1
1.15
1.6
1.6

0.18
0.18
0.42
0.63
0.63

448
448
453
553
588

208
208
3
0.5
0.5

U2-phase

TEM+HREM
TEM+HREM
HRTEM
SEM+XRD
SEM+XRD

[47]
[47]
[72]
[67]
[67]

181
215
138
57
207

High resolution electron microscopy.

Atom probe tomography.
c
Scanning electron microscopy.
d
X-ray diffraction.
e
Electron diffraction.
b

endo

0.005
0
-0.005

exo

heat flow [W/g]

0.01

experiment
simulation

-0.01

373

473

573

673

773

Temperature, K

Si diamond

molar phase fractions

0.004

Mg2Si

Simulating precipitation of AA6016 model alloy with higher Si,

U2 becomes more important in the simulation, whereas the
amount of U1 remains low. This trend correlates with experimental ndings [47].

Mg5Si6

0.003
Al2MgSi GP
0.002 co-clusters

Al4Mg8Si7

U1

0.001

U2

6. Summary

Mg5Si4Al2

373

473

573

673

increases. For an alloy with equal Si- and Mg-content of 1 at%

Mg0.55Si0.45 is calculated.
In AA6016, both co-clustering and ordering can occur. In the
simulation, the DSC-curve at temperatures below 453 K is
resulting from the precipitation of co-clusters and GP-zones.
Mg5Si4Al2 is a low-temperature form of . Experimentally, this
phase has been observed during isothermal aging at 443 K, i.e.
below the peak temperature of formation. This is reproduced by
simulation. Transformation from Mg5Si4Al2 to Mg5Si6 occurs
around 483 K.
All of the Al-pre- phases occur along with . Among Al-pre-
phases, B is the most prominent one. U-phases show considerably lower volume fractions. The deviations between DSC
signal and simulation results may be due to complex transformation kinetics among Al-pre- phases, which are not reected
in our thermo-kinetic model.

773

Temperature,K
Fig. 9. Simulated heat ow versus DSC experiment during continuous heating (a),
predicted evolution of phase fractions (b).

optimized model parameters are applicable for problems of

technological relevance, in Fig. 9b, the predicted evolution of
metastable phases in AA6016 during continuous heating is compared with experiments [13].
The atomic mobilities of species i, Qi used for the thermokinetic simulations are extracted from published diffusion data
[7479]. They are listed in Appendix B in the form Q i Q Si
RlnM 0i  T[80]. Q Si is the activation energy, R is the gas constant
and M 0i is the frequency factor. The diffusion mobility database mc
lmgsi.ddb can be downloaded from Ref. [63] for convenience. For
the interfacial energies of precipitate phases, the generalizedbroken-bond model [81] is employed. Quenched-in vacancies are
treated using a model by Falahati et al. [82].
The following features of metastable phase evolution during
continuous heating of quenched AA6016 are observed in the
thermo-kinetic simulation based on the present assessment:
A chemical composition of co-clusters close to Mg1Si1 is
simulated for AA6016 with excess Si. Moving from Si-rich to
Mg-rich alloy compositions, the Mg-content in co-clusters

Optimized CALPHAD model parameters of a thermodynamic

database for metastable phases in the AlMgSi system are presented,
and their application for thermo-kinetic simulations of the evolution
of metastable phases in AA6016 alloys is discussed. Simulation predicts
the occurrence of MgSi co-clusters up to temperatures as high as
453 K. Overlapping stability ranges are predicted for co-clusters and
GP-zones. Mg5Si4Al2 forms in the low-temperature part of the
metastability range, followed by Mg5Si6 at about 483 K.
Combination of rst-principles calculations, experimental solvus
and heat ux data of continuous-heating DSC proofs to be a useful
strategy for the determination of Gibbs energies of metastable phases.
The potential of thermo-kinetic simulation for the renement of
tentative model parameters is demonstrated, which even allows fast
access to reliable entropy values of metastable phases. This is
particularly useful if rst-principles phonon calculations are not
available or exceptionally time-consuming due to complexity regarding phase structures or number of components of the system of
interest.

Acknowledgement
The contribution of the Vienna Computational Materials
Laboratory (VICOM) is acknowledged in allocating computational
capacities, maintenance and technical support. Financial support
by the Christian Doppler Forschungsgesellschaft (CDG), and by the

E. Povoden-Karadeniz et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 43 (2013) 94104

Austrian Federal Government (in particular from the Bundesministerium fr Verkehr, Innovation und Technologie and the Bundesministerium fr Wirtschaft, Familie und Jugend) and the
Styrian Provincial Government, represented by sterreichische
Forschungsfrderungsgesellschaft mbH and by Steirische
Wirtschafts-frderungsgesellschaft mbH, within the research
activities of the K2 Competence Centre on Integrated Research
in Materials, Processing and Product Engineering, operated by the
Materials Center Leoben Forschung GmbH in the framework of the
Austrian COMET Competence Centre Programme, is gratefully
acknowledged.

103

G4ssl
Si2 AlMg 2uAlSi 2uMgSi uAlMg

Appendix B. Element mobilities used for the thermo-kinetic

simulations
Mobility of Al: [77]
5
Q Al
Al 127; 200 RTln1:39  10

127; 200 RTln1:39  105 77

Q Mg
Al
Al
Q Si
Al Q Al

Appendix A. Thermodynamic model parameters of GP-zones

Mobility of Mg: [77]

119; 000 RTln3:7  105

AlMg

Q Al
Mg

uAlMg 500 0:45185T

5
Q Mg
Mg 112; 499 RTln5:7  10 77

G4ssl
Al2 Mg 2

4u

54; 551 77

Q Mg;Al
Mg

G4ssl
Al3 Mg 3u GAl3 Mg

Al
Q Si
Mg Q Mg

G4ssl
AlMg 3 3u GAlMg3

Mobility of Si: [78]

GAl3 Mg GAlMg3 0
0 dis
LAl;Mg

4ssl
4ssl
4ssl
0 4ssl
G4ssl
Al3 Mg 1:5GAl2 Mg2 GAlMg3 1:5LAlMgrec 4 LAlMg

4
Q Al
Si 136; 400 RTln2:31  10

1 dis
LAl;Mg

4ssl
2G4ssl
Al3 Mg 2GAlMg 3

4
Q Si
Si 448; 400 RTln154  10 78

2 dis
LAl;Mg

4ssl
G4ssl
Al3 Mg 1:5GAl2 Mg2

0 4ssl
LAlMg

3305:252:4T

1 4ssl
LAlMg

56:25 0:025T

2 4ssl
LAlMg

41 L4ssl
AlMg

4ssl
G4ssl
AlMg 3 1:5LAlMgrec

42 L4ssl
AlMg

325 0:17T

L4ssl
AlMgrec uAlMg

Al
Q Mg
Si Q Si

Appendix C. Supporting information

Supplementary data associated with this article can be found in the
online version at http://dx.doi.org/10.1016/j.calphad.2013.03.004.

AlSi
uAlSi 8000
G4ssl
Al2 Si2 4u
G4ssl
Al3 Si

3u GAl3 Si

G4ssl
AlSi3 3u GAlSi3
GAl3 Si 3 750
GAlSi3 5 000
0 dis
LAl;Si

4ssl
4ssl
4ssl
G4ssl
Al3 Si 1:5GAl2 Si2 GAlSi3 1:5LAlSirec 95 ; 6910:096T

1 dis
LAl;Si

4ssl
2G4ssl
Al3 Si 2GAlSi3 2 500

2 dis
LAl;Si

4ssl
4ssl
4ssl
G4ssl
Al3 Si 1:5GAl2 Si2 GAlSi3 1:5LAlSirec 20; 735

L4ssl
AlSirec uAlSi
MgSi
uMgSi 16; 000
G4ssl
Mg2 Si2 4u
G4ssl
Mg3 Si 3u GMg 3 Si
G4ssl
MgSi3 3u GMgSi3
GMg3 Si GMgSi3 0
0 dis
LMg;Si

4ssl
4ssl
4ssl
G4ssl
Mg3 Si 1:5GMg2 Si2 GMgSi3 1:5LMgSirec

1 dis
LMg;Si

4ssl
2G4ssl
Mg 3 Si 2GMgSi3

2 dis
LMg;Si

4ssl
4ssl
4ssl
G4ssl
Mg3 Si 1:5GMg2 Si2 GMgSi3 1:5LMgSirec 24; 000

200; 000 0:89T

AlMgSi
G4ssl
AlMgSi 2uAlMg 2uAlSi uMgSi
G4ssl
Mg2 AlSi 2uAlMg 2uMgSi uAlSi 2800

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