,.rr.* .

AND i!iEiEmM
Journal of Alloy; and Compiwnds 247 (1797
131-42

Investigation of the Al-Mg-Si system by experiments and thermodynamic

calcuiations ’

Abstract

The enthalpies of formation and fusion as well as rhe heat capacity of Mg:Si were measured calorimetrically. The Al comer of the
Al-M@ ternary system was investigated hy DTA and optical micrognphy. of the solvusof the Al(f.c.c.) solid solution
A few points
were determinedby dilatometry.The resultsof theseexperiments.rogerherwith literaturedata. were usedlo redeterminea completeset of
analytical descriprionsof Ihe Gibbs energies of all stable phases of the Al-M@ system.

1. Introduction ternary solubility of the Al(f.c.c.) solid solution show

Phase diagrams are an essential tool for all material
development. A very effective method of evaluating phase
diagrams is thermodynamic optimization using simultan-
eously the phase diagram and thermodynamic data. The
primary goals of this method are
(i) to check the compatibility of the data available from
different sources:
(ii) to extrapolate into regions where no experimental
data are available;
(iii) to combine binary systems to ternary and higher
ones.
For the Al-Mg-Si system such a thermodynamic
optimization was carried out recently in the COST 507
action [I]. Theregion of greatest interest in this system is
the range of homogeneity of the Al(f.c.c.) solid solution.
The available experimental data, however. were not sufti-
cient to evaluate this feature with the desired accuracy.
There is a quasi-binary section between Al and the phase
MgzSi which displays a eutectic. The plane of this quasi-
binary section appeared in the calculation shifted by about
2 mol% to the Mg-rich side, whereas in the literatutz it
was assumed to go through the Al comer of the system.
The experimental literature data for the temperature and
composition of this quasi-binary eutectic as well as for the
‘Correspondingauthor.
‘Dediiated to Pmfessor Riccarda Fern, on Ihe cccacion of his 70th
birthday.
considerable discrepancies.
To improve the accuracy of the thermodynamic dcscrip
tion of this system, some specific experiments were
desirable. To localize the position of the quasi-binary
section. four vertical sections, at 95. 90, 85 and 80 mass%
Al. were investigated by DTA and metallography. The
ternary solubility of Mg,Si in the Al(f.c.c.) solid solution
and its temperature dependence are determined by the.
Gibbs energy and enthalpy of formation of MgzSi rcspec-
tively. Therefore the beat capacity (CFzsi) and the
enthatpies of formation and melting of Mg,Si were
measured. Three single points of the ternary solubility
limit as well as one for each of tbe AI-Si and AI-Mg
binary solubility limits of Al were measuted by di-
latometry. With the resulting data the binary Mg-Si and
AI-Si as well as the ternary Al-Mg-Si system were
thermodynamically re-optimized.
2. Experimenti
All alloy samples were prepared from 99.999% pure AI,
99.98% pure Mg and 99.999% pure Si.
2.1. Calorimetry in the Mg-Si system
2. I. I. Ettthalpyqf formationof M&Si
The calotimeter used for tbe determination of the

om-8388/97/$17.00 Q 19% Elsevier Science S.A. All ri@as reserved

PII SO925-8388(96)02655-2
emhnlpy of mixing of liquid MS-5 alloys and for the summing the transformed heat effects of all the previous
enthalpy of ft~rntatitm of Mg.,Si has been described additions of the same series and dividing by the total
previously 121. The enthalpy of mixing of liquid MS-Si amount of initial Mg plus all added Si. The corresponding
alloys was measured at constant temperature by adding concentration. given in column 4, is the concentration after
successively small atnotmts of Si from room temperature the last addition The partial enthalpies were calcu-
of Si.
to the liquid bath in the calorimeter. starting with pure Mg. lated by dividing the transformed heat effect by the added
The temperature change due to the addition of a sample amount of Si, approximating the differential quotient dHl
was measured with an Ni/NiCr thermopile sitttated below dn by the quotient of differences AH/An. This quotient of
the reaction crucible. The calorimeter was calibrated by differences is exactly equal to the differential quotient at
dropping solid sampies uf magnesium before the addition an unknown concentration between the concentrations of
of silicon or Mg,Si. The standard deviation of the cali- the calorimetric bath before and after the Si addition. As
bration ranges from ?I! to 3%. long as the H,(x) curve in this concentration interval can be
The experimental results for liquid Mg-Si alloys are roughly approximated by a parabola, the mean of the
given in Table I. together with calculated integral and concentrations before and after the addition is a good
partial enthalpies of mixing. The ‘heat effect’ is the effect approximation of the unknown concentration. In column 6
measured by adding the amount of solid Si given in this mean concentration is given.
column 2 from room temperature to the calorimetric bath The intermetallic compound Mg,Si was prepared in an
at measuring temperature. The bath contains all ‘amounts’ induction furnace under argon atmosphere. The sample
of the previous measurements of the same series. For the was first presintered at a temperature slightly above the
calculations the measured heat effects had to be trans- melting point of magnesium and then heated for a short
formed by subtracting the enthalpy difference between time to a temperature above the melting point of the
liquid pure silicon at the calorimetric bath temperature and compound. The alloy was then heat treated under argon at
solid silicon at room temperature. H;;(T) - 600°C for about one week. X-ray diffraction measure-
H$“““““(298 K). This enthalpy difference of pure Si was ments after this heat treatment confirmed that the sample
calculated from the unary data compiled by Dinsdale 131. was single phase. The diffraction pattern of Mg,Si was
The integral enthalpies of mixing were calculated by identified using the data given by Pearson 141.

Table I
Experimenralvalues of the rnthalpy change during dissolution of solid Si at 298 K in liquid Mg-Si alloys at different temperatures and crtculated
enthalpiea of miring of Mg-Si liquids

Measured Calculated

Starting Added MolN Integral Molar Panial enthatpy of

amo”“t o\,l Urn”““,h fraction enthslpy fraction mixing i\‘““HEr
(molt An,, (mol) of Si i,, of mixing of Si .I,, tkJmolV’)
(Sl.8) A”“‘H”Y t&c/c)
(klmot ‘)

Tuwprrunm~ Y 7.~K
0.23168 o.ooo66 2.7 0.003 -0.17x 0.001 -62.92
0.000x4 12.4 0.006 -0.367 0.00s -52.26
O.lWlS3 6.9 0.009 -0.48X O.GQS -53.X8
0.09105 to.7 0.013 -0.740 0.01 I -56.83
O.OOOY5 12.4 0.017 -0.954 0.015 -53.86
o.OQ107 IS.2 0.022 - I.188 0.019 -52.76
O.OlKl93 10.0 0.025 - I .402 0.023 -56.17
0.00126 14,s 0.03 I -I .6xX 0.028 -55.51
Tempumrarr /MU K
0.23621 O.wO80 3.1 0.003 -0.216 0.002 -63.87
0.00189 12.7 0.01 I -0.696 o.M)7 -60.95
O.OLllX4 17.8 0.019 -1.133 0.015 -57.99
0.00167 19.3 0.026 -1.511 0.022 -56.15
0.00122 19.8 0.030 - I.762 0.028 -51.52
Tpmpr,un,,e 1056 K
0.14570 O.cOl73 14.6 0.012 -0.715 O.OLl6 -60.91
O.OOtO8 14.9 0.019 -1.114 0.015 -55.55
0.00173 30.4 0.030 - I.698 0.025 -51.82
0.00190 40.9 0.042 -2.273 0.036 -48.00
0.001 I3 22.5 0.049 -2.621 0.046 -49.43
0. I7436 “.OOlW 43.2 0.2 43.20
0.00124 SO.6 0.4 40.93
0.00126 s9.x 0.7 47.47
o.oo:JI hi.6 0.0 43.63
0.00131 57 6 II 44.10
Mean wlue (A’ “H,,,:,,),=43.X7_2..;5 LJ mol

0.I764s 0.001 ?J 4x.x 0.2 39.47

0.0012x so I 0.5 39.30
O.WI I7 49.1 0.7 41.88
0.00121 91.1 0.9 4?..?4l
0.001 IS 47.1 I.1 40.87
Mean wl”r (A’ “H . . .. .. 1.. =40.76r I.36 M m”l

The standard heat of formation of Mg,Si at room
temperature was determined as the difference of two
different types of solution enthalpy. First the enthalpy of
dissolution of MgzSi in liquid magnesium. A”H,,?s,. was
measured by adding successively small amounts of Mg,Si
from room temperature (298 K) IO the liquid bath in the
calorimeter at 1000+3 K. In a separate solution experi-
ment the enthalpy of dissolution of a mechanical mixture
of pure magnesium and silicon in the correct ratio.
AEH,,+si. was measured at the same temperature. The
experimental results of both types of enthalpy of solution
are given in Table 2 Table 3. AaH, includes the enthalpy
difference of sample i between room temperature and the
temperature of measurement.
To calculate the enthalpy of formation of Mg,Si from
these solution experiments, the thermal effects have to be
extrapolated to intinite dihrbon (x,, = 0). This was done by
linear regression. assuming linear concentration depen-
dence of the AEH, on the molar fraction of Si in the
calorimetric bath, .rs,. Since the two series of measure-
ments of the enthalpy of dissolution of Mg$i deviate
within the accuracy of the measurements, both series of
measurements were separately extrapolater! to infinite
dilution. As “H s,p+, (Table 2). The AEH,,,,, of both
series were simultaneously extrapolated to a single valw
for intinite dilution, AE.“HM,+,, (Table 3). The obtained
values are 43.87’2.35 and 40.76~1.36kJmol- for
At.‘%,.,, and 19.64~1.18lt.t mo-’ for AE~“H,,+si. The
given limits of error are the total standard deviations. The
unit mol refers to one mole of atoms.
In both types of solution experiment the samples were
dropped from rwrn temperature into liquid magnesium at
IO00 K. The enthalpy of formation of Mg$i at mom
temperature. A’.‘HMl,+. can therefore be derived directly

Table 3
Experimental values of the enthalpy change during dirsoluflon of a mechanicsl mixture of *“lid Mg and Si at 298 K in lipid Mg-Si alloys at 1000 K:
mol = mole of atoms

Measured Calculated

Stsning ~m”“nl nMI (mol) Added ilmounts Heat effect L\Q (J , Molar fraction of Si x1, (“I.%) End.dlpy of s”lutkm 4%,,.,, kJ ma-’

L\n,. (mol) An,. (mol)

0. I7645 0.00140 0.00070 43.3 0.4 20.62
o.cOO77 o.ooo39 25.0 0.6 21.71
o.c0109 o.ooos5 34.3 0.9 21.02
0.00091 O.OLW46 30.4 I.1 22.15
0.00085 0.00042 26.9 1.4 21.05
0.001 I6 0.00058 39.6 I.7 22.67

0.22518 O.OO116 0.00059 33.8 0.3 19.27

0.00161 0.0008 I 47.7 0.6 19.72
O.OQl48 o.axl74 52.8 0.9 23.84
0.00167 O.WOU1 56.4 I.’ 22.55
0.00179 o.OcKl89 62.5 1.b 23.26
Linau waxssion: A’,“H. ...= = 19&d+ I .I8WmOl-’
Measured Calculated

O.OIMKl 429 43x 26.X 27.4

42Y 436 2E.R 27.3
42s 430 26.6 26.9
425 427 26.6 26.7
--

from the A”.“H values:

A’.“H = Ali ID
H MgtSl-
Aa.“H,, .1s,. The tw’o different values”~~‘AE.“H,,~,, yield
the two values -24.2353.53 and -21.1222.54 kJ mol-’
for A’.“HMelS,. The measurement series giving the more
negative value of Ae”‘HMrzS, suffers from great scatter of
the calibration factor and therefore the other value, the less
exothermic one, should be considered as more reliable.
2.1.2. Eathairy of fusion ofMg_$i
A sample of Mg$i was introduced into a tightly closed
tantalum ampule (in order to avoid volatilization) and
heated and cooled several times in a calorimeter through
the melting temperature IS]. The resulting heat effects were
recorded. The calorimeter was calibrated using the known
enthalpy of fusion of pure silver [3]. The experimental
values obtained are summarized in Table 4. The mean of
these values gives AfU‘HMglsi= 27.122.7 kJ mol-‘.
2.1.3. Heat capacity of M&G
These measurements were performed in a differential
scanning calorimeter (Perkin-Elmer DSC7). In this device
the difference of the heat flow between a sample-filled and
an empty pan is measured during continuous heating of the
instrument. The recorded heat flow data are calibrated for
each sample separately with the measurement of a standard
sample. The reproducibility of this procedure is about
23% using different samples and about 25% using
different standard samples (i.e. sapphire, Mg). The re-
sulting heat capacities of Mg,Si are summarized in Table
5.
2.2. DTA and tttetallograph,v
The alloy samples were melted in a high frequency
furnace under argon and cast into a cylindrical copper
mould of 8 mm diameter and 100 mm length. The samples
were hammered to a diameter of 6.5 mm and then heat
treated. Alloys inside the range of the ternary eutectic E,:
L=(AI)+ Mg,Si+Si were heat treated for five days at
550°C. those-inside the range of the ternary eutectic E,:
Le(Al)f Mg,Si +J3AI-Mg were annealed for 10 days at
440°C. The alloys below the quasi-binary eutectic er:
L+AI)+MgrSi were first annealed at 440°C to avoid
partial melting due to segregation and finally for two days
at 525 “C.
For differential thermal analysis (DTA), samples of
about 0.3 g were cut from these cylinders and put into
thin-walled crucibles of ultra-pure graphite, which were
sealed in thin-walled (0.2 mm) evacuated silica tubes. DTA
was performed on heating and cooling with rates of 2 to
5 K min-‘. All samples were metallographically investi-
gated after DTA.
Fig. I Fig. 2 Fig. 3 Fig. 4 show the measured DTA
effects in the vertical sections of constant Al contents of
95, 90, 85 and 80 mass% respectively. The temperature of
the quasi-binary eutectic e, was found to be 595 “C, that of
the ternary eutectic E, 558 “C.
2.3. Dilatometric meawrements of the Al solvas
For the dilatometric measurements pieces of I2 mm
length were cut from the annealed cylindrical samples and

Table 5
Measured heat capacities C:““: mol = mole of atoms: values about 20.5 J mol.’ Km’

T(K) C, (J mol.’ K-‘) T(K) C, (J mole’ Km’) T(K) C, (J mol.’ K-‘)

363 23.2 523 24.1 683 25.3
383 23.35 543 24.2 703 25.5
403 23.5 563 24.25 723 25.7
423 23.65 583 24.3 143 25.9
443 23.7 603 24.3 763 26.05
463 23.8 623 24.45 783 25.80
483 23.9 643 24.1 803 25.65
503 24.0 663 24.95
 -++I :I
L
YY

LtMg2S i

831

ml

0 .a2 .M 46 .m .I2 .I4

b .02 .I
calcularcd and crprnmenralpoints.
mass fraction Mg
curves indicate very clearly the start of the dissolution of
the PALMS precipitates around 240°C. The end of this
dissolution process is at tbe solvus tempetature, which is
reduced to 6 mm diameter on a lathe. A I mm axial hole determined as the intersection of the extrupolations of the
was drilled for the thermocouple. nearly linear branches of the curve before and after this
Fig. S(a) shows the ‘technical expansion coefficient‘ effect. The value thus &termined depends on the heating
AI rate. as shown in Fig. 5(a). In Fig. 5(b) the end-of-
of an AI-MS alloy with 9.14 mass%
arrh = /,,(7- 293 K) dissolution temperature is extrapolated to zero heating rate,
Mg obtained at different heating rates. The acch vs. 7 yielding an equilibrium solvus temperature of 348°C for
this alloy. In Fig. 6 the extrapolation of the ettd-of-
dissolution temperature to zero heating rate is shown for an
AI-Si alloy with 0.84 mass% Si and two ternary Al alloys
with 0.54 mass% Mg, 1.06 mass% Si and 0.41 mass% Mg,
0.84 mass% Si respectively.

3. Optimization of the Gii energy descriptbrs

For the optimization. the description of the binary Al-

Mg system of Ref. 161 was accepted. although new
experimental work on the central part of this system 171
shows that it has to be updated. For the present work only
the descriptions of liquid and the f.c.c. and h.c.p. solid
solutions are relevant, which well describe all the related
experimental work.

3.1. Modding

The phases Mg,Si aud pure Si were treated as stoichio-

il .m .o( .k .m .lO metric phases. Their molar Gibbs energy is expressed as
mass fraction Mg
G”(T) - HsER(298 K) = A + BT + CT In T + DT’
Fig. 2. Venicul section of the Al-Mg-Si sysrem at YOmassl Al.
calculatedand experimentalpoints. +m-’ (1)
36

I A Heating
DTA:
y CGGiilIg

, I
I
.m .in .I36 .00 .I0 .12 .I4 .16 .I8 .2tl
mass fraction Mg

2.75 7 I I I

v I K min-’

2.00
300 350 Loo 450
TPC
410 , 1 I I I
__--

350 - To9L60C

0 ( 2 I 6
v I Kmin-’
 The AI,,Mg,, (y-AI-M& phase was modelled by the
compound energy formalism. adopting the description
given by Ref. 161 and neglecting any solubility of Si in this
phase.
For the Gibbs energies of the pure elements (“G, -
H:l’Y) in all stable states. as well as in the metastable
states Mg’ ’’. Alh ’ ‘. Sih.‘~’ and Sir.” . theSGTE values.
compiled by Dinsdale 131. were adopted.

The least-squares calculation works well only if all

independently adjusted coefficients react differently on the
set of experimental data. Coefticients not distinguishable
by the experimental data set tend to diverge. In the
calculated values that correspond to the experimental
points the contribution of the diverging coefficients com-
pensate, but for areas where no experiments exist the
diverging coefticients may lead to very strange results.
The scatter of the experimental points around the final
description should satisfy a Gaussian normal distribution.
For the stoichiometric phases Al,: ,Mg;, ( f3-AI-Mg). Contradictions between different sets of experimental
AI,,Mg,, (e-AI-M%) and AI,,Mg,, (<-AI-Mg) the de- values indicate svstematic errors in at least one of the sets
scriptions of Ref. 161 were accepted, which give the Gibbs and thus contradrft a Gaussian normal distribution. In such
energy of formation referred to the pure elements cases one of the contradicting sets must be rejected in the
Ieaxi.squares calculation. Tbe arguments as to which of the
G”(T) -x(N:‘G:“(T’)) = A + BT (2) contradicting sets is most likely correct must be judged
before the least-squares calculation.

where H’“a(298 K) is an abbreviation of

\‘
-, (N,Hy”“(298 K)) and describes the enthalpy of a me- The Gibbs energy parameters for the liquid phase and
chanical mixture of the corresponding amounts of pure
the Mg(h.c.p.j solid solution were chosen similarly as in
elements in their stable states at the reference temperature
the previous optimizations [l,lO]. Five linearly tempen-
of 298 K. The N, are the amounts of element i in I mol of
ture dependent Redlich-Kister parameters were used for
the phase.
the liquid phase. the first two of them with two in-
The liquid phase. the Al(f.c.c.) and Mg(h.c.p.) solid
dependent coefficients A and B for the linear expression
solutions were described by the Redlich-Kister-Muggianu
“L = A + BT. For Y = 2 to 4, as well as for a single
18.91 formalism
Redlich-Kister parameter “I!$:~ of the Mg(h.c.p.) solid
solution. only one independent coefficient could be ad-
justed. Using the relation proposed by Tanaka et al. [I I],
the excess entropy Es was estimated to be proportional to
the excess enthalpy EH, ES = “HIT”. The factor I IT, = I I
with 8000 K is derived from the mean of the reciprocal melting
temperatures of Mg and Si, divided by the empirical
constant 14.
(refGd - ,YsER) =&b-~(T) - @“a(298 K)) (4)
,=I For the Mp,Si phase the enthalpy and entropy of
formation as well as the heat capacity is measured. This
allows the use of Eq. (I) rather than Eq. (2). The
experimental heat capacity values of Mp,Si are not
sufficiently accurate to adjust more than two of the three
coefticients C to E describing C, in Eq. ( I ). therefore the
idea of Kubaschewski and ijnal [12] was used to fix the
coefficient E to 630 000 J K mol ’ (I mol = 3 moles of
atoms). This procedure seems to be better than the usage of
Kopp-Neumann’s rule. Eq. (2). assuming Crrzs’ to be the
sum of 2CC;“lh‘r’ + C:““‘lm’. C, after this definition
shows a kink due to the change of the Mg reference phase
at the melting tempcrarure of Mg. which surely would be
incorrect for CpM’+. Above 300 K Kubaschewski and
ijttal’s proposal of 2 IO 000 J K molt ’(moles of atoms) for
the coefficient E of Eq. (I ) is virtua!ly equivalent to the
suggestions of the workshop on Thermodynamic Models
und Data for f’ure Elements and Other Epd Members of
Sohtrions [ 131. either with 0, = 570 K or 0, = 450 K.
The literature values of the enthalpy of formation of
MgZSi scatter over a large range. The present measure-
ments are at the lower limit of this range. but the accuracy
of these values is not very high. The standard entropy
revealed by integration of the low temperature heat capaci-
ties of Ref. [ 141 is also of limited accuracy. All other
binary Mg-Si experimental data connect thermodynamic
functions of the liquid phase with those of MgaSi, and
their tit to calculated functions may allow simultaneous
change of the descriptions of both these phases. Thus the
use of only the binary data leaves some ambiguity in the
thermodynamic functions of Mg-Si.
The solvus data for the ternary f.c.c.(Al-Mg-Si) solid
solution in equilibrium with the Mg,Si phase. however.
connect the Gibbs energy of Mg,Si with that of the f.c.c.
phase. The homogeneity range of the f.c.c. solid solution is
restricted to dilute solutions of Mg and Si in Al. Therefore
the G’~‘C~(T~Ur~S,) function cannot have a significant
contribution from a ternary excess term in the Redlich-
Kister-Muggianu formalism, Eq. (3). and the function is
completely defined by the AI-Mg and AI-Si binary Gibbs
energy descriptions. Hence the ternary solvus data can be
used to determine G”“2S’(T), the Gibbs energy of Mg,Si.
The cocflicients A to D of the MgzSi phase were first
tentatively adjusted, together with the parameters for liquid
and the Mg solid solution by a least-squares calculation, to
the binary experimental data. Then the coefficient X”“s’
was adjusted by trial and error to the ternary solvu~ data.
Finally the parameters of liquid and Mg were adjusted
again to the binary data, keeping the Mg,Si coefficients
constant.
A”“mHM”S’ and A’“.HM”‘S’
Besides the C,,, AmtrH~~,
values described in Section 2.1, all the literature values as
reported in the previous optimization [I] were used again
in the present least-squares calculation.
3.2.2. The binary AL.9 system
The parameters for all three phases, liquid, Al(f.c.c.) and
Sudiamond), were chosen as in the previous optimizations
ll.lSl.
In the present least-squares optimization the same

Table6
Binary and tuuwy parameters of the Gibbs energy descriptions. Eqs. (3-7). of the solution phases of the Al-Mg-Si system: mol = mole of atoms

Pbax ?UUll~lW A B Ref.

Liquid - i 2ooO.W 8.56600 161

1894.00 -3.OQOOO 161
2oLKl.o 161
-11340.10 - 1.23394 thir work
- 3530.93 I .35993 this work
2265.39 this work
-83864.26 32.44438 this work
-
I 8027.4
2486.67I -0.31084
19.61202 this work
18541.17 -2.31766 this work
- 12338.84 I .54236 this work
4125.86 -0.51573 this work
-47961.64 5.99520 this work
25813.80 -3.22672 this work

497 I.Gu
900.00 -3sOoml
0.42300 161
I61

-3143.78
950.00 0.39297 this
R work
-7148.79 0.8936 I this work

Mgth.o.p.r solid solution 1950.00 -2.oooM) I61

- 148O.txl 2.08wO 161

-3143.78
3500.00 0.39297 this
161 work
-7148.79 0.89361 this work
litemtuw data as in Ref. [ 11wereused together with the Table 8

dilatometrically determined solability of Si in Al (Fig. 6). Pammeten of the Gibbs energy dcsciip&m~ of the AI,$Q,, ty) phase.
lAI.Mg),~lMg.AI),(Mg),,. after Rd. [6l: mol= I fomwla unit AI,,Mg,,
The chosen weights for the dilatometric measurement of
the Al(f.c.c.) solvus as well as for the eutectic temperature P~llRter A B
(850 K) were very large.

3.2.3. Ternary parumeters ofthe AI-M.:4 system

The Gibbs energy contribution “.“‘G in Eq. (7) reaches
signiticant values only at some distance from the binary
boundary systems. As only the liquid phase extends far
into the ternary composition range, only for this phase is
the ternary contribution to the Gibbs energy likely to be
significant. The experimental data strongly connected with
the tetnary liquid are limited to the ternary liquidus data.
These correspond IO one temperature value for each
composition. Therefore the temperature dependence of
B.‘CrG”qcannot be determined and must be estimated. The
three coefficients “‘I!,:“’ of t.“‘G”q were chosen as “‘L:” =
A,( I + T/T,,) with T,, = 8000 K.
The Gibbs energies of the A1tf.c.c.) and Mg(h.c.p.) solid
solutions are totally determined by the binar] descriptions.
AI-Mg taken from Ref. 161, Mg-Si and AI-% as de-
scribed above, setting “L.$Ts, = “Lki.t, and “Li;:8 =
“La;‘,:;. The dilatometric Al solvus values show up only in
the determination of the Gibbs energy of MgzSi as
described in Section 3.2.1.
The same literature values as used in Ref. [ I] were again
used for the least-squares calculation.

3.3. Results
The selected coefficients were adjusted to the ex-
perimental values by the programs BINCSS and TERGSS
[ 16,171. The resulting set of optimized parameters is given
in Table 6 Table 7 Table 8.
The binary Mg-Si parameters are compared with ex-
perimental data from the literature for the Mg-Si phase
diagram in Fig. 7, with the C~s’“’ data of Table 5 in Fig. 8
and with the partial enthalpies of mixing in liquid of Table
I in Fig. 9. Calculated and measured valws of the standard
enthalpy and entropy of formation as well as the enthalpy
of fusion are compared in Table 9.
The binary AI-Mg system, calculated witb tbe parame-
ters of Ref. 161. is compared with the measured Al solvus
point in Fig. IO. The excellent fit justifies the acceptance of
these parameters.
The calculated Al soivus of the AI4 systetn is
compared with literature data in Fig. I I.

Table 7
Parameters of the Gibbs energy descriptions. Eq. (I) orEq. (2). of the stoic...ometric solid phaes of the Al-M& syslem;md = mok of atoms
 Rg. IO. Solvus of Al in the hinary AI-Mg sy\km calculared with the
thermodynamic dercnpl~on of Ref. IhI and the dilatmmcWically measured

OF --___

.I0

-m

-a

-m f Lh,, .ort
0 1 .? .1 .I .5 .6 .7 .(I .9 I.0

The calculated ternary phase diagram is represented by Fig. 13. In Fig. I4 the Al solvus is shown in the vertical
vertical sect: UI\ at conctant Al contents of 9.5. 9P X.5 and . W$W from A’ IO Mr,Si :
hne ol‘ double sa.urat~~~ of Al with respect to Si and
Mg2Si is projected onto the plane of this vertical section
 H. Fcufrt cd.
t’, I ha n,,, t ,,I A,,,,v, and (‘,mp,wa,,, 2.fzJ; , ,W,, .7,-J?

References

Zhl.
I131 MW. Chase. I. Ansam. A. Dmdale. G. Eriksron. G. GrimvaIl. L.
Hi&md and H. Yokokawa. Cddd. IV t IYYS)437.
II-11 B.C. Gcnlem. F.J. Jrlinek. M. Hahenshuss. W.D. Shickell. J.R.
and shown by a dashed line. The two dilatometrically
MuItaly and PL. Chung. J. fhw Chew.. 47 11967) 2109.
measured points tit excellently. 1151 P. Doma. E.-Th. Hen@ H. Kricg. H.L. Luke and G. Petrow,
The Gibbs energy description of the Al(f.c.c.) solid
solution contains only binary data from the AI-M@ and I Ihl H.L. Lukas. E.-Th. Henig and B. Zimmrmunn. Cdphcd. I (1977)
AI4 systems. The calculated ternary aolvus depends only 2.5.
1171 H.L. Lukar and S.G. Fner. 1. Ptwrr Eqailih.. 1.7 (1992) .5X.
on these data and the Gibbs energy description of the
[ 1x1 R. GrflI.en and E. Miller. Trows. Mrr. Sw. A/ME. 2.U (1%) 1323.
binary Mg,Si phase. Therefore the reliability of the binary II91 E. Schiirmann and A. Fischer. Giujkrr~~~~.~~/~~sl~.29 (19771 I I. I
Mg-Si thermodynamic description is very important for I?01 R. Vogrl. Z. ANII~. Chum.. 61 ,tW9)46.
the quality of the Al(f.c.c.) solvus. The ternary parameters 1211 L. Wiihlrr and 0. Schlie@ke. 2. Awwg. Clrrm.. /.~I ,19X)I.
of the Gibbs energy description for the liquid phase show a I??1 0. Kuhascbwski and H. Villa. Z. E/rPtrw/wn.. -5.7(1949) 32.
1231 R. Blachnik. D. Kunze and A. Schneider. Me/n//.. 25 f 1971 t 119.
signilicant contribution to the tit to the experimental data
I24t W. Frinkcl. Z. Amw#. C/ton.. .58,1908l I.%.
only in the central part of the ternary system. This tit is t.?St E.H. Dix and AC. He&. Trans. AIME. 78 (1928) I64
equivalent to that shown in tigs. 5 to 8 of the previous 1351 L. Losava and R. Smwa. Metal/. /~a/.. 2.3 (1931) 193.
optimization [I], and not reproduced here. 1271 Broniewt.l and Smiatowski. //cr. Ma. 29 (1932) 542.
[33! Sh. Fujikawa. Y. Oyohihi and K. Hiram. J. Jp. hst. Lighr Mmdv.
2Y (19791 331.
1341 L. Aneawiadis. Z. Anor,&,.Chenl.. 17’) , 1929) 14s.
1351 V.G. Kurne~.\ov and ES. Makarov. 1x. Srkr. Pi:.-Khim And.. 1.3
I IYJO) 1177.
I.761 D. Hanwn and M.L.V. Geylrr. J. hr. ,
Mur.. 26 1921, 321.
I.371 E.H. Dix. F. Keller and R.W. Graham. Trrrns. AIME. XI c IY31) 44.
I.381 H. Wealinning and W. Kkmm. Z. Ekktroduvu.. -19 t 19431 IYH.