S e c t i o n II: P h a s e D i a g r a m E v a l u a t i o n s

The Ag-Cu (Silver-Copper) System

P.R. Subramanian
Universal Energy Systems, Inc.
and
J.H. Perepezko
University o f Wisconsin-Madison

Equilibrium Diagram conjunction with the data reported in the various investiga-
tions.
The eutectic temperature has been reported in the range from
The equilibrium phases of the Ag-Cu system are (1) liquid, L, 777 to 780 *C [1897Hey, 07Fri, 27Hir, 29Roe, 31Sto, 63Mos];
with no miscibility gaps; (2) (Ag), a Ag-rich phase, fcc solid [Hansen] accepted the value of 779.8 *C from [29Roe]. More
solution, with a maximum solubility of 14.1 at.% Cu; and (3)
recent thermal analysis by [63Mos] using high-purity starting
(Cu), a Cu-rich phase, fcc solid solution, with a maximum materials (>99.9% pure Cu, 99.994% pure Ag) placed the eu-
solid solubility of 4.9 at.% Ag, resulting in a eutectic equilib- tectic at 779.1 • 0.08 ~ this value is accepted in this assess-
rium, as shown in the assessed phase diagram (Fig. 1). Table 1
ment. The composition values for the eutectic have been re-
summarizes the invariant reactions in the Ag-Cu system. The ported in the narrow range between 39.8 to 41 at.% Cu [07Fri,
Ag-Cu system with its limited solid solubilities is a unique sys-
27Hit, 30Sto, 32Bro]. The selected value of 39.9 at.% Cu has
tem in that it violates the Hume-Rothery rules of solid solubil- an uncertainty of not more than 0.2 at.% [Hansen].
ity. This evaluation supersedes the earlier review by [80Ell].
S o l i d u s and S o l v u s
Llquldus
(Ag). The (Ag) solidus has been determined by DTA [07Fri,
The earliest report of liquidus determination was the cal-
27Hir, 32Bro, 62Dob, 67Ros] and microscopy [31Sto]. The
orimetry work of [ 1875Rob]. Anumber of other liquidus deter-
assessed (Ag) solidus in Fig. i is based on the careful work of
minations have been reported involving investigations based
[31Sto], who performed metallographic examination of small
on pyrometry [1897Hey], DTA [07Fri, 27Hir, 32Bro, 32Smi,
samples, which were annealed and quenched from tempera-
62Dob, 67Ros], emf measurements [70Cho], and the measure-
tures spanning the solidus. The alloys were prepared with
ment of distribution coefficients [61Mar]. The various
high-purity starting materials (99.92% pure Cu and 99.97%
liquidus data are summarized in Table 2. On the Ag-rich side,
pure Ag). The DTA results of [62Dob] and [67Ros] generally
the cooling curve analyses of [1897Hey], [27Hir], and [32Bro]
agree with [31Sto], while the remaining data show a large scat-
essentially agree closely within 5 ~ when corrected to the
ter.
same temperature scale. A higher (Ag) liquidus boundary than
that based on the earlier cooling curve results of [1897Hey], The (Ag) solvus has been examined in a fairly large number of
[27Hir], and [32Bro] is supported by the careful work of studies (see [Hansen]), but only the most comprehensive de-
[67Ros], who used high-purity starting materials and noted the terminations based upon metaUography [31Sto], differential
possible effect of dissolved oxygen on the (Ag) liquidus electrical resistivity [31Sto], and X-ray methods [30Age1,
boundary. However, the DTAresults of [67Ros] are somewhat 35Owe] are considered for the assessed (Ag) solvus in Fig. 1.
scattered, leading to uncertainties in the exact location of the There is general agreement between the results of X-ray and
Ag-rich liquidus. Therefore, the Ag-rich liquidus is tentatively metallographic solubility studies above 550 ~ but the metal-
accepted from the comprehensive work of [1897Hey] with the lographic results are derived from samples subjected to the
qualification that more exhaustive liquidus determination us- long-term annealing necessary for equilibrium. At lower tem-
ing very high-purity starting materials and low oxygen con- peratures, the greater sensitivity of the X-ray method [30Agel,
tamination might very well support the liquidus boundary re- 35Owe], compared to the metallographic and electrical resis-
ported by [67Ros]. On the Cu-rich side, there is less ambiguity tivity measurements [31Sto], yield a lower limit for the solu-
in the location of the liquidus boundary, and the accepted data bility even for shorter annealing periods; therefore, the data
of [1897Hey] and [32Smi], in concurrence with [Hansen], is in from the X-ray measurements are preferred. Figure 2 com-
reasonable accord with the investigations of [32Bro] and pares the assessed (Ag) solidus and solvus with the various in-
[70Cho]. Figure 1 shows the assessed liquidus boundary in vestigations.

"lhble 1 Special Points in theAg-Cu System

Compositionof the Reaction
Reaction respectivephases,at.% Cu Temperature,~ type
Ag ~ L..................................... 0 961.78 Melting
L ~ (Ag)4-(Cu)........................ 39.9 14.1 95.1 779.1 Eutectic
Cu .-* L..................................... 100 1084.62 Melting

62 Journal of Phase Equilibria Vol. 14 No. 1 1993

 P h a s e D i a g r a m E v a l u a t i o n s : S e c t i o n II

(Cu). On the Cu-rich side, the solidus has been determined by tures of [32Smi] are 25 to 50 ~ lower than the data of [31Sto],
DTA [27Hir, 32Bro, 62Dob, 67Ros] and metallography although the alloys of both [31Sto] and [32Smi] were of com-
[31Sto, 32Smi]. The solidus curves from the metallographic parable purity. There is no consistency in the DTA results;
examinations [31Sto, 32Smi] are in good accord above -96 therefore, the assessed (Cu) solidus is based upon a compro-
at.% Cu; however at lower Cu content, the solidus tempera- mise of the data of [31Sto] and [32Smi].

Weight P e r c e n t Copper
1200-0 ~ I0 20 30 40 50 60 70 80 90 100

1084.62"C

I000
L

0
8001 []~_.~ " ~*~.~ ~ 779.1"c (Cu)
o
39.9

600-

E~
400

i[] 1397Hey
Assessed
o 33Smi
07Fri 9 338ch
27Hlr [] 350we
200 30Agel
31Sto
9
Z~ 67Ros
62Dob

32Rro ~ 70Cho
323eh

0 +-
0 10 20 30 40 50 60 70 00 90 100
Ag Atomic Percent Copper Cu

Atomic Percent Copper

0 10 20 30 40 50 60 70 80 90 100
1200 - I ~ ~
1100 1 ~.~1084.62"C
1000~ L ~ / I
9o1.,o.%, / I

7oo~176
o

300

200 -!1 ......... I ......... T. . . . . . . . . I ......... I ......... e ......... I ......... T......... l ......... 1 ........
0 10 20 30 40 50 60 70 80 90 100
Ag Wci~hL P c ' r c e n t C o p p e r Cu

Fig. 1 AssessedAg-Cuphasediagramwithselectedexperimentaldata.

Journal of Phase Equilibria Vol. 14 No. 1 1993 63

Section H: P h a s e Diagram Evaluations

Table 2 E x p e r i m e n t a l Liquidus Data

Composition, Temperature, Composition, Temperature,
Reference at. % Cu ~ Reference at.% Cu *C
[18971-Iey] .................................... 0 959.3 [27Hir] (cont'd) ............................ 3.3 943
5.86 926.1 6.6 926
7.55 917 7.4 921
14.01 883.7 8.2 914
14.83 880 9.0 913
15.73 875.4 9.8 909
16 865.3 15.9 875
16.67 870.7 29.8 805
17.7 866 36.1 783
18.77 861.1 39.9 780
19.86 856.3 40.4 778
20.87 851.8 42.1 781
21.88 847.3 47.8 798
22.03 846.7 53.1 818
23.7 839.5 62.9 856
27.03 825.5 71.8 893
27.08 825.3 79.8 936
32.18 805 87.2 978
34.48 797 93.9 1028
36.67 788.9 96.4 1045
38.7 781.7 96.7 1048
40 778.7 97.0 1055
41.18 779.1 97.3 1057
43.5 790.3 97.6 1060
46.75 805.3 98.8 1072
50.22 818.8 100 1084
51.41 823.7 [32Smi] ........................................ 92.67 1024
54.73 837.2 93.88 1034
58.52 852.9 95.13 1043
61.94 866.5 96.39 1052
65.78 881.6 97.60 1061
70.16 900.2 98.75 1072
73.85 917 [32Bro] ......................................... 3.3 942
77.23 934.4 7.6 910
80.93 953.5 8.2 918
85.02 976 10.6 907
88.33 996.5 11.3 908
91.95 1026.8 13.6 898
95.83 1048.1 14.4 890
97.28 1059.1 15.9 835
98.73 1071.1 23.1 846
99.7 1079.1 29.8 817
100 1081.5 36.1 794
[07Fri] .......................................... 0 961 37.5 787
3.3 943 40.4 779
6.6 931 53.1 830
8.2 922 62.9 877
9.8 918 71.8 911
12.9 904 79.8 950
15.9 890 87.2 996
29.8 819 93.9 1026
39.8 778 96.1 1058
42.1 785 97.0 1068
53.1 817 98.6 1073
62.9 856 [62Dob] ........................................ 0.0 959
71.8 898 4.2 950
75.9 916 5.0 945
79.8 938 9.8 933
83.6 958 12.1 917
87.2 978 18.1 880
90.6 1006 20.2 879
93.9 1028 29.8 810
97.0 1056 33.6 805
100 1084 40.4 775
[27Hir] ......................................... 0 962 44.4 775

(continued)

64 J o u r n a l o f P h a s e E q u i l i b r i a Vol. 1 4 N o . 1 1 9 9 3
 P h a s e Diagram Evaluations: S e c t i o n II

Weight Percent Copper

, ~ 3 ~ 5 8 ? 8 9 ~o
I~00 . . . . . . . . -+ T n . . . .i . . i, , J n ~ . . . . . i. , , , P ] . . l. . . . . . [ L

1000
g61+78*C :

9 m m m
8OO
e
(Ag)

r 600

E
E-, 400

m/~ + 07Fri
F m 27Hir
[ 9 9 30Agel
200 x 31Sto
9 32Bro
[] 3GOwe
9 62Dob
A 67Ros

4 8 12
Ag Atomic Percent Copper

Fig. 2 Assessed(Ag)boundarywith selectedexperimentaldata

Table 2 Experimental Liquidus Data (continued)

Composition, Temperature, Composition, Temperature,
Reference at.% Cu *C Reference at.% Cu *C
[62Dob] (cont'd) ........................... 58.1 857 [67ROS] (cont'd) ............................ 34.3 808
59.1 867 59.1 862
61.0 875 61.5 880
75.1 957 75.9 960
86.5 983 87.9 987
87.2 992 88.6 993
93.9 1030 95.8 1035
95.4 1039 96.7 1048
96.4 1055 97.6 1063
97.0 1054 98.2 1063
100.0 1085 [70Cho] ........................................ 10 908
[67Ros] ........................................ 0 962 20 860
3.4 950 25 840
5 943 30 817
9.8 930 40 779
12.1 920 50 817
18.8 880 60 858
20.9 880 70 900
31.1 808 80 947

A number of studies have been reported for the (Cu) solvus 35Owe] below 500 *C. The (Cu) solvus and solidus results
boundary, based on DTA [27Hit, 67Ros], X-ray [30Age1, from the various investigations are summarized in Fig. 3.
32Sch, 33Sch, 35Owe], metallography [31Sto, 32Smi], and
electrical resistivity [31Sto], together with some partial studies Metastable Phases
by early investigators (see [Hansen]). The various data are in
good accord at temperatures above 650 *C, while some scatter The Ag-Cu system has been the subject of numerous investiga-
was observed at lower temperatures. The assessed (Cu) solvus tions involving metastable phase formation. In contrast to the
in Fig. i has been derived from metallographic investigations relatively simple form of the equilibrium diagram, the trans-
[31Sto, 32Smi] above 500 ~ and X-ray data [30Agel, formation characteristics during rapid quenching and sub-

Journal of Phase Equilibria Vol. 14 No. 1 1993 65

S e c t i o n II: P h a s e Diagram E v a l u a t i o n s

Weight Percent Copper

91 92 93 94 95 96 97 98 99 I00
1"~00 . . . . . . t ............. r .t . . . . . . 1~ ~ 9 ~ 9 , ~ . . . . . ~ . . . . . ~ ~ ' I .t . . . . . . t . i . . . . I . . . . .

084.62~C

I000

~00 779.I*C
o

600

L
E
400

~Assessed
200 27Hir o 32Smi
30Agel O 33Sch
x 31Sto [] 3 5 0 w e
9 32Bro 9 62Dob
9 32Sch ~ 67Ros

0 . . . . . . .. .. .. .. . . r . . . . . . . . . I 7" ' ' ' I . . . . . . . . . F . . . . . . . . .

94 95 96 97 98 99 I00
Atomic Percent Copper Cu

Hg.3 Assessed(Cu)boundarywith selectedexperimentaldata.

Table 3 Metastable Phases in the Ag-Cu System 69Sto, 76Can, 80Bar], liquid quenching or rapid solidification
Approximate [60Duw, 64Gen, 65Duw, 66Nag, 66Lin1, 66Lin2, 67Sto,
composition, 69Sto, 72Pre, 77Bos, 79Fra], plasma jet spraying [64Mos], la-
Phase at.% C u Description Reference ser-melt quenching [72Ell, 73Ell, 81Becl, 81Bec2], electrical
9r '. ............... 14.1 to 95 Solid solution with - 1 % [60Duw, 66Lin] discharge machining [63Mut], ion implantation [77Poa], and
deviation from Vegards ion-beam mixing [80Tsa]. Table 3 summarizes the numerous
rule
9~ ". .............. 14.1 to 95 Solid solution with -3% [69Sto]
metastable phases that have been observed in Ag-Cu alloys.
deviation from Vegard's The various phases are labeled in accordance with the nomen-
rule clature generally adopted in the literature.
c~'. ............... 14.1 to 75 Nonequilibrium solid [67Sto]
solution of Cu in Ag. Can [60Duw] showed that different metastable phases can be pro-
develop as a duced, depending on the cooling rate employed during
discontinuous reaction quenching. Under optimum cooling conditions, the metastable
product with 15' fcc solid solution, designated y' [66Nag], is formed over a
[3'................. 30 to 90 Metastable solid solution of [77Bos]
Ag in Cu; discontinuous wide range of compositions. This phase was shown to exhibit
product developing with a ' a 1% deviation from Vegard's rule. Most detailed studies
13"................ -50 Cu-rich solid solution; [77Bos] [69Sto, 72Pre, 77Bos] have demonstrated that metastable 7'
develops with 7" cannot be retained at room temperature following rapid liquid
5..................... Hexagonal solid solution; [67Sto, 69Sto] quenching without a transformation reaction resulting in a par-
exact structure and
composition uncertain
tial decomposition. For example, only in the very thin, electron
Tetragonal . . . . . . a = 0.415 rim; c = 1.167 nm [57Pin] transparent regions of liquid-quenched foils in a Ag-50 at.%
Develops from 7 ' by a Cu alloy, where the cooling rate is presumably at a maximum,
precipitation reaction; was the 7' phase retained completely [67Ros]. This observa-
exact structure and tion was made during examination by TEM immediately fol-
composition uncertain
lowing sample preparation. Any significant aging at room tem-
perature results in some decomposition of V' [77Bos].
sequent solid state reaction indicate that several metastable The initial reports of the lattice parameters and compositions
phase sequences are possible. Metastable phases and solid so- of the metastable fcc solid solution phases, a' (Ag-rich solid
lutions have been obtained in Ag-Cu alloys by a wide range of solution) phase and [5' (Cu-rich solid solution) [66Nag, 67Sto],
methods, specifically, vapor quenching techniques such as co- suggested that these structures developed during a precipita-
evaporation and sputtering [57Pin, 66Fuj, 67Sto, 67Mad, tion reaction from the V ' phase upon cooling. However, in con-

66 Journal of Phase Equilibria Vol. 14 No. 1 1993

 P h a s e Diagram Evaluations: S e c t i o n II

trast to equilibrium (Ag) and (Cu), which have maximum solu- There have been numerous measurements of the lattice spac-
bility limits of 14.1 at.% Cu and 95.1% Cu, respectively, the ct' ings as a function of composition throughout the regions of
and [5' showed residual supersaturations of 16 at.% Cu and 91 solid solution. [32Meg] used a back-reflection method to
at.% Cu [66Nag], respectively, which indicated that the y' de- measure the lattice constant of (Cu) with a stated accuracy of
composition reaction did not result in equilibrium structures 0.00005 nm and the lattice constant of (Ag) with an accuracy
with compositions corresponding to the solvus boundaries. of 0.00003 nm; their alloys were quenched from 728 ~ The
[84Rau] showed the formation of ct' over the entire range of lattice parameters of (Ag) were measured by [30Age2] on al-
compositions in Ag-Cu by ion-beam mixing; decomposition loys annealed at 770 ~ for 6 days prior to quenching, while
of the alloys occurred in stages upon annealing between 50 and [30Age1] performed similar measurements for (Cu) with a
300 *C. Based on an analysis of contrast modulations and dif- back-reflection method and an accuracy of 0.0001 rim. Lattice
fraction patterns, [69Sto] and [77Bos] treated the observed de- spacings of two-phase alloys quenched from various tempera-
composition behavior of y' as a spinodal decomposition reac- tures were also determined by [30Age1] and [30Age2].
tion. [77Bos] concluded that the spinodal decomposition
occurred during aging at room temperature. However, certain
details of the composition remain to be resolved, as it appears Table 4 Ag-Cu Crystal Structure Data
possible to produce a sample consisting entirely of the ct' Composition, Pearson Space Strukturbertcht
phase. Phase at.% Cu symbol group designation Prototype
(Ag) .... 0to 14.1 cF4 FrOm A1 Ca
A number of additional metastable phases have been reported (Cu) .... 95.1 to 100 cF4 Fm3m A1 Ca
for Ag-Cu alloys. The `/" (solid solution) phase is similar in
structure to the y' phase [69Sto], but it exhibits a 3% deviation
(from Vegard's rule behavior) in the composition dependence Table 5 Lattice Parameters ofAg-Cu Sofid Solution Alloys
of the lattice parameters. The observation of'/" has been asso- Composition, Lattice
ciated with conditions in which the quenching efficiency is not Phase at. % Cu parameter, nm Reference
optimum [79Fra]; further, '/" may also be a product related to Ag ................ 3.9 0.40715 [30Age2](a)
the decomposition behavior of the '/' phase. 7 0.40604 [30Age2l(a)
10.2 0.40475 [30Age2l(a)
The 15"(Cu-rich solid solution) phase is also a possible decom- 12.1 0.40395 [30Age2](a)
position product of the y ' phase [77Bos] and observed by 17.3('o) 0.40369 [30Age2](a)
XRD evaluation to be present in association with the'/" phase 1.33 0.40855 [32Meg](c)
in as-quenched, splat-cooled Ag-50 at.% Cu foils; this phase 2.37 0.40776 [32Meg](c)
3.69 0.40724 [32Meg](c)
could not be detected by TEM. 2.19 0.4077 [35Owe](d)
4.17 0.40711 [35Owe](d)
The 5 phase has been reported to form during the annealing of 6.93 0.40608 [35Owe](d)
rapidly quenched samples as a hexagonal precipitate structure 0 0.40857 [Massalsld2](e)
[67Sto, 69Sto], but other studies of the annealing behavior of Cu ................. 93.503) 0.3615 [30Agel](a)
quenched samples did not confirm this observation. Instead, 96.3 0.3637 [30Agel](a)
most studies indicate that the evidence for 6 may be obscured 97.25 0.3633 [30Agel](a)
97.9 0.3629 [30Agel](a)
by a thin layer of a Cu20 film that has been reported to form on 99.05 0.3623 [30Agel](a)
the surface of rapidly quenched samples [77Bos]. 98.28 0.36269 [32Meg](c)
98.87 0.36227 [32Meg](c)
[57Pin] reported the precipitation of a tetragonal phase from 99.43 0.36193 [32Meg](c)
'/' upon annealing of vapor-quenched films at 250 ~ Further 94.18 0.36421 [325ch](f)
annealing at 350 ~ resulted in the dissolution of this phase. 94.32 0.36418 [32Sch](f)
96.06 0.36382 [32Sch](f)
Last, an amorphous structure has been reported in rapidly 96.75 0.36344 [32Sch](f)
quenched alloys following vapor deposition, but no observa- 96.8 0.36342 [32Sch](f)
tions of amorphous phases have been reported with liquid 96.91 0.36330 [32Sch](f)
quenching techniques [67Sto]. [67Mad] reported that vapor 96.98 0.36327 [32Sch]( 0
97.05 0.36323 [32Sch](0
quenching of alloys between 35 and 65 at.% Ag resulted in an 97.28 0.36315 [32Sch](0
amorphous phase, while outside this composition range, me- 97.53 0.36295 [32Sch](f)
tastable solid solutions were observed. [76Can] observed 97.7 0.36281 [32Sch](O
amorphous structures only in a thermally evaporated Ag-50 98.19 0.36265 [32Sch](f)
at.% Cu alloy; however, no amorphous phases were found in 95.18 0.36151 [35Owe](g)
97.36 0.36300 [350we](g)
sputtered alloys. 98.57 0.36224 [350we](g)
99.23 0.36192 [350we](g)
100 0.36146 [Massalski2l(e)
Crystal Structures and Lattice
Parameters (a) Annealed at 770 "C for 6 days and quenched; (b) Two-phase alloys; (c)
Quenched from 728 *C; (d) Homogenized alloys annealed at 765 ~ for 1 hour
and quenched; (e) At 25 "C; (0 Homogenized at 760 *C for 22 to 48 days and 780
"C for 24 to 70 days; (g) Homogenized alloys annealed between 700 and 765 ~
Crystal structure data for the equilibrium phases are presented for 1 to 6 hours and quenched.
in Table 4.

Journal of Phase Equilibria Vol. 14 No. 1 1993 67

Section II: P h a s e Diagram Evaluations

Weight Percent Copper

0 i0 20 30 40 50 60 70 80 90 I00
041

D o
9 9 9 ~ a f

0.4-
[] )

039 Vegard's L
%
0 Massalski
m 64Mos
0~
n 66Llnl
0 38 9 66Nag
o 67Sto
9 72Pre
c~ m 73Eii
.2 9 77Bos
A 79Fra
X 81Bee
0.37 + 82Bec

o 9
o%
@ &

0 36 ...... ~T . . . . . . l .... r ,~ V-
0 I0 20 3O 40 50 60 70 80 90 100

A~ ALomie P{.'rcent Copper Cu

Hg~4 Latticeparametervs compositionfor Ag-Cumetastablephases.

[35Owe] obtained lattice parameters of both (Ag) and (Cu) on possible dependence of lattice parameter of a' and I~' on
homogenized alloys, which were annealed at 765 ~ for 1 h quench rate is also consistent with the claim that these phases
and quenched. The measurements from the various investiga- form during a partial decomposition of the initial product
tors are compared in Table 5. The results for both (Ag) and structure, possibly at different decomposition temperatures.
(Cu) are in comparatively good agreement. Anumber of other The maximum deviation from Vegard's law is -1% at 50 at.%
investigations involving measurements of the lattice parame- Cu for ? ',while that for ? " i s - 3 % .
ters of the primary solid solutions over a portion or through the
entire composition range have been reported [Hansen]. Metastable Equilibrium
The variation of lattice parameters with composition for the
various metastable phases are summarized in Fig. 4. In spite of The information on phase formation that has been derived
the variety of rapid quenching studies, note that the measured from rapid quenching studies has served as a basis for analysis
lattice parameters for the 7' phase are generally in very good of some of the metastable equilibrium relationships in the Ag-
agreement. This suggests that when the critical condition for Cu system. From the results establishing a continuity of metas-
? ' formation is achieved, characteristics such as molar volume table solid solution throughout the alloy composition range,
are largely independent of the quench rate and method em- [73Mas] and [77Bos] suggested that the TOcurve, which repre-
ployed such as vapor deposition or liquid quenching. In con- sents the locus of temperature and composition values where
trast, the reported lattice parameters for both the a ' and 13' the Gibbs energies of the liquid and solid are equal, is continu-
phases, which are also plotted in Fig. 4, exhibit more scatter in ous. A further examination by [77Bos] was based upon an ap-
the comparison of results between different investigators. proximate thermodynamic analysis. With the assumption that
However, the results from a given study give a clear trend with the Gibbs energy function for both solid solution phases is con-
little scatter and seem to indicate that the lattice parameters for tinuous with composition, a metastable solid state miscibility
both the ct' and 15' phases are constant with increasing Cu con- gap was constructed by extending the (Ag)/(Ag) + (Cu) and
tent. The rapid quenching treatment in a given study is likely to (Cu)/(Ag) + (Cu) solvi, as shown in Fig. 5. From the graphi-
be more uniform than the conditions employed in different in- cally determined consolute point, further estimates of the spi-
vestigations with a variety of rapid quenching techniques and nodal curve were made by calculation. The TOpoints at the eu-
apparatus. In this case, it appears that the lattice parameters of tectic were assessed by the intersections of a solid Gibbs
the a ' and 13' phases may be affected by quench rate. Since ac- energy curve calculated by [66Sun] and the experimental liq-
curate measurements of cooling rate during rapid quenching uid Gibbs energy curve from [Hultgren, B], which was dis-
are not available usually, the form of the dependence of lattice placed in temperature to satisfy the eutectic equilibrium. The
parameter on quench rate is difficult to assess reliably. The entire trace of TOwas extrapolated by a smooth curve extend-

68 Journal of Phase Equilibria Vol. 14 No. 1 1993

 P h a s e D i a g r a m E v a l u a t i o n s : S e c t i o n II

Weight Percent Copper

0 ~0 30 40 50 60 70 80 90 100
1200

1000

o
800

~5

600

400

200
0 10 20 30 40 50 60 70 80 90 ]00

Ag Atomic Percent Copper Cu

Fig. 5 Calculatedmetastableequilibriain theAg-Cusystem.

Table 6 Ag-Cu Thermodynamic Parameters [84Mur] ing required below the equilibrium melting point for the for-
marion of the "/' phase [77Bos].
In more recent efforts to define the metastable equilibrium fea-
+ (a'L+/'r I)XA~XC~ tures of the Ag-Cu system, specific models were employed to
+ (a' L + b' L T)XAiXoj (XAg - X c ~ ) J/g-atom
express the Gibbs energy functions for liquid and solid alloys.
A solution model proposed by [52Lum] was employed by
GOAs = 0 J/g-atom
[81Bec2] to evaluate AmixGfor the solid; the AmixGvalues for
G L = 0 J/g-atom the liquid were calculated from the Gex results averaged from
aL = 15 171J/g-atom [79Gol], [71Wag], [65Gol], [70Cho], and [70Nak]. These cal-
bL = -2.537 J/g-atom culations agreed with the alloy phase equilibrium conditions at
a' L = -2425 J/g-atom the eutectic. The trace of TOand the metastable extensions of
b' L ~- 0.946 J/g-atom the solidi and liquidi for a modest excursion below the eutectic
were determined from the modeled Gibbs energy functions.
Another estimate of a portion of the metastable Ag-Cu system
was reported by [82Ish] and [84Ish], who developed the Gibbs
+ (afee.b~ r)x^sXc.
energy functions following the descriptions of [69His]. The
+ (a'fee + b'fee T)XAgXcu (XAg- Xcu) J/g-atom
Gibbs energy functions were optimized by requiring conform-
fl ity to the phase diagram. However, this procedure involved an
G~g = -11 945 + 9.67T J/g-atom
adjustment of the known entropies of fusion for Ag and Cu to
GL = -13 054 + 9.62T J/g-atom yield an approximate fit to the phase diagram. The calculation
afee = 34 532J/g-atom was applied to examine the trend of TO, which was shown to lie
bfee = -9.178 J/g-atom at only ~40 *C below the liquidus at the eutectic. The Ag-rich
t
a fee ~" -5996 J/g-atom TO curve calculated by [83Kat], based on a regular solution
b'~ = 1.725 J/g-atom model, was observed to agree well with the more rigorous cal-
culations of [77Bos], [82Ish], and [81Bec2].
Note: Standard states are liquid Ag and liquid Cu.
The most detailed examination of the metastable equilibrium
features was performed by [84Mur]. The analysis was based
ing through the eutectic TO points and the pure component upon a computer optimization calculation with Gibbs energy
melting points. The TOminima was located at 688 ~ and at functions that are represented according to a sub-regular solu-
-49 to 50 at.% Cu. The TOline gives the minimum undercool- tion model with a linear temperature dependence. The result-

Journal of Phase Equilibria Vol. 14 No. 1 1993 69

S e c t i o n II: P h a s e D i a g r a m E v a l u a t i o n s

ing Gibbs energy function for a solution phase is given by culated as 688 ~ which is in accord with [77Bos] and -40 ~
[84Mur] as: lower than the value of [82Ish].

AmixGi=XAgGOAg + XcuGOcu + RT (XAg InXAg + Xcu InXcu ) Pressure

+ (a i + b i T ) X A g X c u + (a' i + b' i T)XAgXcu(XAg - X c u )
[67Lel]studied the effect of varying pressure in the range from
18 to 62 kbar on the positions of the liquidus, solidus, and
where Xcu and XAg are the atom fractions of Cu and Ag, re- solvus, together with the fusion of Ag and Cu by DTA. The re-
spectively, R is the gas constant, and Tis the temperature in K. suiting Ag-Cu phase diagram at a pressure of 50 kbar is com-
The set of parameters ai, bi, a'i, and b' i, which define the inter- pared in Fig. 6 with the assessed equilibrium diagram at ambi-
action free energy, and the quantities G~ and G~ which are ent pressure. As expected, the application of pressure shifted
the lattice stability parameters of the pure metals, are listed in the elemental melting points as well as the positions of the
Table 6. The optimized Gibbs energy functions were used to phase boundaries toward higher temperatures.
reproduce the phase diagram by [84Mur] with good agree- The variation in the equilibrium melting temperature with
ment. However, the calculation yielded rather poor agreement pressure is described by the Clausius-Clapeyron equation as
with the measured thermodynamic excess quantities, usually follows:
yielding values that were larger than the measured values. The
details of some of the metastable features were claimed to be dT AfusV AfusV
relatively insensitive to the discrepancies noted and to the type dP - TM AfusH - AfusS
of the analysis model. The calculated metastable phase dia-
gram is described in Fig. 5 and includes a solid phase miscibil-
where Tm is the absolute melting temperature, P is the pressure,
ity gap with a consolute or critical temperature of 1112 ~ a AfusVis the molar volume change upon fusion, AfusHis the en-
liquid phase miscibility gap, metastable liquidi, metastable thalpy of fusion, and AfusS is the entropy of fusion. Based on this
solidi which exhibit a retrograde behavior for both Ag and Cu- relationship, the value of dT/dP for the fusion of Ag was calcu-
rich solid solutions, and a continuous TOtrace lying ~70 ~ be- lated as 4.14 K/kbar, which is in close accord with a value of 3.7
low the liquidus at the eutectic. The retrograde points are lo- K/kbar obtained by fitting the experimental data of [67Lel]. In the
cated at 16.5 at.% Cu, 683 ~ for (Ag) and 94.9 at.% Cu, 837 case of pure Cu, dT/dP for fusion was calculated as 3.3 K/kbar,
~ for (Cu); this retrograde behavior was not observed in the which compares reasonably well with the measured value of 2.66
earlier calculations [82Ish, 81Bec2]. The TOminima was cal- K/kbar from [67Lel]. [67Lel] reported the value ofdT/dP as 2.58

Weight Percent. Copper

0 10 20 30 40 50 60 70 80 90 I00
1300 ~ ~T,, ~ . T. ~ , ~ ~ . ~ 1 ~

t216"C
1200

1130"C
11oo ........::::::::...~.............

1000 "'""'"-...
"ill[" ~ : : ' ' ~1084"62"r
................................................. ............
61.780C
........................................
~oo ~---.~ .............
:'"
::..........
45
:,.::::::::::iL....~*...c. ............ ~
~
................ ..:
'~ib';i:...
.....-"
800 "" 779.1"C
.J
a9.9

L 700-

6OO

50O

400-

300-
I .......... 67Lel, P=50kbar
Assessed (rig. 1)
200 ......... J ......
0 lO 20 30 40 50 60 70 80 90 100
Ag Atomic Percent Copper Cn

Hg.6 Ag-Cu phase diagramat a pressure of 50 kbar comparedwith assessedphase diagramat atmosphericpressure.

70 Journal of Phase Equilibria Vol. 14 No. 1 1993

 P h a s e Diagram Evaluations: S e c t i o n IX

K/kbar for the variation of the eutectic temperature as a function [62Dob] agree weU with the data for (Cu) in Table 7 while
of pressure. showing m o r e endothermic values for (Ag). [66Sar] reported
low-temperature heat capacity data for (Cu) in the temperature
Thermodynamics range 1.6 to 4.2 K.
[72Pre] examined the decomposition of the y ' phase in a rap-
S o l i d Alloys idly quenched Ag-39.9 at.% Cu sample by calorimetry at 600
K. The enthalpy difference between y' and the equilibrium
Enthalpies of formation of solid alloys have been determined phases was measured at 4180 • 210 J/g-atom.
by calorimetry [58Oril, 60Orr, 62Dob]. The review of [Hult-
gren, B] listed values for the heat of formation of the solid al- Liquid Alloys
loys based upon the calorimetric studies of [58Oril] and
There are several published reports on the enthalpies of mix-
[60Orr], after adjusting to the eutectic temperature by assum-
ing the Kopp law of additivity o f Cpvalues. The AmixGvalues ing, AmixH, of liquid Ag-Cu alloys based on calorimetry
[30Kaw, 58Ori2, 62Dob, 65Dok, 75Ita, 82Kle], Knudsen-ef-
were calculated from the solvus boundaries by [Hultgren, B]
fusion-mass spectrometry [70Nak, 71Wag, 79Goi], vapor
based on a Raoult law behavior for the solvent and the Henry
pressure [56Edw, 65Gol], and emf measurements [70Cho].
law behavior for the solute. The entropy was determined from
The results of several different studies are summarized in Fig.
AmixG and A"mixH. [61Kuc] measured the activity of Ag in
7.
solid Ag-Cu alloys at 1000 K, using a radioisotope tracer tech-
nique. No other activity data are available for the solid alloys. The direct calorimetric values of Am'tx/'/of [75Ita] and [82Kle]
Table 7 lists the integral thermodynamic properties of the solid show a reasonable accord with one another and agree reason-
alloys at 1052 K from [Hultgren, B]. The enthalpy data of ably well with the ernf results of [70Cho], where the [Link].H

Table 7 Thermodynamic Data forAg-Cu Solid Alloys at 1052 K

Phase Xcu AmixG,kJ/g-atom AmixH,k J/g-atom An~xS,J/K. g-atom G 'z,kJ/g-atom S~z,J/K. g-atom
(Ag)......................................... 0.05 -0.90 1.20 2.00 0.88 0.30
0.10 -1.17 2.25 3.26 1.68 0.54
0.141 -1.21 3.00 4.00 2.35 0.61
(Cu).......................................... 0.951 -0.48 1.74 2.11 1.23 0.48
0.98 -0.38 0.76 1.06 0.50 0.24

Note: From [Hultgren, B].

I0000

8000

2
V

6000
V
V

~ooo g ~ o8o o g+

c~

c~
2000 V D
' 9 • 9 56Edw v 70Nak "~
9 71Wag
o 75Ira
9 79Goi "~
9 70Cho + 82Kle x~

0.~ 04 0 6 0 8
AV Atomic Per(ent Copper

Fig. 7 Enthalpy of mixing of liquid Ag-Cu alloys.

Journal of Phase Equilibria Vol. 14 No. 1 1993 71

S e c t i o n II: P h a s e D i a g r a m E v a l u a t i o n s

values were obtained from measured AmixG and AmixS results. compositions, with most studies displaying a nonuniform
[70Cho] noted that the measurements can be influenced con- trend of the interaction parameter. The AmixH values of
siderably by the solubility of oxygen in liquid [Link] 1300 [70Cho], [75Ita], and [82Kle] yield a uniform and fairly linear
K, liquid Ag-Cu alloys were estimated to dissolve oxygen to a dependence of the interaction parameter, Q, with composition
maximum of i at.% when equilibrated with Cu20. The mass and have been used to arrive at the selected values that are
spectrometry results of [70Nak] as well as the vapor pressure listed in Table 8.
data of [56Edw] appear to have a wide scatter,and show a large
The activities and excess Gibbs energies, G ex, in liquid Ag-Cu
discrepancy compared to the other investigations. D T A work
alloys were measured by vapor pressures [56Edw, 65Gol,
by [62Dob] yielded values of AmixH in good agreement with 83Tab], distribution equilibria [74Mob], emf [70Cho], Knud-
the calorimetry data, especially for the Cu-rich alloys. In the sen effusion-mass spectrometry [70Nak, 71Wag, 79Gol,
Ag-rich region, the mass spectrometry data of [71Wag] and the 89How], and radiochemical techniques [65Gol]. A compari-
compiled results of [Hultgren, B] are more endotherrnic than son of the results of several different studies and the values re-
most of the other investigations. ported by [Hultgren, B] are given in Fig. 8 for the excess Gibbs
An evaluation of the reported AmtxH values was performed in energy values. The activity results were examined in terms of
terms of the enthalpy interaction parameter given by Q = the ct function parameter given by ctA = log~a/[(1-XA)2].
AmixH/[XAg(1- XAg)]. There is a good general agreement be- There is a good agreement between most recent measure-
tween the different studies for the Cu-rich compositions. The ments, the values of [Hultgren, B], and the selected values that
results differ with an increasing divergence toward Ag-rich are listed in Tables 9 and 10. A similar evaluation of the Gex

Table 8 Thermodynamic Data For Liquid Ag-Cu Alloys at 1400 K

Xcu AmixG, k J / g - a t o m AmixH, k J / g - a t o m AmirS, J / K " g-atom G ex, k J / g - a t o m Sex, J / K . g-atom
0.1 ..................................... -2.54 1.15 2.63 1.24 -0.06
0.2 ..................................... -3.61 2.13 4.10 2.21 -0.05
0.3 ..................................... -4.22 2.90 5.08 2188 0.02
0.4 ..................................... -4.54 3.46 5.71 3.29 0.12
0.5 ..................................... -4.64 3.73 5.98 3.42 0.22
0.6 ..................................... -4.50 3.72 5.87 3.33 0.30
0.7 ..................................... -4.15 3.36 5.36 2.95 0.29
0.8 ..................................... -3.54 2.65 4.42 2.28 0.27
0.9 ..................................... -2.47 1.54 2.87 1.30 0.17

5000-

E/
0
[]
[]
4000
[3
E [3

>~ 3000

rM

L~ 2000

A21

1000
/ + 70Cho. 1330 K \
o
X / * 71Wag, 1389 K \
Ld / 9 7 9 G o l , 1400 K \
/ 9 Hultgren. B 1 4 2 3 K \
/ -- Assessed, 1400 Z \

y i i .
0.~ 014 0.6 0.~

Ag ALomic Percent Copper

Fig. 8 ExcessGibbs energyof mixingof liquidAg-Cu alloys.

72 Journal of Phase Equilibria Vol. 14 No. 1 1993

 P h a s e Diagram Evaluations: S e c t i o n II

Table 9 Partial Molar Quantities For Cu in Liquid [Link] Alloys at 1400 K

Xcu at. 7cu Gcu, kJ/g-atom G~tu, k J/g-atom Hce, k J/g-atom Scu, J / K . g-atom S~., J / K . g-atom
0.1 ....... 0.259 2.589 -15.72 11.07 10.816 18.95 -0.18
0.2 ....... 0.424 2.120 -9.98 8.74 9.238 13.73 0.36
0.3 ....... 0.533 1.778 -7.31 6.69 7.597 10.65 0.65
0.4 ....... 0.616 1.539 -5.64 5.01 5.986 8.30 0.70
0.5 ....... 0.679 1.358 -4.50 3.56 4.405 6.36 0.60
0.6 ....... 0.733 1.222 -3.61 2.33 3.010 4.73 0.48
0.7 ....... 0.786 1.123 -2.80 1.35 1.783 3.29 0.31
0.8 ....... 0.845 1.056 -1.96 0.63 0.837 2.00 0.15

Table 10 Partial Molar Quantities For Cu in Liquid Ag-Cu Alloys at 1400 K

XCu aA$ ~/Ag GAg, k J/g-atom G~g, kJ/g-atom HAg, kJ/g-atom SAg,J / K . g-atom SeXAg,J / K . g-atom
0.1 ........ 0.912 1.013 -1.07 0.15 0.076 0.82 -0.05
0.2 ........ 0.841 1.051 -2.01 0.57 0.353 1.69 -0.15
0.3 ........ 0.779 1.113 -2.90 1.24 0.887 2.70 -0.25
0.4 ........ 0.721 1.202 -3.80 2.14 1.776 3.98 -0.26
0.5 ........ 0.663 1.326 --4.78 3.28 3.055 5.60 -0.16
0.6 ........ 0.606 1.514 -5.83 4.82 4.785 7.58 0.02
0.7 ........ 0.533 1.778 -7.31 6.69 7.040 10.25 0.25
0.8 ........ 0.428 2.142 -9.86 8.86 9.902 14.12 0.74
0.9 ........ 0.266 2.662 -15.40 11.39 13.419 20.58 1.45

measurements was performed and also yielded general agree- and 95.2 at.% Cu, respectively, which are in excellent agree-
ment between the different studies; values of [56Edw] are ment with the assessed diagram, with the exception of the (Ag)
much less endothermic than the other values. composition. The calculated (Ag) composition at the eutectic
is -0.5 at.% lower than the assessed value, but in light of the
Thermodynamic Modeling scatter evident in the experimental (Ag) phase boundary, this
discrepancy is within the limits of error. In a similar approach,
[86Hay] performed a least-squares optimization based on the
A number of calculations involving stable and metastable experimental phase diagram and measured thermodynamic
phase equilibria are presented in the literature. Thermody- quantities, using lattice stability parameters from [86Din]. The
namic calculations of the Ag-Cu system have been performed excess integral Gibbs energies of mixing of the liquid and fcc
based on theory [74Udo, 77Udo, 83Yam], regular solution phases from the optimization are given in the form of Redlich-
modeling [80Gop], optimization of experimental phase dia- Kister polynomials as follows:
gram alone [83Wan1, 83Wan2], and in conjunction with se-
lected thermodynamic information [84Mur, 86Hay].
[74Udo] and [77Udo] determined the solubility boundaries of GeX(L)=X(1 -X) [(17 534.6- 4.45479/')
(Ag) and (Cu) as well as their metastable extensions from first-
principles calculations, based on nearest neighbor interac- + (1 - 2X) (-2251.3 +2.6733/) + (1- 2.1")2 (492.7)]
tions. [83Yam] performed cluster-variation method (CVM)
calculations of the (Ag) and (Cu) solubility and the miscibility GeX(fcc)=X(1-X) [(33 819.1- 8.1236/)
gap. The agreement with the experimental phase diagram was
at best marginal. [80Gop] calculated the phase diagram f~om + (1 -2,t') (5601.9 - 1.32997/)]
regular-solution interaction parameters derived from the Kauf-
man approach. The interaction parameters were given as fol- where X is the atomic fraction of Cu, and T is the absolute tem-
lows: WL = 14 903 J/tool; Wfcc = 25 066 J/tool. Again, there perature in K. The resulting data are observed to be consistent
was little agreement with the experimental phase diagram. with most of the thermodynamic and phase boundary measure-
[84Mur] accepted the thermodynamic data for (Ag) and (Cu) ments.
from [Hultgren, B] and the data from calorimetry [82Kle] and
emf [70Cho] for the liquid phase as the input in their optimiza- Cited R e f e r e n c e s
tion, while the phase boundaries were taken from [1897Hey],
1875Rob:[Link],"On theLiquidationand Densityof CertainAl-
[67Ros], and [70Cho]. The resulting thermodynamic parame- loys of Silver and Copper," Proc. R. Soc. (London), 23, 481-495
ters are listed in Table 6. The calculated boundaries were (1875). (EquiDiagram; Experimental)
within the range of the input experimental data, with the (Ag) 1897Hey: C.T. Heycock and EH. Neville, "Complete Freezing Point
liquidus lying between the values of [1897Hey] and the higher Curvesof Binary Alloys Containing Silveror CopperTogetherwith
values of [67Ros]. The calculated eutectic temperature and Another Metal," Philos. Trans. R. Soc. (London) A, 189, 25-69
compositions of (Ag), liquid, and (Cu) are 781 *C, 13.6, 39.8, (1897). (Equi Diagram; Experimental)

Journal of Phase Equilibria Vol. 14 No. 1 1993 73

S e c t i o n II: P h a s e D i a g r a m E v a l u a t i o n s

07Fri: K. Friedich and A. Leroux,"Copper, Silver,and Lead,"Metallur- 61Mar: J. Markali and P. Thoresen, "The Ag-Rich Side of the Binary
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27I-Iir: T. Hirose, "On the Silver-Copper Alloys," Rept lmp. Mint Acta Chert Scan,I, 15, 31-35 ( 1961). (Equi Diagram; Experimental)
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43,193-211 (1930). (Equi Diagram; Experimental) 64Gen: M.Y. Gen, E.A. Velichenkova,I.V. Erimina, and M.S. Znskin,
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74 Journal of Phase Equilibria Vol. 14 No. 1 1993

 Phase Diagram Evaluations: Section II

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Ag-Cu evaluationcontributedby P.R. Subramanlan, Materials ResearchDivision, UniversalEnergySystems,Inc., 4401 Dayton-XeniaRoad, Dayton,OH
45432, andJ.H. Perepezko,DepartmentofMetallurgy,UniversityofWisconsin-Madison,Madison,[Link]
supportedby ASMInternationalthrougha grant fromthe NationalInstituteof Standardsand [Link]. Subramanianand Perepezkoare AlloyPhaseDia-
gram ContributingEditorsfor selectedbinarysilveralloys.

Journal of Phase Equilibria Vol. 14 No. 1 1993 75