Ag-Au

Provisional Ag-Au (continued) Ag-Ge

Fig. 2 Lattice Parameters of A g - A u Solid Fig. 3 Variation of the Lattice Parameter
Solutions of A g - A u (50 at.%) Alloy with Temperature

4,55o!
4085
/ 4.1450
i

/ 4"1350

080 I / 44250

/ 41150

4-1050
4 075
10 20 30 40 50 60 70 80 90 i'00
4'0950
x [atC/oAg]

4.0850

From [51] with permission.

4 0750

53. B. Predel and U. Schallner, Determination of the 4"0650 [ I I I I I I I

O lO0 200 300 400 500 600 700 800 900
Electronic Contribution to the Bonding in Binary
TEMPERATURE ~
Copper, Silver, and Gold Alpha-Solid Solutions
from Thermodynamic Investigations, Metall. Chem.
Proc. Syrup. (London, 1951), p 289-299 (1972). From [58] with permission.

54. W. Schfile and G. Grestoni, Short Range Order in

Gold-Silver Alloys, Z. Metallkunde, 66 (12), p. 728-
733 (1975). (Electrical resistivity in two alloys,
15.0 and 26.82 at.% Ag)
55. A.B. Bhatia and N.H. March, Phase Diagrams of
Ascending and Minimum Type in Terms of Con-
centration Fluctuations in Binary Liquid and Solid
Solutions, Phys. Chem. Liq., No. 1, p 45-60 (1976).
(Ag-Au binary phase diagram was calculated based
on conformal solution theory)
56. P.P. Safronov, Short-Range Order and Ordering
Energy in Au-Ag Alloys, Fiz. Met. Metalloved.,
43(4), p 879-882 (1977) in Russian; translated as
Phys. Met. Metallogr., 43(4), p 181-184 (1977). (25
to 80 at.% Au, 5 compositions, various treatments
for each)
57. M.L. Kapoor, An Approach to Thermodynamics of
Binary Substitutional Solutions, Trans. Jpn. Inst.
Met., 19(10), p 519-529 (1978). (Using free volume
theory and available experimental data,
derived thermodynamic functions for liquid
alloys)
58. Y. C. Venudhar, L. Iyengar and K. V. K. Rao, Tem-
perature Dependence of the Lattice Parameter
and the Thermal Expansion of Silver-Gold
(50 at.%) Alloy by an X-Ray Method, J. Less-
Common Met., 60(2), p 41-46 (1978). (Lattice
parameters from room temperature to 900 ~ See
Fig. 3.

The Ag-Ge
System
( Si Iver-German ium )
107.868 amu 72.59 amu

Figure 1 shows the Ag-Ge phase diagram. Large-scale
versions of the Ag-Ge phase diagram plotted in both
at.% and wt.% appear in the Tear-Out section in the
back of this issue. The whole system was investigated
twice by thermal and microscopic analysis [1, 2]. The
liquidus curves agree fairly well; the eutectic was
given as 26.0 at.% (19.1 wt.%) Ge, 650 ~ [1], and 24.1
at.% (17.6 wt.%) Ge, 649 ~ [2].
Table 1 gives the solid solubility of Ge in Ag as reported
by [1], [2}, [3] and [4]. The more careful work is that of
[4], who u~ed lattice spacing studies of well-annealed

Bulletin of Alloy Phase Diagrams Vol. 1 No. 2 1980 47

Ag-Ge Provisional

Fig. 1 Ag-Ge Phase Diagram

Weight Percent Germanium
10 20 30 40 50 SO 70 80 90 100
1100 ......... ,'") ..... , ...... J''l ........ I~ . . . . . . . . . I ......... II . . . . . . . . J, . . . . . . . I..~ . . . . . I....,..1 .....

1000
960.8~
957.25~
900

800 9
(D
o
q)
L 700
651~
o
L 9 69 25.9
600 -

500 -

400 -

(oe)
300 -

200 . . . . . . . . . i . . . . . . . . . i . . . . . . . . . I . . . . . . . . . r . . . . . . . . . i . . . . . . . . . i . . . . . . . . . i ......... i . . . . . . . . . F . . . . . . . . .
10 20 30 40 50 60 70 80 90 100
Ag Atomic Percent Germanium Oe
From [Elliott; IITRI] with permission.

Table 1 Solid Solubility of Ge in Ag (0.004 at.% Ag) a t 875~ a n d 4 x 10 TM atoms

per cm 3 (0.009 at.% Ag) a t 800 ~ [7].
Solubility, Solubility,
Temperature, ~ wt.% Ge at.% Ge Ref [8, 9] have developed a formula to calculate the solidus
650 (eutectic) -4.5 -6.5 1 curves for Ag-Ge alloys a n d claim good a g r e e m e n t with
649 (eutectic) ---5.5 -8.0 2 the e x p e r i m e n t a l results.
650 (eutectic) -5.6 -8.1 3
651 (eutectic) 6.7 (extrapo-
lated)
9.6 (extrapo-
lated)
4 Metastable Ag-Ge
575 5.46 7.9 4 (Silver-Germanium) System
470 4.6 6.7 4
375 2.6 3.8 4 M e t a s t a b l e phases were produced by r a p i d undercooling
308 1.8 2.7 4 from the m e l t [10-14]. The t e r m i n a l solubility of Ge in
270 1.0 1.5 4 A g was increased to 13.5 at.% Ge by this technique [10].
[10] indicated t h a t at - 2 2 to 23 at.% Ge a cph meta-
alloys. Results of microscopic work [5] on alloys with 10 stable phase existed; p r e l i m i n a r y i n t e r p r e t a t i o n indi-
to 20 at.% Ge are in accordance w i t h Fig. 1; the eutectic cated this to be a 7 : 4 e l e c t r o n / a t o m compound [11].
t e m p e r a t u r e was a c c u r a t e l y d e t e r m i n e d as 651 • The 3 : 2 e l e c t r o n / a t o m compound could not be m a d e by
0.5 ~ Lattice p a r a m e t e r s of the Ag-rich phase with up such techniques [11]. [12] r e p o r t e d p a r a m e t e r s for the
to 7.16 at.% Ge were reported by [4]; the A g lattice was m e t a s t a b l e cph s t r u c t u r e at 26 at.% Ge. [13] stated t h a t
expanded by about 0.05%. the structure could be obtained between 15 and 26 at.%
Ge and was s i m i l a r to the ~ phase (hP2 type) in Ag-Sn
By radioactive t r a c e r techniques, t h e solubility of A g in alloys. [14] reported t h a t the m e t a s t a b l e cph structure
Ge increased from 10 TM atoms p e r cm 3 (2.3 x 10-7 at.% occurred between 10 a n d 30 at.% Ge a n d t h a t the
Ag) at 700 ~ to a m a x i m u m of 1015 atoms per cm 3 (2.3 • composition r a n g e of h o m o g e n e i t y was 20 to 22 at.%
10 -6 at.% Ag) at 875 ~ [6]. The solubility then decreased Ge. It is probable t h a t t h e r a n g e of occurrence of the
to about 2 x 10 TM atoms per cm 3 (4.6 • 10 -7 at.% Ag) cph structure depends on t h e efficiency of the under-
j u s t below the m e l t i n g point. A n accuracy of 5 to 10% cooling technique.
was estimated. Diffusion e x p e r i m e n t s with single-
crystal Ge and isotopic Ag showed the existence of a
"slow" and a "fast" diffusion component [7]. The Ag-Ge evaluation contributed by Rodney P. Elliott, Cleveland State
solubilities indicated by "fast" diffusion were those University, Department of Metallurgical Engineering, Cleveland,
reported by [6]. The solid solubility of A g in Ge Ohio 44115 and Francis A. Shunk, 3120 South Princeton, Chicago,
Illinois 60616. Work done at lIT Research Institute, Chicago, Illinois,
indicated by ~%low" diffusion was 6 • 10 I7 a t o m s per under contract to the Office of Standard Reference Data, National
cm 3 (0.001 at.% Ag) at 925 C, 2 • 10 atoms per cm o 18 3
Bureau of Standards. From [Elliott; IITRI];bibliography through 1966.

48 Bulletin of Alloy P h a s e D i a g r a m s Vol, 1 No. 2 1980

Provisional
Metastable Crystal Structures
Approximate
composition, Lattice
at. % Ge designation
22-23 . . . . . . . . . . . . . . . . . . . . . . cph 0.2898 -+ 0.0003
26 . . . . . . . . . . . . . . . . . . . . . . cph 0.28995 + 0.00008
Cited References
1. T.R. Briggs, R.O. McDuffie and S.H. Willisford,
J. Phys. Chem., 33, p 1080-1096 (1929).
2. H. Maucher, Forschungsarb. Metallk. Roentgen-
metaUogr., No. 20 (1936).
3. H. Nowotny and K. Bachmayer, Monatsh. Chem.,
81, p 669-678 (1950). 17.
4. E.A. Owen and V.W. Rowlands, J. Inst. Metals, 66,
p 361-378 (1940).
5. W. Hume-Rothery, G.V. Raynor, P.W. Reynolds
and H.K. Packer, J. Inst. Metals, 66, p 237-238 18.
(1940).
6. A.A. Bugai, V. N. Vasilevskaya, V. E. Kosenko and
E.G. Miselyuk, Tr. Vses. Nauch.-Tekh. Konf.
Primen. Radioakt. Stabil. Isotop. Izluch. Nar. Khoz.
Nauke (Moscow), MetaU. MetaUoved., p 304-309
(1957); A. A. Bugai, V.E. Kosenko and E. G. Misel-
yuk, Vopr. Met. Fiz. Poluprov. Akad. Nauk SSSR, 19.
Tr. 3-go (Tretego) Soveshch. (Moscow), p 52-56
(1957); A. A. Bugai, V.E. Kosenko and E. G. Misel-
yuk. Zh. Tekh. Fiz., 27, p 1671-1675 (1957); Soy.
Phys.--Tech. Phys., 2, p 1553-1557 (1957).
7. V.E. Kosenko, Fiz. Tverd. Tela, 4, p 59-61 (1962); 20.
Soy. Phys.--Solid State, 4, p 42-43 (1962); see also
V.E. Kosenko. Fiz. Tverd. Tela, 3, p 2102-2104
(1961); Soy. Phys.--Solid State, 3, p 1526-1527
(1962). 21.
8. G.M. Kuznetsov, Dokl. Phys. Chem. Proc. Acad.
Sci. USSR, 167, p 193-195 (1966); translated from
Dokl. Akad. Nauk SSSR, 167, p 852-854 (1966).
9. G.M. Kuznetsov, Izv. Vyssh. Ucheb. Zaved. Tsvet.
Met., 9(4), p 95-98 (1966). 22.
10. W. Klement, Jr., J. Inst. Metals, 90, p 27-30 (1961-
1962).
11. P. Duwez, R.H. Willens and W. Klement, Jr., J.
Appl. Phys., 31, p 1137 (1960).
12. M. Moss, D. L. Smith and R. A. Lefever, Appl. Phys.
Lett., 5, p 120-121 (1964). 23.
13. P. Duwez, in Energetics in Metallurgical Phe-
nomena, Vol. 1, Gordon and Breach, Science Pub-
lishers, Inc., New York, p 193-204 (1965).
14. T.R. Anantharaman, H.L. Luo and W. Klement,
Jr., Nature, 210 p 1040-1041 (1966).
Additional References 24.
15. V.N. Eremenko, G.M. Lukashenko and V.L. Pri-
tula, Thermodynamic Properties of Liquid Solu-
tions in the Silver-Germanium System, Izv. Akad.
Nauk SSSR Neorg. Mater., 3(9), p 1584-1590
(1967) in Russian; translated as Inorg. Mater., 3(9),
p 1379-1384 (1967). (Activities, free energies of 25.
mixing, entropies and heats of formation at
1378 K)
16. N.Kh. Abrikosov and N.N. Glagoleva, Study of
Melts Belonging to the G e r m a n i u m - - o r Silicon--
Metal Systems, Izv. Akad. Nauk SSSR Neorg.
Bulletin of Alloy Phase Diagrams
Ag-Ge
Lattice p a r a m e t e r s , n m
e Ref
0.4723 -+ 0.0003 10
0.47163 -+ 0.00016 12
Mater., 5(12), p 2055-2059 (1969) in Russian;
translated as Inorg. Mater., 5(12), p 1750-1753
(1969). (Viscosity isotherm data indicate existence
of a metastable compound, Ag3Ge, in the liquid
phase)
R. Castanet, Y. Claire and M. Laffitte, Enthalpy of
Formation at 1280 K of Liquid Alloys of Silver with
Germanium, Tin and Lead, J. Chim. Phys., 66,
p 1276-1285 (1969) in French.
P. Ramachandrarao and T. R. Anantharaman, New
Metastable Phases in Silver-Germanium and Gold-
Germanium Alloys Quenched from the Melt, Trans.
Met. Soc. AIME, 245(4), p 886-887 (1969). (A Ag-Ge
[21 at.% Ge] alloy yielded the expected cph phase
and a co-existent metastable tetragonal phase
[a = 0.5093 nm; c = 0.7009 nm])
P. Ramachandrarao and T. R. Anantharaman, For-
mation of Faulted Close-Packed Structures in
Silver-Germanium Alloys Quenched from the Melt,
Philos. Mag., 20, p 201-203 (1969). (1 to 25 at.% Ge,
X-ray patterns)
R. Castanet, Y. Claire, M. Gilbert and M. Laffitte,
Entropies of Formation of Liquid Alloys of Silver
and B Group Metals: Critical Study, Rev. Int.
Hautes Temp. Refract., 7, p 51-60 (1970) in French.
P. Furrer, T. R. Anantharaman and H. Warlimont,
Electron-Microscopic Evidence for Heavy Faulting
in Silver-Germanium Alloys on Rapid Solidifica-
tion, Philos. Mag., 21, p 873-877 (1970). (5 to 22
at.% Ge)
P. Ramachandrarao, P. R. Rao and T. R. Ananthara-
man, X-Ray Line Broadening in Splat-Cooled Sil-
ver and Silver-Germanium Alloys, Z. MetaUkunde,
61(6), p 471-475 (1970). (fcc and cph structure
observed in quenched Ag alloys with 10 to 20 at.%
Ge)
G.I. Batalin, E. A. Beloborodova and V. A. Stukalo,
Thermodynamic Properties of Germanium and Sil-
ver Molten Alloys, Zh. Fiz. Khim., 45(10), p 2697
(1971) in Russian. (emf measurements for liquid
Ag-Ge [7 to 87 at.% Ge] between 1270 and 1440 K;
activity, free energy, entropy and enthalpy deter-
mined at 1430 K)
B. Predel and D.W. Stein, Thermodynamic Analy-
sis of the Binary Systems of Germanium with Cop-
per, Silver and Gold, Z. Naturforsch. A, 26(4), p
722-734 (1971) in German. (Enthalpies of mixing
of Ag-Ge solid solution, as well as enthalpies of
formation in liquid Ag-Ge)
H.O. Kirchner and P. Ramachandrarao, Decompo-
sition of the Metastable Phase in the Ag-Ge System,
Philos. Mag., 25(5), p 1151-1160 (1972). (A two-
stage decomposition process was observed on heat-
ing in the metastable cph phase of a Ag-Ge [23
at.%] splat-cooled alloy)
Vol. 1 No. 2 1980 49
 Ag-Ge Provisional
26. B. Predel and U. Schallner, Thermodynamic Prop-
erties of Molten Binary Alloys of Ag and of Au with Fig. 2 Phase Diagram of The Ag-Ge
Ga, In and Ge, Z. Metallkunde, 63(6), p 341-347 System
(1972) in German.
27. B. Predel and U. Schallner; Determination of the G~-%Ge

Electronic Contribution to the Bonding in Binary

Copper, Silver and Gold Alpha-Solid Solutions
from Thermodynamic Investigations, proceedings
of an international symposium on metallurgical
chemistry (1971); Metall. Chem. Proc. Symp., 0.
Kubaschewski, Ed., HMSO, London, England, p
289-299 (1972). (emf measurements and theo-
retical discussion in terms of electronic structure.
Note updated data in [28])
28. B. Predel and U. Schallner, Estimation of Densi-
ties of State of Silver in Alpha-Solid Solutions of
Silver with Gallium, Indium, Germanium and Tin
Based on Thermodynamic Investigations by Solid
State Galvanic Cells, Z. Naturforsch. A, 27(7),
Ag
p 1098-1108 (1972) in German. (Partial free en- Xc~
thalpies of formation determined at 1000 K from
emf) Data of h [1], <> [2], [] [4], 9 [6], 9 [Hultgren, Binary]
29. N.A. Vatolin, V. F. Ukhov and V. P. Chentsov, Free and o [35]. Adapted from [35] with permission.
Surface Energy of Silver-Based Binary Eutectic
Melts, Tr. Inst. Met. Akad. Nauk S S S R Ural.
Nauch. Tsentr, 27(4), p 86-91 (1972) in Russian.
30. O. Uemura and S. Ikeda, Electrical Resistivity,
Magnetic Susceptibility, and Heat of Mixing of Fig. 3 Lattice Parameter as a Function of
Liquid Silver-Germanium Alloys, Trans. Jpn. Inst. Composition in Ag-Ge Alloys
Met., 14, p 351-354 (1973). (Anomaly near 10 to 20
at.% Ge in all three properties)
31. B.P. Burylev and V.D. Ivanova, Extension of the 4095 1-

Distribution Method for Studying Thermodynamic I

Properties of Metallic Melts, Tr. Krasnodar. Poli- I

tekh. Inst., 63, p 111-113 (1974) in Russian. I O

32. K.T. Jacob, C.B. Alcock and J. C. Chan, Chemical

Potential of Germanium and its Alpha-Solid Solu-
tions with Copper, Silver and Gold, Acta Met.,
22(5), p 545-551 (1974). (emf measurements for
about 1 to 6 at.% Ge in Ag. Disagrees with [28])
33. S. Barat and J. K. Mukherjee, Silver-Rich Alloys of

the Systems Ag-A1-Ge and Ag-AI-Sn, Indian J.
Technol., 13(11), p 510-519 (1975). (Lattice param-
eters for 2 to 8 at.% Ge)
34. L. Martin-Garin, M. Gomez, P. Bedon and P.
Desr~, Densities of Silver, Germanium and Silver-
Germanium Alloys in the Liquid State, J. Less-
Common Met., 41(1), p 65-76 (1975) in French.
(Excess volumes showed negative deviations from
ideal behavior. New phase diagram results are
presented which show 6 agreeing points on the
liquidus and a somewhat different [23.97 at.% Gel
eutectic composition at 651 ~
35. B. Predel and H. Bankstahl, Thermodynamic Prop-
erties of Liquid Silver-Germanium, Silver-Silicon,
Gold-Germanium and Gold-Silicon Alloys, J. Less-
Common Met., 43, p 191-203 (1975) in German.
(Activities and free energies of mixing of the liquid
alloys were calculated) A phase diagram with new
experimental points is shown in Fig. 2.
36. M.C. Bellissent, P. Desr~, R. Bellissent and G.
Tourand, Neutron Diffraction Studies of Liquid
Silver and Liquid Ag-Ge Alloys, J. Phys., 37, p
1437-1444 (1976). (Pair correlation and interfer-
ence functions in alloys of 14.2 to 59.8 at.% Ge at
1123 K)
i
o 5!o ,o!o ,'o
At % Ge
X (equilibrium data) [4], 9 (liquid-quenched) [10], o [37].
Adapted from [37] with permission.
37. S.C. Agarwal and H. Herman, Liquid Quenched
Ag-Ge Alloys--Formation and Evolution of Meta-
stable Phases, J. Mater. Sci., 12(10), p 2021-2027
(1977). (Ag-Ge [7 to 22.5 at.% Ge] were studied. An
amorphous phase was observed at 22.5 at.% Ge.
Lattice parameters were determined) See Fig. 3.
38. E.A. Beloborodova, G. I. Batalin and V.A. Stukalo,
Laws Governing the Thermodynamic Properties of
Binary Molten Ge-Base Alloys, Ukr. Khim. Zh.,
43(1), p 34-38 (1977) in Russian. (Correlations
between atomic radii, electronegativities and
thermodynamic properties)
39. K.L. Komarek, Thermodynamics of Liquid Alloys
--Experimental Techniques and Results, Bet Bun-

50 Bulletin of Alloy Phase Diagrams Vol. 1 No. 2 1980

 Ag-Ge
Provisional Ag.oo(co~ Au-Ge
senges, 81(10), p 936-950 (1977) in German. (Aria- Binary Substitutional Solutions, Trans. Jpn. Inst.
lyzes thermodynamic anomalies of many molten Met., 19(10), p 519-529 (1978). (Using free volume
binary alloys in terms of the formation of hetero- theory and available experimental data, derives
atomic "associates" in the liquid) thermodynamic functions for Ag-Ge and twelve
40. M.L. Kapoor, An Approach to Thermodynamics of other liquid Ag alloys)

The Au-Ge
System
(Gold-Germanium)
196.9665 72.59
amu amu

Fig. 1 Au-Ge Phase Diagram

Weight Percent Germanium
0 10 20 30 40 50 60 70 80 90 100
"|1 . . . . . . . . . i ......... i ''j ...... i ......... rI . . . . . . . . . I '''1 ...... t ''''I ..... J 'J . . . . . . II . . . . . . I ' " l ' Z ' ' " l " '

1100

937.25~
900 -

(D
0
ID
700 -

j~
J
ID_
E
500 -
.(Au) J

,.3.2 u [] "~""'" 556~ n u []

300 -
27

(Ge)
100 ......... I ......... I ......... I ......... ~ ......... l ......... I ......... I ......... I ......... I .........
10 20 30 40 50 60 70 80 90 100
Au Atomic Percent Germonium Ge

From [Elliott; IITRI] with permission. Open squares indicate thermal analysis data from [1].

Thermal analysis [1] showed the simple eutectic na- Table 1 Solid Solubility of Ge in Au
ture of the system; these investigators assigned an
accuracy of --15 ~ to their liquidus data (see Fig. 1). Temperature, ~ Composition, at.% Ge
Large-scale versions of the Au-Ge phase diagram 443 2.7
plotted in both at.% and wt.% appear in the Tear-Out 395 3.0
section in the back of this issue. Previously, in [2], the 382 3.0
eutectic composition had been reported as 24 at.% Ge; 363 (eutectic) 3.1
however, microscopic examination of a 24 at.% Ge alloy 336 1.7
by [1] revealed (Au) dendrites. 290 0.8
220 0.3
The solid solubility of Ge in Au (see Table 1) was deter-
mined from precise parameter data by [3], who esti- From [3] with permission.

Bulletin of Alloy Phase Diagrams Vol. 1 No. 2 1980 51