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18 Ag–Cu–In

Silver – Copper – Indium


Ortrud Kubaschewski, Alan Prince†, updated by Joachim Gröbner

Introduction
[1951Geb] and [1952Geb] investigated phase relationships in the indium poor region of this system by
thermal analysis, metallography and electrical conductivity measurements. They established six four-phase
equilibrium reactions and represented their findings by constructing three isothermal sections and four
isopleths. [1955Val], [1967Mcd] and [1979Dri] reviewed the work of [1951Geb] and [1952Geb]. Later
work by [1988Woy] is in substantial disagreement with [1951Geb] and [1952Geb]. The 1 phase occurring
at high temperatures in the Cu-In system, forms a solid solution series with the low-temperature 2 phase
of the Ag-In system. [1951Geb] and [1952Geb] assumed the bcc high temperature phases of Cu-In(1) and
Ag-In(2) both to be stabilized in the ternary and to decompose eutectically at 490 and 475°C, respectively.
[1988Woy] found both  phases to be already decomposed at 505°C. Since [1951Geb] and [1952Geb]
identified the phases by metallography only and not by X-ray diffraction, a partial explanation of the
disagreement with [1988Woy] may be a misinterpretation of the phase as ternary solutions of the 
phases. Nevertheless only part of the micrographs of annealed specimen published by [1952Geb] can be
interpreted by the isothermal sections given by [1988Woy].

Binary Systems
The binary Ag-Cu system was taken from the recent, published in the MSIT Evaluation Program by
[2002Rom]. Ag-In and Cu-In are accepted from [Mas2].

Solid Phases
The solid phases of Ag-In and Cu-In are listed in Table 1. No ternary phases have been reported.

Invariant Equilibria
Almost the entire reaction scheme can be derived from the liquidus surface given by [1988Woy] (Fig. 1)
but without temperatures for the four-phase equilibria. This disagrees with the partial reaction scheme given
by [1952Geb] in as far the two  phases react and disappear before the L + 1 + 2 three-phase field reacts
with another three-phase field. Since temperatures of Gebhardt's [1952Geb] scheme are tentatively assigned
to the invariant equilibria, which probably explain the thermal analysis effects of Gebhardt's isopleths, it is
not possible to reinterpret all measured points of these isopleths to be consistent with the findings of
[1988Woy]. Invariant solid-state reactions were not studied by [1988Woy]. The superstructure phases are
ignored in the reaction scheme.

Liquidus Surface
In Fig. 2 the liquidus surface according to [1988Woy] is shown. In the In poor part some isotherms from
[1951Geb] are inserted. For comparison the partial liquidus surface published by [1951Geb] is shown in
Fig. 3.

Isothermal Sections
In Fig. 4 and Fig. 5 the 676 and 505°C isothermal sections as published by [1988Woy] are shown. Figure 5
shows the overwhelming influence of the phase on the ternary equilibria. The 676°C isothermal section
(Fig. 4) does not correspond with the isopleths at 20 and 25 mass% In (Fig. 7 and Fig. 8). In particular
[1952Geb] indicates that the liquid phase occurs at 676°C on the 20 mass% In section. [1988Woy] shows
the liquidus isotherm located at higher In contents. It should be noted that the liquid apexes of the four tie
triangles in Fig. 4 do not correspond with points on the monovariant curves in Fig. 2. The L + +  field in

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Ag–Cu–In 19

the 505°C isotherm is changed because the original disagrees with the liquidus surface. The L + 2 + 2
field in Fig. 4 fits more closely Gebhardt's liquidus surface (Fig. 3) than to Fig. 2. Gebhardt's 500°C
isothermal section is shown in Fig. 6 for comparison.

Temperature – Composition Sections


Figures 7 and 8 show the isopleths at 20 and 25 mass% In, respectively, according to [1952Geb].

Notes on Materials Properties and Applications


The effect of quenching on the stress-strain characteristics of Ag alloy with 2 mass% Cu and 0.5 mass% In
was investigated in the temperature range from 500 to 650°C by [2004Nad].

References
[1951Geb] Gebhardt, E., Dreher, M., “On the Constitution of the Copper-Silver-Indium System”
(in German), Z. Metallkd., 42, 230-238 (1951) (Experimental, Phase Relations, 6)
[1952Geb] Gebhardt, E., Dreher, M., “On the Constitution of the Copper-Silver-Indium System”,
Z. Metallkd., 43, 357-363 (1952) (Experimental, Phase Relations, 3)
[1955Val] Valentiner, S., “Indium Alloys” (in German), Z. Metallkd., 46, 442-449 (1955) (Review, 86)
[1967Mcd] McDonald, A.S., Price, B.R., Sistare, G.H., “Ternary and Higher-Order Alloys of Silver”,
Silver-Economics, Metallurgy and Use, 272-303 (1967) (Phase Diagram, Review, 38)
[1972Jai] Jain, K.C., Ellner, M., Schubert, K., “On Phases in the Vicinity of the Composition
Cu64In36” (in German), Z. Metallkd., 63, 456-461 (1972) (Experimental, Crys. Structure,
Phase Relations, 6)
[1979Dri] Drits, M.E., Bochvar, N.R., Guzei, L.S., Lysova, E.V., Padezhnova, E.M., Rokhlin, L.L.,
Turkina, N.I., “Cu-In-Ag” in “Binary and Multicomponent Copper-Base Systems”, Nauka,
Moscow, 128-129 (1979) (Phase Diagram, Review, 3)
[1988Woy] Woychik, C.G., Massalski, T.B., “Phase Stability Relationships and Glass Formation in the
System Cu-Ag-In”, Metall. Trans., A19, 13-21 (1988) (Experimental, Phase Relations, 13)
[1994Sub] Subramanian, P.R., “Cu (Copper)”, in “Phase Diagrams of Binary Copper Alloys”,
Subramanian, P.R., Chakrabarti, D.J., Laughlin, D.E. (Eds.), ASM International, Materials
Park, OH, 1-3 (1994) (Crys. Structure, Review, 16)
[2002Rom] Van Rompaey, T., Rogl, P., “Ag-Cu (Silver - Copper)”, MSIT Binary Evaluation Program,
in MSIT Workplace, Effenberg, G. (Ed.), MSI, Materials Science International Services
GmbH, Stuttgart; Document ID: 20.14511.1.20, (2002) (Phase Diagram, Crys. Structure,
Thermodyn., Assessment, 29)
[2004Nad] Nada, R.H., “Precipitation Kinetics in Ag-2wt.% Cu and Ag-2wt.% Cu-0.5wt.% In Alloys
During Transformation”, Physica B, 349(1-4), 166-173 (2004) (Experimental, Kinetics,
Mechan. Prop., Morphology, Phase Relations, 22)

Table 1: Crystallographic Data of Solid Phases


Phase/ Pearson Symbol/ Lattice Parameters Comments/References
Temperature Range Space Group/ [pm]
[°C] Prototype
2, (Ag) cF4 a = 408.57 at 25°C [Mas2]
< 961.93 Fm3m
Cu
1, (Cu) cF4 a = 361.46 at 25°C [Mas2]
< 1084.62 Fm3m melting point [1994Sub]
Cu

Landolt-Börnstein
New Series IV/11C3
MSIT®
20 Ag–Cu–In

Phase/ Pearson Symbol/ Lattice Parameters Comments/References


Temperature Range Space Group/ [pm]
[°C] Prototype
(In) tI2 a = 325.3 at 25°C [Mas2]
< 156.634 I4/mmm c = 494.7
In
2, Ag3In(h2) cI2 a = 336.82 [V-C2]
695 - 660 Im3m
W
, Ag3In(r) hP2 a = 295.63 [Mas2]
< 670 P63/mmc c = 478.57
Mg
’, Ag3In cP4 a = 414.4  0.4 [Mas2]
< 187 Pm3m
AuCu3
, (Cu,Ag)9In4 cP52
P43m
2, Ag9In4(h) Cu9Al4 a = 992.2 [V-C2]
 314
1, Cu9In4(h) a = 925.03 [V-C2]
684 - 614
’, AgIn2 tI12 a = 688.1 [V-C2]
< 166 I4/mcm c = 562
Al2Cu
1, Cu4In(h) cI2 a = 304.6 [Mas2, V-C]
710 - 574 Im3m
W
, Cu7In3(r) aP40 a = 1007.1 [V-C2]
< 631 P1 b = 912.6
Cu7In3 c = 672.4
 = 90.22°
 = 82.84°
= 106.81°
, Cu2In(h3) hP6 a = 412.0 [V-C2]
667 - 440 P63/mmc c = 526.3
Ni2In
Cu7In4(h2) oP55 a = 2137.5 [1972Jai] superstructure of the Ni2In
480 - 350 P* b = 740.5 type
c = 521.8
Cu7In4(h1) oP88 a = 3419.4 [1972Jai] superstructure of the Ni2In
450 - 298 P* b = 739.5 type
c = 526.2
Cu7In4(r) - - [1972Jai]
< 390
Cu15In8 - - [1972Jai]
< 355
Q, Cu11In9 mC20 a = 1281.4 [V-C2]
< 310 C2/m b = 435.43
CuAl c = 735.3
 = 54.49°

MSIT® Landolt-Börnstein
New Series IV/11C3
New Series IV/11C3
Landolt-Börnstein

Ag-Cu Ag-In Ag-Cu-In Cu-In

779.1 e1
710 p1
l œ α1 + α2 695 p2 l + α1œ β1
l + α2 œ β2 678 e2
670 p4 l œ β1 + γ
α2 + β2 œ ζ 667 p3
660 e3 l + γœ η
β2 œ ζ + l β2 œ L + α2 + ζ E1 L + β1 œ α1 + γ U1
L+α1+γ 616 e4
600? L + α1 œ α2 + γ U2 γœ β1 + δ
L+α2+ζ β1+α1+γ 614 e5
L+α2+γ γœ δ + η
574 e6
575? L + α2 œ γ + ζ U3 β1œ α1 + δ

Ag–Cu–In
β1 œ α1 + γ + δ E2
α2+γ+ζ L+γ+ζ α1+α2+γ
α1+γ+δ
<505 L+γœη+ζ U4
470? α1 + 㠜 α2 + δ U5
L+η+ζ γ+η+ζ 310 p5
205 e7 α1+α2+δ γ+α2+δ
l + ηœϕ
ζœγ+l ζœL+γ+η E3
L+γ+η
L+ηœγ+ϕ U6
166 p6 L+γ+ϕ γ+η+ϕ
γ + l œ AgIn2
L + 㠜 ϕ + AgIn2 U7

144 e9 L+ϕ+AgIn2 γ + ϕ + AgIn2 153 e8


l œ (In) + AgIn2 l œ (In) + ϕ
L œ (In) + ϕ + AgIn2 E4
(In)+ϕ+AgIn2
MSIT®

Fig. 1: Ag-Cu-In. Reaction scheme

21
22 Ag–Cu–In

In Data / Grid: at.%


E4 e8 (In) e
Fig. 2: Ag-Cu-In. 9 Axes: at.%
ϕ AgIn2
Liquidus surface U7 p6
projection p5 U γ
6
[1988Woy] E3 e7
20
80

40
60

η
ζ
60
40
p3 U4 e3
U3 E1
γ β2
e2 p2
U1 U2
80 β1
p1 20

750 α2
850 α1 850
950°C
20 40 e1 60 80
Cu Ag

In Data / Grid: at.%


Fig. 3: Ag-Cu-In. Axes: at.%
Indium poor liquidus
surface projection
[1951Geb]
20
80

40
60

60
40

β1 p3
p2
p1 β2
U U
80
20
750 650 (Ag)
850
950 (Cu) 850
1050°C
20 40 60 e 80
Cu 1 Ag

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New Series IV/11C3
Ag–Cu–In 23

In Data / Grid: at.%


Fig. 4: Ag-Cu-In. Axes: at.%
Isothermal section at
676°C

20
80

40
60

60
40

γ L+γ
L+β 1 L+β 2
γ +β 1 β2
L+α1 β 2+α2
80
β1 20
α1+β 1 L+α2
α2
α1
α1+α2
20 40 60 80
Cu Ag

In Data / Grid: at.%


Fig. 5: Ag-Cu-In. Axes: at.%
Isothermal section at
505°C

20
80

40
60
L+η

η
60 L+ζ
40
γ +η γ +ζ
δ+η L+γ
γ
δ ζ
80
ζ +α 2
20
α 1+δ α 1+α 2+γ
α1+δ+γ
α2

α1 α1+α2
20 40 60 80
Cu Ag

Landolt-Börnstein
New Series IV/11C3
MSIT®
24 Ag–Cu–In

In Data / Grid: at.%


Fig. 6: Ag-Cu-In. Axes: at.%
Isothermal section at
500°C

20
80

40
60

60
40

β2 ζ
(Cu)+β 1+δ
β1 (Ag)+β 2+ζ
80
20
(Cu)+(Ag)+β 2
(Cu)+β 1+β 2 (Ag)

(Cu)

20 40 60 80
Cu Ag

1000
Fig. 7: Ag-Cu-In.
Isopleth at 20 mass%
In, plotted in at.% 900

800
L+(Cu)
Temperature, °C

L+(Ag)
700
L+(Cu)+β 1
L+(Ag)+β 2
L+(Cu)+β 2
600
(Cu)+β 1
L+(Ag)+(Cu) (Ag)+β 2
(Cu)+β 2
(Cu)+(Ag)+β 2
(Cu)+β 1+β 2
500
(Ag)
(Cu)+β2+δ
400
(Cu)+(Ag)+δ
(Cu)+δ (Cu)+β 1+δ
(Ag)+δ
300
Cu 87.90 10 20 30 40 50 60 70 80 Cu 0.10
Ag 0.00 Ag 80.90
In 12.10 Ag, at.% In 19.00

MSIT® Landolt-Börnstein
New Series IV/11C3
Ag–Cu–In 25

900
Fig. 8: Ag-Cu-In.
Isopleth at 25 mass%
In, plotted in at.%
800

L+α L
L+α '
700
Temperature, °C

L+α +β L+α '+β '


L+α +α '
L+α +β ' β '+γ' γ'
600
α +β α '+β '+γ'
L+β '
β'
α +β +δ
α +β '
α +β +β '
500
α '+γ'
α +δ α +δ +β ' α +α '+β '
α '+δ
α +β '+δ
400

δ +α '+α
α '+δ +γ'
300
Cu 84.40 10 20 30 40 50 60 70 Cu 0.00
Ag 0.00 Ag 76.10
In 15.60 Ag, at.% In 23.90

Landolt-Börnstein
New Series IV/11C3
MSIT®