J. Phase Equilib. Diffus.
(2019) 40:115–125
https://doi.org/10.1007/s11669-019-00709-z
Experimental Thermodynamics and Surface Properties
of Ag-Cu-Ge Solder/Braze Alloys
Simona Delsante1,2 • Gabriella Borzone1,2 • Rada Novakovic2
Submitted: 29 October 2018 / in revised form: 12 January 2019 / Published online: 1 February 2019
Ó ASM International 2019
Abstract Ag-based alloys have industrial importance in
relation to their use as high-temperature solders in jew-
ellery or braze alloys for thermoelectric modules. Good
wetting properties and a tarnish-resistance of Ag-Ge and
Ag-Cu-Ge alloys together with appropriate mechanical
properties make them good candidates for bonding sterling
silver (Ag-7.5Cu, in wt.%). The melting temperature and
the heat of melting of Ag-Cu, Ag-Ge and Ag-Cu-Ge
eutectic alloys have been measured by differential scanning
calorimetry. From a technological point of view, particular
attention should be paid to the surface tension, a key
property of the joining processes. The aim of this study is
to correlate the thermodynamic properties of the Ag-Cu-Ge
system and its subsystems with their surface properties and
to compare the model predicted property values to the data
available in the literature.
Keywords Ag-Cu-Ge alloys  Butler’s model 
calorimetry  surface tension  thermodynamic modeling
This invited article is part of a special issue of the Journal of Phase
Equilibria and Diffusion in honor of Prof. Jan Vrestal’s 80th birthday.
This special issue was organized by Prof. Andrew Watson, Coventry
University, and Dr. Ales Kroupa, Institute of Physics of Materials,
Brno, Czech Republic.
& Rada Novakovic
rada.novakovic@ge.icmate.cnr.it
1
Department of Chemistry and Industrial Chemistry, Genoa
University and Genoa Research Unit of INSTM, Via
Dodecaneso 31, 16146 Genoa, Italy
2 predictions. In this work, new experimental data on the
Institute of Condensed Matter Chemistry and Energy
Technologies, National Research Council (ICMATE-CNR),
Via de Marini 6, 16149 Genoa, Italy
1 Introduction
Silver is prone to tarnishing while its alloys containing Ge
with either Zn or Cu exhibit good tarnish resistance, and
Ag-Ge-X (X = Zn, Cu) alloys are used as high-temperature
solders for Ag-7.5Cu (in wt.%) sterling silver.[1,2] A rapid
quenching of Ag-Cu-Ge melt results in the formation of an
amorphous phase with particular thermal and electrical
properties over a wide range of composition and temper-
ature.[3,4] Indeed, these alloys are suitable for the investi-
gation of non-magnetic disordered metallic systems in
terms of their electron transport properties.[4] On the other
hand, Ag-Cu and Ag-Ge alloys are employed as braze
material for ceramics[5–7] and thermoelectric systems,[8,9]
respectively. Cu-Ge alloys are low-room-temperature
resistance contact materials for optical devices,[10] semi-
conductors[11,12] and storage industries.[13]
The Ag-Cu-Ge system has been experimentally[14–16]
and theoretically[16,17] studied. In order to improve the
operating conditions of the joining process particular
attention has been paid to the L ¡ (Ag) ? (Ge) ? g-
Cu3Ge eutectic alloy and its thermal properties. There are
many datasets related to its melting temperature and
composition that differ within experimental error,[15,17] but,
until now, the melting enthalpy data are lacking. Con-
cerning the Ag-Cu, Ag-Ge and Cu-Ge systems, there is
much literature on their thermodynamic properties as well
as the corresponding phase diagrams.[18] For each of the
three binary subsystems, the surface property data are also
available.[19–21] In contrast, the surface tension of liquid
Ag-Cu-Ge alloys is not yet experimentally determined and
the lack of such data can be compensated by theoretical
melting temperature and melting enthalpy of binary and
ternary eutectics have been experimentally determined. In
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addition, the surface tension of the binary and ternary
alloys was calculated using the Butler model,[22,23] and the
calculated values have been compared to the available
literature data.
2 Experimental
2.1 Materials and Sample Preparation
Binary and ternary alloys ingots were prepared starting
from pure elements (Ag, 99.99%, Johnson-Matthey; Ge,
99.999%, Koch Light Lab.; Cu, 99.999%, NewMet Koch).
The surface of the Ag and Ge bars were mechanically
cleaned, while Cu was cleaned in a H2 flow at 150 °C for
2 h to remove the oxide. Proper amounts of Ag, Cu and Ge
were weighed with an accuracy of ± 0.05 mg and then
melted in an arc-melting furnace. The weight of the buttons
varied between 0.7 and 1.0 g, and they were subsequently
divided into several pieces. The samples were homoge-
nized during a first cycle in a calorimeter.
2.2 DSC Measurements: Experimental Details
Two kind of differential scanning calorimeters (DSC) from
Setaram were used to measure the melting temperature and
the heat of melting of the binary and ternary eutectic
mixtures. A LABSYS Evo (working temperature up to
1500 °C) was employed for the Ag-Ge and Ag-Cu eutectic
alloys, while the measurements on the Ag-Cu-Ge were
performed by using the DSC 111 (working temperature up
to 800 °C). For the LABSYS Evo, temperature correction
and enthalpy calibration were carried out by measuring the
melting temperature and the heat of melting of a known
mass of standard materials (pure metals: In, Bi, Zn, Al, Ag
and Cu) at 5°/min. Literature data have been taken from.[24]
The DSC 111 exploits a Joule Effect Calibration (using an
EJ3 module) and the temperature scale and sensitivity were
checked with standard materials (pure metals: In, Sn and
Bi). All samples were flushed several times with high-pu-
rity argon and subsequently sealed in evacuated quartz
ampoules or in Ta crucibles. The weight of the DSC
samples varied between 300 and 400 mg. Calorimetric
experiments were carried out in a continuous mode with a
heating/cooling rate of 5°/min in argon atmosphere. The
melting temperature was defined from the heating curves at
the onset point of the peaks.[25,26]
After DSC analysis, the microstructure of samples was
investigated by optical and scanning electron microscopy
(SEM). A Leica Digital Microscope and a Zeiss Evo 40
equipped with a Pentafet Link Energy Dispersive x-ray
Spectroscopy (EDS) system managed by the INCA Energy
software (Oxford Instruments Analytical, High Wycombe,
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J. Phase Equilib. Diffus. (2019) 40:115–125
Bucks, UK) were employed. The SEM operates at an
acceleration voltage of 20 kV and calibration for the
quantitative measurements was performed with a Co
standard.
3 The Surface Tension Calculations: Butler’s
Model
The use of Butler’s model mainly is associated with the
surface tension calculations of binary and ternary alloys.[27]
The surface tension model predicts values of weakly
interacting systems, in particular those characterized by the
eutectic type phase diagram, for example the Pb-Sn, Bi-
Sn,[28] Ga-Sn, Ga-Zn,[29] Ag-Cu,[19,30] and Cd-Zn,[31]
showing that the values calculated by the Butler model are
very close or even overlap with the corresponding values
obtained by the first or the quasi-chemical approxima-
tion (QCA) for regular solutions.[27,32] Based on the
aforementioned considerations, the validity of Butler’s
model for ternary alloy systems having weakly interacting
binaries was experimentally substantiated.[28,31–33]
Assuming the regular solution model, and considering
the surface phase as an additional phase being in thermo-
dynamic equilibrium with the bulk phase, the surface ten-
sion can be calculated as:
RT Xis 1 n xs;s    o
r ¼ ri þ ln b þ Gi T; Xjs  Gxs;b i T; Xjb
Si Xi S i
ðEq 1Þ
where Xkj denotes an alloy composition, and subscript j and
superscript k refer to the corresponding component j in the
bulk b or in the surface phase s. Gxs,b b
i (T, Xj ) and
xs,s s
Gi (T, Xj ) are partial excess Gibbs energies of component
i in the bulk phase and the surface phase, respectively, both
expressed as functions of temperature and composition. ri,
Si, R, and T are the surface tension and surface area of
component i, the gas constant and the temperature,
respectively. The surface area of component i is calculated
by:
Si ¼ 1:091  N0 ðMi =qi Þ2=3 ðEq 2Þ
where N0, Mi, and qi are Avogadro’s number, the atomic
mass and the density data of component i, respectively,
Gxs,b
i and Gxs,s
i are related to the respective coordination
numbers in the bulk phase and the surface phase, and it is
postulated that the free energy of an alloy is always pro-
portional to the number of interactive contacts between
neighbouring atoms, as follows:
   
Gxs;s T; X s
¼ ~ xs;b T; X s
bG ðEq 3Þ
i j i j
where b~ is a parameter describing the reduced coordination
J. Phase Equilib. Diffus. (2019) 40:115–125
at the surface phase that is given as the ratio between the
two coordination numbers. In typical close-packed solid
structures (fcc, hcp) the coordination numbers are 12 and 9
for the bulk and the surface phases, respectively. Accord-
ingly, taking into account the fcc crystal structures of Ag
and Cu together with the hcp of Zn, the reduced coordi-
nation b~ = 0.75 was taken as input for the surface tension
calculations of the Ag-Cu-Ge and its subsystems. In the
framework of the CALPHAD method,[34] the excess Gibbs
free energy of the solution phases of binary, ternary and
multicomponent systems is described by the Redlich–Kis-
ter polynomials. Indeed, it is possible to approximate the
excess Gibbs free energies of higher order systems from
those of their boundary systems, if they are already opti-
mized. In particular, the extrapolation from the binary
subsystems into a ternary system, known as the Redlich–
Kister–Muggianu (RKM) model, is appropriate for weakly
interacting ternary systems having small ternary interac-
tions in the liquid phase with respect to those which arise
from the binaries. If the experimental data on ternary alloys
are available,[34] the excess Gibbs free energy is defined by
adding the term x1x2x3L123 to the RKM model which can
be calculated by:
X X
n
xs
GLABC ¼ xi xj  ðAt þ Bt  T=K Þ
i;j
 t¼0
t
 xi  xj þx1 x2 x3 L123 : ðEq 4Þ
4 Results and Discussion
The thermodynamic and surface properties of liquid Ag-
Cu, Ag-Ge and Cu-Ge alloys have been determined for
different temperatures and compositions and their phase
diagrams are available.[18] In the case of the Ag-Cu-Ge,
neither thermodynamic nor the surface properties have
been reported. For all alloy systems, the surface tension
calculations have been carried out for T = 1000 °C and, in
the case of binaries, the calculated property values have
been compared to the corresponding literature data.
4.1 DSC Results on Ag-Cu, Ag-Ge and Ag-Cu-Ge
Eutectic Alloys
The melting temperature and enthalpy of the melting of
Ag-Cu, Ag-Ge and Ag-Cu-Ge eutectic alloys have been
determined using the experimental procedure described in
Sect. 2 and the results are summarized in Table 1. The Ag-
Cu and Ag-Ge systems show simple eutectic phase dia-
grams in which the invariant reactions occur at 780 °C for
117
L ¡ (Ag) ? (Cu) and at 651 °C for L ¡ (Ag) ?
(Ge), and are well established.[18] Concerning the Ag-Cu-
Ge ternary eutectic L ¡ (Ag) ? (Ge) ? g-Cu3Ge, differ-
ent values of its composition and temperature have been
reported. Indeed, the eutectic composition (in at.%) varies
between: 38.5 \ Ag \ 44.3, 29.0 \ Cu \ 33.4 and
23.0 \ Ge \ 29.6, while the temperature is within
520–540 °C.[14–17,35]
From the present DSC measurements, the following
eutectic temperatures were determined: 779.5 ± 0.4 °C for
the Ag-Cu and 649.9 ± 0.3 °C for the Ag-Ge systems.
Both values are in very good agreement with the literature
data.[18] The melting enthalpy values of 123.7 ± 1 J/g and
130.9 ± 1.1 J/g for the binary eutectic mixtures (Ag) ? (
Cu) and (Ag) ? (Ge), respectively, have been obtained by
integrating the heating peak area considering the proper
calibrations. In the case of the Ag-Cu system, a lower value
was obtained in comparison with that of 166.4 ± 13.3 J/g
reported by Cagran et al.[36] It is worth mentioning that
those authors determined the melting enthalpy of a com-
mercial Ag-28.1Cu (in wt.%) wire-shaped specimen by
using a fast pulse-heating technique. The value of 166.4 J/g
was estimated by extrapolation from electrical resistivity
versus specific enthalpy dependence, with an uncertainty of
about 8%, evaluated according to the Guide to the
Expression of Uncertainty in Measurement.[37] For the Ag-
Ge system, no experimental melting enthalpy data are
available for comparison.
The heating curves of the Ag-Cu and Ag-Ge samples are
displayed in Fig. 1(a) and (c) together with the back-scat-
tered electron (BSE) images (Fig. 1(b) and (d)). Both
samples show a single peak on heating and on cooling in
the DSC curves, confirming the eutectic composition of the
alloys. In both cases, the microstructure shows a typical
eutectic mixture, and the EDS analysis confirmed the
composition of the eutectic points reported in literature.[18]
Concerning the Ag-Cu-Ge system, we have prepared
several samples near the ternary eutectic composition,
according to the literature data.[14–16] From the EDS analy-
sis, we identified a ternary eutectic composition of
Ag37.0Cu32.5Ge30.5 (in at.%). The melting enthalpy
associated to the ternary eutectic mixture is 12.5 ±
0.1 kJ/mol and the melting temperature is 538.0 ± 0.5 °C,
in very good agreement with the value (539 °C) reported by
Akhmetova et al.[15] Figure 1(e) shows the heating curve
obtained for the Ag37.0Cu32.5Ge30.5 alloy. Similarly to the
binary systems, the DSC heating/cooling curves of the Ag-
Cu-Ge sample show only one peak and, after DSC mea-
surements, the microstructure has a peculiar ternary eutectic
aspect, as can be easily recognized in the BSE image shown
in Fig. 1(f).
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Table 1 Melting temperature
Invariant reaction
(Tfus) and melting enthalpy
(DfusH) of the investigated L ¡ (Ag) ? (Ge)
eutectic mixtures
(24.5 at.% Ge)
L ¡ (Ag) ? (Cu)
(39.9 at.% Cu)
L ¡ (Ag) ? (Ge) ? g-Cu3Ge
(Ag37Cu32.5Ge30.5, in at.%)
4.2 Thermodynamic Properties of Liquid Ag-Cu,
Ag-Ge, Cu-Ge and Ag-Cu-Ge Alloys
Thermodynamic properties such as the enthalpy of mixing
and the activities together with the phase diagrams[18]
suggest different types of interactions in liquid Ag-Cu, Ag-
Ge and Cu-Ge alloys, and these systems can be classified as
segregating, mixed and compound forming, respec-
tively.[38] The term ‘‘mixed’’ indicates the presence of both
endothermic and exothermic reactions in an alloy system,
such as in the case of the Ag-Ge. Indeed, the enthalpy of
mixing and activity data for Ag-rich alloy compositions
exhibit negative deviation from Raoult’s law, while for
other Ag-Ge alloys the opposite trend was observed
(Fig. 2). Thermodynamic modeling of thermophysical
properties of liquid Ag-Ge alloys and detailed analysis of
available experimental data was recently reported in Ref
39. The mixing properties of the Ag-Ge, i.e., the Gibbs free
energy of mixing,[38,40] enthalpy of mixing[38,41] and
activities[38,42] were calculated for T = 1000 °C and com-
pared to the literature data. The normalized form of the
Gibbs free energy of mixing GM/RT, calculated for
T = 1000 °C, shows a minimum of about - 0.72 at xGe-
= 0.4, indicating a small shift from the equiatomic com-
position due to a weak compound formation tendency
experimentally observed for Ag-rich alloys,[43] while Ge-
rich and intermediate alloy compositions exhibit slight
demixing.[44] Both types of interaction between the atomic
species in the Ag-Ge liquid phase are weak.
The study of thermodynamic, structural and surface prop-
erties of Ag-Cu liquid alloys have been detailed in Ref 30.
Based on the more recent phase diagram data,[45] the calcu-
lated integral Gibbs free energy of the Ag-Cu liquid phase, the
enthalpy of mixing and activities together with corresponding
literature data[38,45–47] are shown in Fig. 3. The calculations
were carried out for T = 1100 °C and the predicted property
values are in good agreement with the available experimental
data. All thermodynamic data of the Ag-Cu system indicate
positive deviation from Raoult’s law (Fig. 3) and thereby
support a weak demixing tendency in this system.[30]
The Cu-Ge system is compound forming system with
three intermetallic compounds of which g-Cu3Ge is ener-
getically favored.[48] The calculated thermodynamic
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J. Phase Equilib. Diffus. (2019) 40:115–125
DfusH, kJ, mol Tfus, °C Notes
13.0 ± 0.1 649.9 ± 0.3 Labsys Evo, v = 5°/min
(130.9 ± 1.1 J/g) (Ta crucible)
11.2 ± 0.1 779.5 ± 0.4 Labsys Evo, v = 5°/min
(123.7 ± 1.0 J/g) (Ta crucible)
12.5 ± 0.1 538.0 ± 0.5 DSC 111, v = 5°/min
(146.8 ± 1.3 J/g) (Quartz crucible)
property curves for the Cu-Ge liquid phase reproduce all
available thermodynamic data fairly well, including the
asymmetry of the curve describing the Gibbs free energy of
mixing in its normalized form having a minimum of
- 1.35 at xGe = 0.35 (Fig. 4). The observed composition is
slightly shifted with respect to the composition of g-Cu3Ge.
The tendency of compound formation in this system is
moderate.[49] The enthalpy of mixing and activities of
liquid Cu-Ge alloys calculated for T = 1100 °C as well as
the corresponding experimental datasets[50–53] exhibit
negative deviation from Raoult’s law (Fig. 4).
The enthalpy of mixing datasets Ref 50 and 51 differ up
to 40% in the composition range 10 \ Ge \ 40 (in at.%),
although the measurements have been performed at tem-
peratures close to each other, i.e., T = 1075 and
T = 1090 °C, respectively, while the data measured at
T = 1150 °C[52] exhibit good agreement with Ref 51.
Concerning Cu and Ge activity, the calculated values are
compared to the experimental data obtained at
T = 1265 °C.[53] Both activity datasets agree well for Cu-
and Ge-rich alloy compositions, while for intermediate
alloy compositions 30 \ Ge \ 70 (in at.%), significant
differences can be observed (Fig. 4).
The experimental datasets on the Ag-Cu-Ge system
have been obtained from metallographic analyses of
annealed alloy samples and from the measurements of the
enthalpy of dissolution of solid Ge into Ag-Cu liquid
alloys, the enthalpy of the formation and activities of liquid
alloys and were summarised in Ref 15 and 16. The ther-
modynamic data analysis indicates that the Ag-Cu-Ge
system is a weakly interacting one. Recently, Guo et al.[16]
reported the thermodynamic parameters used for the first
assessment of the Ag-Cu-Ge phase diagram. Therefore, the
excess Gibbs free energies of the mixing of Ag-Cu,[45] Ag-
Ge[40] and Cu-Ge[48] liquid alloys were combined by means
of the Redlich–Kister–Muggianu model (RKM) adding the
ternary term of the excess Gibbs free energy x1x2x3L123
(Eq 4).[16] L123 is expressed by the Redlich–Kister poly-
nomials of the second order (Table 2). The calculations
were carried out for T = 1100 °C, and the difference
between the excess Gibbs free energies of the Ag-Cu-Ge
liquid phase obtained by the RKM model and (Eq 4) is
very small.
J. Phase Equilib. Diffus. (2019) 40:115–125 119

Fig. 1 DSC heating curve (5°/min) of (a) the Ag-Cu, (c) Ag-Ge and alloy: (Ag) bright phase and (Cu) black phase, (d) the Ag-Ge alloy:
(e) Ag-Cu-Ge samples at the eutectic composition. Eutectic mixture (Ag) light gray phase and (Ge) black phase, and (f) the Ag-Cu-Ge
micrograph (BSE image) after DSC measurement of (b) the Ag-Cu alloy: (Ag) bright phase, g-Cu3Ge gray phase and (Ge) black phase

123
120 J. Phase Equilib. Diffus. (2019) 40:115–125

Fig. 4 Concentration dependence of GM/RT (curve 1),[48] HM/RT

Fig. 2 Concentration dependence of the Gibbs free energy of mixing
(GM/RT; curve 1), the enthalpy of mixing (HM/RT; curve 2), the
activity of silver (aAg; curve 3a) and germanium (aGe; curve 3b) of
liquid Ag-Ge alloys calculated for T = 973 °C together with the
experimental data on the enthalpy of mixing (open triangle, filled
inverted triangle) obtained at 977 and 1007 °C, respectively,[38,41] aAg
(open square, filled star)[38,42] and aGe (open circle, big plus)[38,42]
both measured at 977 °C. The Ag-Ge liquid phase description[40] was
compared to GM dataset (filled circle) obtained from compilations of
critically evaluated thermodynamic property data.[38] (dashed lines—
the ideal solution model)
(curve 2), aCu (curve 3a) and aGe (curve 3b) for liquid Cu-Ge alloys
calculated for T = 1100 °C. The experimental data on HM (filled
circle, filled triangle, open square) obtained at 1075, 1090 and
1150 °C, respectively,[50–52] aCu (filled diamond)[53] and aGe (large
plus sign)[53] both measured at T = 1265 °C were taken for a
comparison (dashed lines—the ideal solution model)
Table 2 Thermodynamic data of the excess Gibbs free energy of the
Ag-Cu-Ge liquid phase described by Redlich–Kister polynomials
(Eq 4) and its binary constituents together with the surface tension
reference data of liquid Ag, Cu and Ge
xs
System m GA–B
L , J mol
-1
Ref

Ag-Cu 0 14,463–1.516T 45
1 - 934 ? 0.319T
Ag-Ge 0 7636.87–6.822T 40
1 - 14,500.14 ? 5.761T
2 - 7029.56
Cu-Ge 0 - 22,422.37–3.993T 48
1 - 37,961.74 ? 9.446T
2 - 19,505.73 ? 5.595T
xs
Ag-Cu-Ge GA–B–C
L , J mol-1
0 - 169,830.50 ? 98.2367T 16
1 - 14,312.23–74.1606T
2 - 16,172.41
Fig. 3 Concentration dependence of GM/RT (curve 1), HM/RT (curve Pure metal Melting point, K r0/Nm-1 dr/dT/N m-1 K-1
2), aAg (curve 3a) and aCu (curve 3b) for liquid Ag-Cu alloys
calculated for T = 1100 °C. The experimental data on HM (filled Surface tension
diamond, filled circle) obtained at 1150 and 1102 °C, respec- Ag 1234 0.914 0.15 9 10-3 30
tively,[38,46] aAg (filled inverted triangle, open square)[38,47] and aCu
Cu 1357 1.339 0.18 9 10-3 30
(filled triangle)[38] were taken for a comparison. The Ag-Cu liquid
phase description[45] was compared to GM (filled star), obtained from Ge 1214 0.616 0.07 9 10-3 54
compilations of critically evaluated thermodynamic property data.[38]
(dashed lines—the ideal solution model)

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J. Phase Equilib. Diffus. (2019) 40:115–125
4.3 Surface Properties
The surface properties of liquid Ag-Cu, Ag-Ge, Cu-Ge and
Ag-Cu-Ge alloys have been calculated using the Butler
model in the regular solution approximation (Eq 1). For
each binary system, the input data, such as the surface
tension reference data of liquid Ag,[30] Cu,[30] Ge,[54] molar
volume of pure components[55] and the Gibbs free excess
energies of the Ag-Ge,[40] Ag-Cu,[45] and Cu-Ge[48]
(Table 2), have been used to calculate the surface tension
isotherms as well as the surface segregation. Subsequently,
the results obtained for the binaries were combined in order
to obtain the surface properties of liquid Ag-Cu-Ge ternary
alloys. Numerically solving the system of two or three
equations describing the surface tension with respect to
each alloy component (Eq 1), the surface compositions of
the binary and ternary systems were obtained and the
surface tension isotherm can be calculated by inserting the
surface composition values into Eq 1.
For all the alloy systems, the calculations have been
performed for T = 1000 °C, while in the case of Ag-Ge
liquid alloy, additional calculations have been carried out
aiming to compare the calculated results to the experi-
mental data measured at T = 900 °C.[20,56] Concerning the
surface enrichment, it is well known that an alloy com-
ponent having a lower surface tension segregates on the top
surface layer (monolayer) of a melt.[27] Indeed, Ge atoms
segregate to the surface of the Ag-Ge liquid alloys (Fig. 5).
The degree of segregation decreases with an increase in
temperature. Once the surface composition was obtained,
the surface tension isotherm was calculated by Butler’s
model (Eq 1) and firstly compared to the so-called perfect
solution isotherm.[55,57] The two Ag-Ge isotherms intersect
Fig. 5 Surface composition (CsGe) versus bulk composition (CGe) in
liquid Ag-Ge alloys calculated by the Butler model for regular
solutions for T = 900 °C (dashed line—the additive rule)
121
and the point of intersection corresponds to an alloy
composition with 30 at.% Ge, as already observed in the
case of the thermodynamic properties (Fig. 2), indicating
the change of exothermic to endothermic behavior in this
system. The calculated surface tension values were com-
pared to the experimental data[20,56] and, for Ge-rich alloys,
the model’s predicted values are in a good agreement with
Ref 56, otherwise are closer to the dataset,[20] exhibiting
differences in surface tension up to 10% (Fig. 6).
The surface enrichment of Ag-Cu melts by Ag atoms
has been experimentally determined by Williams and
Norris.[58] Their results obtained at T = 1108 °C are
slightly lower with respect to the model-predicted values,
but are good enough to substantiate the calculated surface
composition of liquid Ag-Cu alloys for T = 1100 °C
(Fig. 7). The surface tension of Ag-Cu liquid alloys has
been experimentally determined by many authors and the
datasets obtained at T = 1100 °C were taken into account
for a comparison.[16,30,59–61] The surface tension isotherm
calculated by the Butler model agrees fairly well with the
datasets,[30,59] while the other experimental data are sig-
nificantly lower with respect to the model-predicted values
(Fig. 8), probably due to a higher oxygen concentration in
the surrounding atmosphere during the measurements.[27]
The calculated surface composition of liquid Cu-Ge
alloys indicates the segregation of Ge atoms to the surface
(Fig. 9). For Cu-Ge alloy compositions with Ge [ 55 at.%
the surface tension isotherm obtained by the Butler model
and that calculated by the perfect solution model[61] over-
lap. The experimental data measured at T = 1100 °C
(Fig. 10) exhibit good agreement with the corresponding
calculated values.[21] An exception represents the surface
Fig. 6 Surface tension isotherm of liquid Ag-Ge alloys calculated for
T = 900 °C by the Butler model for the regular solution (dashed
line—the perfect solution model). For a comparison the surface
tension literature data (filled circle, filled triangle) were taken from
Ref 20 and 56, respectively
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122 J. Phase Equilib. Diffus. (2019) 40:115–125

Fig. 7 Surface composition (CsAg) versus bulk composition (CAg) for Fig. 9 Surface composition (CsGe) versus bulk composition (CGe) in
liquid Ag-Cu alloys calculated by the Butler model for regular liquid Cu-Ge alloys calculated by the Butler model for regular
solutions for T = 1100 °C together with the experimental data solutions for T = 1100 °C (dashed line—the additive rule)
measured at T = 1108 °C.[58] (dashed line—the additive rule)

Fig. 10 Surface tension isotherm of liquid Cu-Ge alloys calculated

for T = 1100 °C by the Butler model for the regular solution (dashed
Fig. 8 Surface tension isotherm of liquid Ag-Cu alloys calculated for line—the perfect solution model). For a comparison the surface
T = 1100 °C by the Butler model for the regular solution (dashed tension literature dataset (filled circle) obtained at the same temper-
line—the perfect solution model). For a comparison, the surface ature was taken from Ref 21
tension literature data (filled triangle, open square, large plus sign,
filled circle, large multiplication sign) obtained at the same temper- descriptions of the liquid phases of the Ag-Ge, Ag-Cu and
ature were taken from,[16,30,59–61] respectively
Cu-Ge binary and ternary excess Gibbs energy term
(Table 2), the surface tension of liquid Ag-Cu-Ge alloys
tension data of pure liquid copper that is significantly lower
has been calculated for T = 1100 °C by using the Butler
with respect to the Cu reference data reported in Ref 30.
model in the regular solution approximation. The predicted
The large scatter in the surface tension datasets is related to
surface tension values of ternary alloys vary between 625
different experimental methods and operating conditions.
and 1150 (Fig. 11). The results of the calculations indicate
Concerning the surface tension calculations, the choice of
that the surface tension of ternary alloys gradually increase
the surface tension reference data has to take into account
with a decrease of Ge content or with an increase of Cu
the accuracy and reproducibility of the chosen data.[27]
content. The iso-surface tension lines of liquid Ag-Cu-Ge
The input data used for the surface tension calculations
alloys are shown in Fig. 11. The surface tension-predicted
of the Ag-Cu-Ge system and its binary subsystems are
value for the Ag37.0Cu32.5Ge30.5 (in at.%) eutectic alloy
given in Table 2. Combining the corresponding
is about 809 mN m-1. Due to the lack of surface tension

123
J. Phase Equilib. Diffus. (2019) 40:115–125
Fig. 11 Iso-surface tension lines (in mN m-1) of liquid Ag-Cu-Ge
alloys calculated for T = 1100 °C. Filled circle indicates the eutectic
composition
Fig. 12 Iso-surface concentration lines of Ge in liquid Ag-Cu-Ge
alloys calculated for T = 1100 °C. Filled circle indicates the eutectic
composition
experimental data on Ag-Cu-Ge ternary alloys, it was not
possible to compare the calculated values.
Taking into account that liquid Ge has the lowest sur-
face tension in comparison to those of Ag and Cu, a
preferential segregation of Ge atoms to the surface of liquid
Ag-Cu-Ge alloys is expected, and the iso-surface concen-
tration lines of Ge were calculated for T = 1100 °C
(Fig. 12). Concerning the Ag37.0Cu32.5Ge30.5 (in at.%)
eutectic melt, the composition of its surface layer is esti-
mated to be rich in Ge (about 70 at.%) and Ag atoms with a
123
sporadic presence of Cu atoms. Generally, for the Ag-Cu-
Ge system, some segregation of Cu atoms may be expected
close to limiting Ag-Cu and Cu-Ge binaries.
5 Conclusions
The thermodynamic functions of mixing classify Ag-Cu
and Ag-Ge as weakly interacting systems with a tendency
for demixing, while Cu-Ge and Ag-Cu-Ge exhibit no
strong compound-forming tendencies. In view of applica-
tions, the new experimental data obtained by DSC mea-
surements, i.e., the melting temperature and melting
enthalpy of Ag-Cu, Ag-Ge and Ag-Cu-Ge eutectic mix-
tures together with the surface properties of the above-
mentioned alloy systems are important for joining
processes. The analysis of the surface tension datasets
available in the literature and their subsequent comparison
to the corresponding values obtained by the Butler model
indicate a scatter between the datasets. The main reason for
scattering of experimentally determined surface tension
data is the presence of oxygen in a surrounding atmosphere
during the measurements. In the case of Ag-Cu-Ge alloys,
to compare the surface tension predicted values, the ex-
perimental data are needed.
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