INSTITUTE OF PHYSICS PUBLISHING MEASUREMENT SCIENCE AND TECHNOLOGY

Meas. Sci. Technol. 16 (2005) 438442 doi:10.1088/0957-0233/16/2/015

Temperature dependence of surface

tension of liquid SnAg, InAg
and InCu alloys
Joonho Lee, Wataru Shimoda and Toshihiro Tanaka
Department of Materials Science and Processing, Graduate School of Engineering,
Osaka University, 2-1 Yamadaoka, Suita, 565-0871, Japan
E-mail: tanaka@mat.eng.osaka-u.ac.jp

Received 1 June 2004, in final form 3 December 2004

Published 19 January 2005
Online at stacks.iop.org/MST/16/438
Abstract
It is usually known that the surface tension of liquid metals and alloys
decreases with increasing temperature, i.e., the temperature dependence of
the surface tension is negative. We found, however, that some liquid alloys,
which have large difference of the surface tension of pure components, show
positive temperature dependence in certain composition ranges. Some
Pb-free alloys, for which information on the surface tension is indispensable
to be developed as environmental-friendly material, can be listed in this
special category. The experimental results and the thermodynamic analysis
of the temperature dependence of those alloys are discussed in the paper.
Keywords: surface tension, density, constrained drop method, temperature
dependence, wetting diagnostics

1. Introduction 2. Experimental details

In recent years, great efforts have been made to develop new
lead-free solders to substitute for tinlead eutectic solders.
In order to understand the wetting and spreading behaviour
of newly developed candidate solder alloys, it is necessary
to evaluate the surface tension and its temperature coefficient.
The lead-free solder alloys must be developed in a short period
due to the restriction especially in Europe, so that the surface
tension of various candidate alloys is usually estimated by
thermodynamic analysis. Generally, Butlers model [1] is used
in the thermodynamic analysis, and many researchers [212]
have shown that the surface tension of various liquid alloys
can be predicted using this model. However, analysis of the
temperature coefficient of surface tension (d/dT ) for liquid
alloys has not been satisfactory, because the surface tension
measurements show large scatter. Recently, the authors
[1316] showed that more reliable surface tension values can
be obtained by the constrained drop method. In this paper,
the surface tensions of liquid SnAg, InAg and InCu alloys,
measured using the constrained drop method, are given. In
addition, the applicability of Butlers model to the evaluation
of the surface tension and its temperature dependence of liquid
SnAg, InAg, InCu alloys is discussed.
In the present work, the surface tension was measured by
the constrained drop method. The experimental apparatus
is illustrated in figure 1. A carbon heating element furnace
(TMax = 1973 K) was used in this study. To make a large axi-
symmetric liquid drop, we applied a graphite crucible specially
designed at Osaka University.
The experimental procedure is as follows. A graphite
crucible was placed in the even temperature zone at the centre
of the furnace. It was possible to level the graphite crucible by
adjusting three poles supporting the furnace. The level of the
graphite crucible was confirmed with two CCD cameras from
two horizontal directions. Then, an alumina crucible with a
hole (1.4 mm) in the bottom, containing high purity metals
(Ag: >99.99 mass%, Sn: >99.999 mass%, Cu: >99.998
mass% and In: >99.9999 mass%) equivalent to a target
composition, was set about 15 mm above the graphite crucible.
The tip of the crucible has a flat surface less than 100 m
wide. At the edge of the crucible tip, the true local contact
angle remains constant, whereas the apparent contact angle
can vary between 90 and +45 . The optimum condition for
measurements is the case when the local contact angle and
the apparent contact angle are the same. For that the amount

0957-0233/05/020438+05$30.00 2005 IOP Publishing Ltd Printed in the UK 438

 Temperature dependence of surface tension of liquid alloys

considering that the experimental scatter in the traditional

sessile drop method and the levitation method is more than
3% for those metals, the accuracy of the present method is
remarkable.

3. Thermodynamic calculation

Butlers model [1] was applied to estimate the surface tension,

surface concentration and the relationships between them.
Butlers model for an AB binary alloy system is expressed
by equation (1).


RT 1 NBs 1  Ex,s  
= A + ln + GA T , NAs
AA 1 NBb AA
Ex,b  
GA T , NA b

s
RT NB 1  Ex,s 
= B + ln b
+ GB T , NBs )
AB NB AB
 
GEx,b
B T , NBb (1)
where R is the universal gas constant, T is the temperature, Nis
is the mole fraction of i in the surface, Nib is the mole fraction
 
Figure 1. Schematic diagram of the experimental apparatus. of i in the bulk, GEx,s T , Nis is the partial excess free energy
i  
of i in the surface as a function of T and Nis and GEx,b
i T , Nib
of the sample was prepared by a preliminary simulation to is the partial excess free energy of i in the bulk as a function
satisfy the optimum condition. Once the sample was placed in of T and Nib . The molar surface area of component i can be
2/3
the furnace, the furnace was sealed and evacuated to 1.33 Pa obtained by Ai = 1.091 (6.02 1023 )1/3 Vi [2, 3],
and filled with a purified Ar10% H2 gas mixture. This where Vi is the molar volume of the element i. The partial
procedure was repeated three times to eliminate residual excess free energy in the surface is obtained using equation (2)
oxygen in the furnace. Then, the Ar10% H2 gas mixture was assuming that the partial excess Gibbs energy in the bulk and
flowed for more than 12 h to exclude any possible residual the surface have the same concentration dependence.
 
oxygen in the furnace. Then, the furnace was heated to the GEx,s
i (T , Nis ) = GEx,b
i T , Nis . (2)
experimental temperature. The temperature was measured
The constant (= 0.83 [3, 4]) is the ratio between the
with a Pt30% Rh/Pt6% Rh thermocouple located directly
bonding energy difference between the surface and the bulk,
under the crucible. When the temperature was stabilized, the adopted from the value of pure metals. Solving equation (1)
sample alloy in the alumina crucible was dropped onto the by instituting the thermo-physical data and the excess free
graphite crucible using an alumina rod. During experiments, energy, one can calculate the surface tension and the surface
the furnace was maintained in a strong reduction atmosphere concentration as a function of the bulk concentration and the
by flowing 10% H2Ar gas mixture, which was purified using temperature.
columns of silica-gel, ascarite, cold-trap (dry icemethanol)
and Mg chips at 773 K to eliminate reported contaminants,
essentially H2O, CO, CO2 and O2, which may cause a decrease
4. Results and discussion
in the surface tension of the sample due to oxygen adsorption. In the calculation of the surface tension of liquid alloys, the
The shape of the liquid metal drop was investigated with a accurate surface tension of the component pure liquid metals
high-resolution CCD camera (1636 1236 pixels). A pixel is necessary. In figure 2, the surface tension of liquid In
corresponds to 8.824 m with the CCD camera. A HeNe is shown as a function of temperature with literature values
laser beam ( = 632.8 nm) along the investigating direction [1825]. The surface tension of liquid In can be expressed
was used to capture a much clearer image profile of the liquid as a linear function with respect to temperature. The present
drop. Then, the surface tension of the liquid metal was work shows a constant slope for a long range of temperature,
calculated with a computer program [17]. After experiments, so that it is considered that the oxygen contamination was
the reliability of the axi-symmetry of the liquid drop can be suppressed enough in the present experiments.
confirmed by investigating the displacement of the centre from
In (mN m)1 = 616 0.099 T (K) (3)
the mean value, yielding the distortion of the shape of the
liquid drop. The inclination of each sample is about 0.5 . In where T is the temperature in K. Similarly, the surface tension
addition, the apparent contact angles of the right and the left of liquid Ag, Cu and Sn has been measured and given by the
are almost the same. Accordingly, it can be concluded that the following equations [16]:
present method provides a very accurate axi-symmetric surface Ag (mN m)1 = 1207 0.228 T (K) (4)
profile of a large liquid drop. Using this experimental set-up,
Cu (mN m)1 = 1585 0.211 T (K) (5)
the surface tension of liquid Ag, Cu and In was determined
within the experimental scatter of less than 1%. Generally 1
Sn (mN m) = 580 0.065 T (K). (6)

439
J Lee et al

1000
Pure Ag
600 In-90at%Ag
5 Present Work 900 In-70at%Ag
In-50at%Ag

Surface Tension, /mNm-1

Surface Tension, /mNm-1

In-30at%Ag
1 In-10at%Ag
800
550 Pure In
Calc.
7 700 Linear Reg.
4a
4b 2
500 3
8 600
6
9

500
450

400
600 800 1000 1200 1400 400 600 800 1000 1200 1400 1600
Temperature/K Temperature, T/K

Figure 2. Surface tension of pure liquid In as a function of Figure 4. Temperature dependence of the surface tension of liquid
temperature in 10% H2Ar atmosphere. (1, Yastenko et al [18]; 2, InAg alloys.
Lazarev [19]; 3, Khokonov et al [20]; 4, Lang et al [21]; 5, White
[22]; 6, Konig et al [23]; 7, Melford et al [24]; 8, Keene [25]; 9, 1400
Keene [25].) Pure Ag
In-90at%Ag
In-70at%Ag
1000 1200
In-50at%Ag
Surface Tension, /mNm -1

Pure Ag In-30at%Ag
Sn-90at%Ag In-10at%Ag
900 Sn-70at%Ag Pure In
1000
Sn-50at%Ag Calc.
Surface Tension, /mNm-1

Sn-30at%Ag Linear Reg.

800 Sn-10at%Ag
Pure Sn 800
Calc.
700 Linear Reg.
600
600
400
500 600 800 1000 1200 1400 1600
Temperature, T/K

400 Figure 5. Temperature dependence of the surface tension of liquid

400 600 800 1000 1200 1400 1600 InCu alloys.
Temperature, T/K

Figure 3. Temperature dependence of the surface tension of liquid
SnAg alloys.
The surface tensions of liquid SnAg [16], InAg and
InCu alloys are shown in figures 35, respectively. The solid
lines represent linear regressions of the measurements at each
composition and the broken lines are the calculated values
using Butlers model. The surface tension measurements
show reasonable accordance with the calculated values. It
is known that usually the surface tension of liquid metals
and alloys decreases with increasing temperature, i.e., the
temperature dependence of the surface tension is negative.
However, some liquid alloys (Sn50, 70 at% Ag, In50% Cu)
show positive temperature dependences, which can be found
in the calculation results. One exception is that the calculated
results of the surface tension of In70% Cu show positive
temperature dependence, even though the experimental results
show a negative one. This should be considered in further
investigations. Nevertheless, the behaviour of the composition
dependence of the temperature dependence is acceptable.
Figure 6 shows (a) the surface tension and (b) the surface
concentration of Sn for liquid SnAg alloys at 1273 K. It is
found that the surface tension dropped dramatically when the
surface concentration of Sn rose sharply. This behaviour is
also shown for the liquid InAg and InCu alloys, namely, the
decrease in the surface tension is considered to be caused by
the enhanced level of the Sn or In in the surface, which has
much lower surface tension than Ag or Cu.
Bearing in mind that the calculation results show
reasonable accordance with the measurements, it is considered
very helpful to testify to the effect of surface tension difference
between component metals on the positive temperature
dependence of the surface tension. For simplicity, the surface
tension at two different temperatures (673 and 1273 K) of an
ideal AB binary system was simulated. In this calculation,
the melting temperature (Tm ) and the surface tension at Tm of
pure liquids A and B are assumed as 1000, 500 K and 1000,

440

900
Surface Tension, /mNm-1
800
700
600
500
0 0.2
(a) Concentration in the bulk, NSn
1
Concentration in the surface, NSnS
0.8
0.6
0.4
0.2
0
0 0.2
(b) Concentration in the bulk, NSn
Figure 6. Composition dependence of (a) the surface tension and
(b) the surface concentration of liquid SnAg alloys at 1273 K.
500 mN m1, respectively. In addition, the temperature
coefficient and the molar volume of pure liquid metals
were assumed as 0.1 mN m1 K1 and 105 m3 mol1,
respectively. The calculated results are shown in figure 7.
In the high concentration region of component A, the
enhancement of the surface concentration of B is remarkable
with decreasing temperature, yielding the positive temperature
coefficient. Firstly, from an ideal solution model, Egry [26]
has reported that positive temperature dependence could be
found by the surface segregation of one component element.
In our study, from a series of calculations with a regular
solution model, it was found that the temperature coefficient
increases as the surface concentration having lower surface
tension increases, which is regarded as increasing when the
surface tension difference and the positive interactions is
large [16]. As a result, it could be concluded that the
temperature coefficient becomes positive as the difference
of the surface tensions and the interactions between the
component metals increase. It is reported that thermodynamic
interactions of the liquid SnAg [27], InAg [28] and InCu
[29] systems are negative. Among them, InAg has the most
negative interactions, while SnAg and InCu show almost the
same values. Considering the factors described above, it can be
concluded that positive temperature coefficients in the SnAg
and InCu systems are mainly due to the enhanced level of
Sn and In in the surface, caused by the large difference in the
Temperature dependence of surface tension of liquid alloys
Exp.
Calc.
0.4 0.6 0.8 1
B B
(a) Concentration in the bulk, NB
Calc.
(b) B
Concentration in the bulk, NB
0.4 0.6 0.8 1 Figure 7. Composition dependence of (a) the surface tension and (b)
B the surface concentration of ideal liquid AB alloys at 673, 1273 K.
surface tensions between the component metals. In contrast, in
the InAg system, there is no positive temperature dependence
due to the very negative thermodynamic interactions.
5. Conclusions
In this paper, surface tension of liquid SnAg, InAg, and
InCu alloys was measured by the constrained drop method
and compared with the results calculated by Butlers model.
The experimental results and the calculation analysis show
reasonable agreement. Although the surface tension of liquid
metals and alloys is usually known to decrease with increasing
temperature, some liquid alloys show positive temperature
dependence. It is considered that the positive temperature
coefficient is mainly due to the enhanced level of component
metal in the surface having lower surface tension, caused by the
large difference in the surface tensions between the component
metals.
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