Materials Transactions, Vol. 45, No. 3 (2004) pp.

625 to 629
Special Issue on Lead-Free Soldering in Electronics
#2004 The Japan Institute of Metals

Effect of Oxygen on Surface Tension of Liquid Ag-Sn Alloys

Joonho Lee1 , Toshihiro Tanaka1 , Masaya Yamamoto2 and Shigeta Hara1
1
Department of Materials Science and Processing, Osaka University, Suita 565-0871, Japan
2
Formerly Graduate Student, Department of Materials Science and Processing, Osaka University, Suita 565-0871, Japan

The effect of oxygen on the surface tension of liquid Ag-Sn alloys used as one of the main components in lead-free soldering alloys was
measured by the sessile drop method. The surface tension of liquid Ag-Sn alloys decreased with increasing tin content. The effect of oxygen was
investigated for oxygen partial pressure ranging from about 10
17 to 10
12 atm. The effect of oxygen on the surface tension of liquid Ag-Sn
alloys is closer to pure tin rather than pure silver. Thermodynamic simulation using Butler’s equation showed that the surface of liquid Ag-Sn
alloys is enriched with tin. Accordingly, the effect of oxygen adsorption on the surface tension of liquid Ag-Sn alloys was considered to be closer
to that of tin than silver.

(Received September 22, 2003; Accepted December 2, 2003)

Keywords: surface tension; liquid silver-tin alloys; sessile drop method; lead-free soldering

1. Introduction In the present work, the surface tension of liquid Ag-Sn

Since the surface tension of liquid solder alloy determines
its wetting behavior, many researchers have investigated the
surface tension of the lead-free soldering alloys (e.g. Ag-Sn
after Moser et al.1)). Although oxygen in atmosphere is
known to decrease the surface tension of liquid metals and
alloys,2–10) studies on the effect of oxygen for lead-free
solders have been only restricted to pure metals.8–10)
Generally, Gibbs adsorption isotherm (1) may express the
oxygen adsorption (
O ) on liquid metals and alloys.11)
1 d
2 d


O ¼
¼

RT d ln aO RT d ln pO2
where R: universal gas constant, T: temperature,
: surface
tensions of liquid metal or alloy, aO : oxygen activity in the
metal or alloy and pO2 : oxygen partial pressure, respectively.
Hence, the information of the surface tension dependence on
the oxygen partial pressure reflects the oxygen adsorption
behavior in the surface of liquid metals and alloys. For
example, if the surface of liquid metals and alloys is saturated
with oxygen, d
=d ln pO2 have a constant slope, yielding the
surface excess concentration of oxygen (oxygen adsorption)
at saturation. The oxygen adsorption for pure metals has been
investigated by many researchers. Table 1 summarizes some
of the reported oxygen adsorption at saturation for pure
metals after Bernard and Lupis.9) However, there is no
research on the oxygen adsorption for lead-free solder alloys
as far as the authors concern.
alloys, one of the main components in lead-free solders, was
measured by the sessile drop method with varying oxygen
partial pressure in atmosphere. In order to investigate the
surface tension in the whole composition range, the exper-
imental temperature was determined as 1253 K. Then, the
oxygen adsorption behavior on the surface of liquid Ag-Sn
alloys was interpreted by the surface concentration calculated
using thermodynamic database.
2. Experimental
ð1Þ The experimental apparatus used for the measurements of
the surface tension of liquid Ag-Sn alloys consisted of an
image capturing system with a He-Ne laser and a SiC heating
element furnace. Figure 1 shows a schematic diagram of the
experimental setup. A quartz reaction tube (5.5 cm O.D.,
5.0 cm I.D., 20.0 cm high) with investigation windows from a
horizontal direction was used. The tube was sealed by means
of O-rings fitted onto copper water-cooled jackets at the ends
of the tube. High purity samples (Ag: 99.99+% and Sn:
99.999+%) installed in an alumina crucible with a hole
Gas inlet
Alumina rod
Oxygen sensor
Cooling water inlet
Alumina crucible
siliconit

Table 1 Saturation parameters of oxygen at the surface of pure liquid

metals.9)

Maximum surface excess Area per adsorbed atom, He-Ne laser CCD camera
Temp.
2 2
System concentration, S/10 nm Sample alloy Alumina substrate
T/K

O.sat /10
6 molm
2 experiment calculation Copper jacket Thermocouple
Ag 1253 5 33 23 /38þ Connected to
Gas outlet
Cu 1423 9.3 17.8 18 /30þ a vacuum pump

Fe 1823 18:123:4 7:19:2 8þ Fig. 1 Schematic diagram of experimental apparatus for the sessile drop
 þ
(100) face and (111) face of the solid compound measurements of surface tension.
626 J. Lee, T. Tanaka, M. Yamamoto and S. Hara

fitted with an optical zoom lens and filters, where a pixel

Alumina tube corresponds to 18.7166 mm with the CCD camera. The
threshold shape of the drop was determined using image
Alumina cement
analysis software. Then, this drop profile was used to
Glass determine the surface tension by comparing the observed
Alumina particles shape with that of the solution to the Laplace equation using a
computer program developed by Krylov et al.13)
Reference electrode
(Metal/Metal oxide, p ref. )
O2

Solid electrolyte tube

3. Results and Discussion
(ZrO2 –8mol%Y2O3)
3.1 Surface tension of liquid Ag-Sn alloys
Platinum wire
Initially the method was applied to liquid Ag-Sn alloys in
Gas ( pO )
2 Ar-10%H2 atmosphere. In Fig. 3, the experimental results are
plotted as a function of concentration of tin in the bulk phase.
Fig. 2 Schematic diagram of zirconia oxygen sensor. For comparison, the surface tension of pure silver and tin
measured by Bernard and Lupis9) (1253 K), and Taimatsu and
Sangiorgi10) (1273 K) are also plotted. In addition, the
(1.4 mm) at the bottom side, was set about 15 mm above an experimental results for alloys were compared with the
alumina (sapphire) substrate. The alumina substrate was set calculated results based on Butler’s eq. (6) using thermody-
in the uniform-temperature area of the furnace, and accu- namic database.
rately leveled by adjusting three poles sustaining the furnace. !
S
The temperature was measured with a Pt/Pt-13%Rh thermo- RT 1
NAg

¼
Sn þ ln B
couple, which was set directly under the substrate. After the SSn 1
NAg
sample was placed in the furnace, the quartz tube was 1
 Ex,S 
evacuated with a mechanical pump producing a vacuum of þ GSn ðT; NAg S
Þ
G Ex,B
Sn ðT; N B
Ag Þ
1 Pa and filled with high-purity Ar-10%H2 gas mixture. This SSn
!
S
procedure was repeated for three times to eliminate residual RT NAg
oxygen in the reaction tube. Then, the furnace was ¼
Ag þ ln B
SAg NAg
programmed for the heating cycle up to 1253 K in 3 h. When

temperature in the furnace was stabilized, the sample alloys 1
þ G Ex,S S  Ex,B
Ag ðT; NAg Þ
GAg ðT; NAg Þ
B
ð6Þ
in the alumina crucible were dropped onto the alumina SAg
substrate using an alumina rod. During experiments, the
where R: universal gas constant, T: temperature,
Sn ,
Ag :
oxygen partial pressure was controlled with introducing a
surface tensions of pure liquid tin and silver, respectively,
suitable mixture of purified Ar-10%H2 and CO2 gases. In
SSn , SAg : molar surface areas of pure liquid tin and silver,
order to confirm the oxygen potential in the gas, zirconia S S S
oxygen sensor equipped with reference electrodes (Fe/FeO, NAg : mole fraction of silver in the surface (NSn ¼ 1
NAg ),
B B B
Ni/NiO and Cu/Cu2 O couples) was placed in the furnace. A NAg : mole fraction of silver in the bulk (NSn ¼ 1
NAg ).
schematic illustration of the oxygen sensor is shown in Fig. 2. Here, the ‘‘surface’’ is defined as outermost monolayer.
When the effect of the electronic conduction is negligible, G Ex,S
i ðT; NiS Þ: partial excess Gibbs energy of i in the surface
from the electromotive force (E) expressed by eq. (2) one can as a function of T and NiS , G Ex,B
i ðT; NiB Þ: partial excess Gibbs
obtain the oxygen potential in the atmosphere (pO2 ).
!
RT pO 2
E¼ ln ref. ð2Þ 900 Calculation
4F pO 2
Experiment
-1

where F: Faraday’s constant, pref. Bernarad et al.

O2 : the oxygen potential in the
Surface Tension, σ /mN m

800 Taimatsu et al.

reference electrode. Here, the oxygen potential in the
reference electrodes was determined using reported values
below.12) (pref. 
O2 ¼ expðG =RT)) 700

Fe þ 1/2O2 ¼ FeO G ¼
263:4 þ 64:81T ðkJÞ ð3Þ

Ni þ 1/2O2 ¼ NiO G ¼
233:6 þ 83:94 ðkJÞ ð4Þ 600
2Cu þ 1/2O2 ¼ Cu2 O G ¼
166:9 þ 71:13 ðkJÞ ð5Þ
Preliminary experiments showed that the equilibrium oxygen 500
potential was obtained in 60 min in the present experimental
condition. Surface tension measurements, therefore, were 0.0 0.2 0.4 0.6 0.8 1.0
conducted after 150 min to confirm the oxygen partial Concentration in the Bulk, N
B
Sn
pressure. In order to capture a clear drop shadow image, a
He-Ne laser ( ¼ 632:8 nm) was used. The drop shadow Fig. 3 Change in surface tension of liquid Ag-Sn alloys as a function of tin
profile was taken using a CCD camera (512  512 pixels) content at 1253 K.
 Effect of Oxygen on Surface Tension of Liquid Ag-Sn Alloys 627

Table 2 Thermo-physical data and partial excess Gibbs energies for the calculation of the surface tension of Sn-Ag alloys.14,17,18)

Sn ¼ 601
00886T

i /mN m
1

Ag ¼ 1207
0:2279T
VSn ¼ 17:0  10
6 f1 þ 0:87  10
4 ðT
504:99Þg
Vi /m3 mol
1
VAg ¼ 11:6  10
6 f1 þ 0:98  10
4 ðT
1233:65Þg
Ex
G / NAg NSn fð
3902:15
4:96927TÞ þ ð
16974:05 þ 7:424515TÞðNAg
NSn Þ
Jmol
1 þð
14299:05 þ 10:67712TÞðNAg
NSn Þ2 þ ð
5979:25 þ 6:497125TÞðNAg
NSn Þ3 g

energy of i in the bulk as a function of T and NiB . The molar Table 3 The maximum limit of oxygen partial pressure forming SnO2 .
surface area of component i can be obtained by eq. (7).15,16) Composition, at% aSn 28) pO2 /10
8 Pa
Si ¼ 1:091  ð6:02  1023 Þ1=3  Vi2=3 ð7Þ Ag 0 —
Ag-10%Sn 0.087 1.78
where Vi is molar volume of the element i. G Ex,B
i ðT; NiB Þ can
Ag-20%Sn 0.132 3.18
be obtained directly from thermodynamic database, and
G Ex,S
i ðT; NiS Þ is obtained using eq. (8) assuming that the Ag-30%Sn 0.183 2.29
partial excess Gibbs energy in the bulk and the surface have Ag-40%Sn 0.253 1.66
the same concentration dependence. Sn 1 0.419

G Ex,S
i ðT; NiS Þ ¼ 0:83  G Ex,B
i ðT; NiS Þ15Þ ð8Þ
the calculations.
Thermo-physical data and excess Gibbs energy used in the
present calculation are listed in Table 2.14,17,18) This method 3.2 Surface tension of liquid Ag-Sn-O alloys
has already been applied to various alloy and slag systems by 3.2.1 Thermodynamics of Ag-Sn-O system
the authors with succeed.15,16,19–27) As shown in Fig. 3, the In order to understand oxygen behavior on the surface of
agreement between calculations (solid line) and measure- Ag-Sn alloys, it is necessary to calculate the thermodynamic
ments (solid circles) in the present work is also reasonable. limits for experiments (no oxides formation). In liquid Ag-Sn
Accordingly, the surface tension of liquid Ag-Sn alloys at alloys, SnO2 is preferentially formed by the reaction (9).
different temperatures could be obtained by the above
Sn(l) þ O2 (g) ¼ SnO2 (s) ð9Þ
calculation method.
The thermodynamic calculations using eq. (6) also suggest where the equilibrium constant of eq. (9) is expressed as eq.
us information on the surface concentration of tin as shown in (10).
Fig. 4. Even though the actual surface concentration of tin 1
would not be exactly the same plotted in Fig. 4 due to the K¼ ¼ 2:415  1013 ðat 1253 KÞ28Þ ð10Þ
aSn  pO2
simple assumption of the surface by a monolayer, it may be
acceptable that tin preferentially adsorbs on the surface of Using the reported thermodynamic data for the activity of tin
liquid Ag-Sn alloys. In Fig. 4, the surface concentration at in the alloys,29) the maximum limit of oxygen partial pressure
493 K (the eutectic temperature of Sn-3.8%Ag solder alloy1)) to prohibit the formation of SnO2 is calculated. In Table 3,
is also plotted for comparison. The surface concentration of the calculated results of thermodynamic limits for experi-
tin dramatically increased with decreasing temperature from ments are shown.
3.2.2 Effect of oxygen on surface tension of liquid Ag-Sn
1.0 alloys
Figure 5 shows the measured surface tensions for pure
silver and tin and Ag-5, 10, 20, 30, 40%Sn alloys as a
S

493K
Concentraion in the Surface, NSn

0.8 1253K function of logarithm of the oxygen partial pressure. The

dependence of the surface tension for liquid Ag-Sn alloys on
0.6 the oxygen potential (the slope of d
=d ln pO2 in Fig. 5) was
found different from those for pure tin or silver. Nevertheless,
it is noteworthy that the oxygen potential dependence on the
0.4 surface tension of liquid Ag-Sn alloys was much closer to
pure tin even for the samples containing 10% tin.
As described previously, when d
=d ln pO2 has a constant
0.2
slope, we can determine the oxygen adsorption at saturation
in the surface. Table 4 shows the maximum surface excess
0.0 concentration of oxygen and the minimum area occupied by
0.0 0.2 0.4 0.6 0.8 1.0 single oxygen atom at saturation on the liquid metals and
B
Concentration in the Bulk, N alloys. Here, the minimum area (S) occupied by an oxygen
Sn
atom was calculated from eq. (11).
Fig. 4 Relationship between the concentrations of tin in the bulk and the
S ¼ 1=ðNA
O,sat. Þ ð11Þ
surface at 493 and 1253 K in liquid Ag-Sn alloys.
628 J. Lee, T. Tanaka, M. Yamamoto and S. Hara

tin and Ag-Sn alloys are much larger than that of pure silver.
As shown in Table 1, the minimum area occupied by single
900
oxygen atom at saturation on the surface of metal M is close
-1

to those for oxide compound Mn O at about the melting

Surface Tension, σ /mN m

800 temperature of the metals. Taimatsu et al.10) and Yuan et al.8)

Bernard et al. reported that the dependence of oxygen partial pressure on
700 the surface tension of pure tin increased with lowering
Ag
Ag-5% Sn
temperature. Hence, we may consider that on the surface of
600 Ag-10% Sn liquid Ag-Sn alloys segregated with tin, oxygen adsorption
Ag-20% Sn would decrease with increasing temperature. Probably, the
Ag-30% Sn reason for the increase in the minimum area occupied by
500 Ag-40% Sn single oxygen atom in the surface of pure tin and Ag-Sn
Sn alloys is that the experimental temperature of the present
Taimatsu et al.
400 work is much higher than the melting temperature of pure tin.
-15 -10 -5 0
In addition, we may expect that the oxygen adsorption on the
log pO / atm
2 surface of liquid Ag-Sn alloys at much lower temperature (for
example, eutectic temperature of Sn-3.8%Ag alloy, 493 K as
Fig. 5 Surface tension of liquid Ag-Sn alloys as a function of logarithm of
oxygen partial pressure at 1253 K.
shown in Fig. 4) would be close to that of pure tin rather than
pure silver, because the surface segregation of tin increases
with decreasing temperature as shown in Fig. 4. Conse-
Table 4 The maximum surface excess concentration of oxygen and the quently, the effect of the oxygen on the surface tension of Sn-
minimum area occupied by single oxygen atom at saturation on liquid Ag- Ag based soldering alloy, of which silver content is not so
Sn alloys.
much, is estimated to be almost the same as that for pure tin
Maximum surface excess reported by Yuan et al.8) near the liquidus temperature.
Area per adsorbed atom,
Composition, at% concentration,
O,sat /

7
2
S/10
2 nm2
10 molm 4. Conclusions
36.0
Ag 46.7
329) In the present work, the effect of oxygen on the surface
Ag-10%Sn 9.24 180 tension of liquid Ag-Sn alloys at 1253 K was investigated
using the sessile drop method. The followings are the major
Ag-20%Sn 8.49 196
conclusions of the present work.
Ag-30%Sn 7.01 237
(1) The surface tension of liquid Ag-Sn alloys decreased
Ag-40%Sn 6.37 261 with increasing the concentration of tin, and the
460 experimental results were reasonably accord with the
Sn 3.61
69010) calculated results using Butler’s equations.
(2) The dependence of the surface tension for liquid Ag-Sn
alloys on the oxygen potential was found different from
where NA and
O,sat denote Avogadro number and the those for pure tin or silver. The oxygen potential
maximum surface excess concentration of oxygen at satu- dependence for liquid Ag-Sn alloys was much closer to
ration, respectively. Even though the present results for pure pure tin even for the samples containing 10% tin.
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