Corrosion Science 44 (2002) 887898

www.elsevier.com/locate/corsci

Corrosion of tin alloys in sulfuric and nitric acids

Masato Mori a, Kazuma Miura b, Takeshi Sasaki a,*,
Toshiaki Ohtsuka a
a

Research Group of Interface Control Engineering, Graduate School of Engineering, Hokkaido University,
Sapporo 060 8628, Japan
b
Production Engineering Research Laboratory, Hitachi Co. Ltd., Totsuka-ku, Yokohama 244-0817, Japan
Received 12 April 2001; accepted 10 May 2001

Abstract
To obtain a fundamental understanding of the corrosion behavior of lead-free solder, the
corrosion behavior of tin-based eutectic alloys in sulfuric and nitric acids saturated with
oxygen was investigated. The presence of bismuth in a SnBi alloy (43Sn57Bi (wt.%)) slightly
accelerated the preferential dissolution of tin instead of dissolving itself in 0.05 M H2 SO4 and
greatly accelerated, in 0.1 M HNO3 compared with that of pure tin. In both acids, dissolution
of both tin and zinc from a SnZn alloy (91Sn9Zn (wt.%)) occurred depending on the ratio of
composition, and dissolution of tin from a SnAg alloy (96.5Sn3.5Ag (wt.%)) was accelerated. Dipping tests in H2 SO4 and HNO3 of pH 4 showed that dissolution of only zinc and lead
occurred, suggesting that the tin-based alloys investigated in this study are preferable to
substitutes for lead solders in terms of corrosion resistance. 2002 Elsevier Science Ltd. All
rights reserved.
Keywords: Lead-free solder; Corrosion in aqueous solution; Tin-based alloy

1. Introduction
In order to prevent pollution of the environment with lead, the use of lead will be
limited in many parts of the world in the near future. In the electronics industry,
eorts are now being made to develop a usable lead-free solder, and several tin-based
alloys have already been proposed. The goal in the development of lead-free solder is

Corresponding author. Tel.: +81-11-706-6352; fax: +81-11-706-7813.

E-mail address: txsasaki@eng.hokudai.ac.jp (T. Sasaki).

0010-938X/02/$ - see front matter 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 0 - 9 3 8 X ( 0 1 ) 0 0 0 9 4 - 4

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to produce alloys with nearly the same properties as those of lead solder, and most
research up to now has focused on melting points and physical strengths of alloys [1].
The physical strength is related to metallography, which depends on thermal history
and time. However, there has been little consideration of the corrosion properties of
base alloys for lead-free solder.
The metals proposed for lead-free solder are tin alloys including three or more
metals, and the proposed base alloys are eutectic tin alloys with elements such as
bismuth, silver, and zinc. In this study, the corrosion behavior of base eutectic tin
alloys and their component pure metals in H2 SO4 and HNO3 saturated with oxygen
was studied. Although the alloys tested were dierent from those used to lead-free
solders in the real world, and although the corrosion environments were dierent
from real environments in which solders are used, but a fundamental understanding
of corrosion behavior of the lead-free solder alloys was obtained.
2. Experimental method
The specimens investigated were eutectic tin alloys consisting of bismuth, zinc and
silver with weight percentages of 43Sn57Bi, 91Sn9Zn, and 96.5Sn3.5Ag, and the
component metals, tin, bismuth, zinc, and silver. For comparison, the eutectic 62Sn
38Pb (wt.%) alloy and pure lead were also employed. The eutectic alloy specimens
were prepared by molding granular metals mixed with prescribed amounts of the
component metals followed by rapid cooling and solidifying with the use of a chill
plate of graphite. The purity of the granular metals, obtained from High Purity
Chemicals Co. Ltd., was 99.999%. The alloy plates cut to 10  20  12 mm3 in
size were polished with SiC paper of #600, rinsed with distilled water, degreased with
isopropyl alcohol, and nally rinsed again with distilled water. An ultrasonic cleaner
was used at each step. After quick drying, each specimen was placed in a test cell.
The apparatus used for the dissolution test is illustrated in Fig. 1. It is composed
of a temperature-controlled bath, in which six small test cells were placed. The
specimens were set in each test cell using a setting tool made of a glass rod as shown
in the gure. The volume of each test solution was usually 15 ml, but in cases in
which rapid corrosion occurred, such as in the case of 0.1 M HNO3 , a volume of 40
ml for each test solution was used. The tests were carried out under oxygen bubbling,
but a glass cover was placed around each nozzle for oxygen so that the specimen
would not be directly hit by bubbles.
After immersion for the subscribed period, each specimen was taken out from the
cell, and the amount of dissolution of each component metal of the alloy was determined by analysis using an atomic adsorption spectrometer (Z-6100, Hitachi Co.
Ltd.). To avoid precipitation of the tin compound formed from tin dissolved into the
solution, analysis was carried out as soon as possible after the specimen had been
taken out of the cell. However, when a precipitate was found in the solution, sodium
phosphate was added to dissolve the precipitate before analysis.
The corrosion potentials of the alloys and the pure metals immersed in the test
solutions under oxygen bubbling were monitored by using a potentiometer (HA501,

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Fig. 1. Apparatus used for the dissolution test: (a) thermocouple hole, (b) heater hole, (c) thermostat, (d)
magnetic stirrer, (e) sample plate, (f) setting tool, and (g) test solution.

Hokuto Denko Co. Ltd.), and the potential was recorded by reference to an Ag
AgCl electrode. All of the experiments on dissolution and corrosion potential were
carried out at 30C.
SEM images of the specimens and cross sections of corroded surfaces were obtained using EPMA (JXA-8900M, JEOL Co. Ltd.) equipped with a SEM function.

3. Experimental results
3.1. Composition of alloys
The metallographic structures of the alloys prepared for this experiment can be
explained by reference to an equilibrium diagram [2]. SEM image of each alloy
is shown on the left side of each photograph of a cross section of the corroded
specimen in Fig. 2. The specimens are composed of the following phases: 43Sn57Bi,
an almost pure bismuth phase (bright area in the gure) and a tin-rich solid solution
phase with bismuth (maximum 21%Bi, dark area); 91Sn9Zn, an almost pure tin
phase as a matrix and a sub-micrometer-sized phase of almost pure zinc particles
scattered in the matrix; 96.5Sn3.5Ag, an almost pure tin phase as a matrix and submicrometer-sized particles of an intermetallic compound, Ag3 Sn, scattered in the
matrix; and 62Sn38Pb, a tin-rich solid solution phase (with maximum 2.8% Pb,
dark area) and a lead-rich solid solution phase (with maximum 18.3% Sn, bright
area).

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Fig. 2. Cross-sectional component images of specimens after corrosion tests for 5 h.

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891

3.2. Corrosion potential

Time variation of the corrosion potentials of specimens in 0.05 M H2 SO4 saturated with oxygen are shown in Fig. 3. The pure metals showed their intrinsic potentials from just after immersion in the solution: silver at around 230 mV, bismuth
at around 80 mV, tin at around 440 mV, lead at around 450 mV, and zinc at
around 1020 mV. On the other hand, all of the alloys except for SnZn alloy
showed around 440 mV immediately after immersion, almost the same as that of
pure tin. The potential of SnZn alloy increased from nearly the same potential as
that of pure zinc to 440 mV within several minutes after immersion.
Time variation in the corrosion potentials of specimens in 0.1 M HNO3 saturated
with oxygen are shown in Fig. 4. The potential of silver was nearly the same as that
in 0.05 M H2 SO4 , and that of bismuth shifted slightly toward the negative region.
The potentials of the other pure metals and alloys were 50150 mV more positive
than those in 0.05 M H2 SO4 . The sudden increase in the potential of the SnZn alloy
was almost the same as that in 0.05 M H2 SO4 .

Fig. 3. Time variations in corrosion potentials of tin-based alloys and their component metals in 0.05 M
H2 SO4 saturated with oxygen at 30C.

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Fig. 4. Time variations in corrosion potentials of tin-based alloys and their component metals in 0.1 M
HNO3 saturated with oxygen at 30C.

3.3. Dissolution of alloy components

Time variation in the amounts of dissolution of the components of alloys in 0.05
M H2 SO4 are shown in Fig. 5. Tin dissolved from the SnBi alloy in nearly the same
manner as that of pure tin. Dissolution of bismuth from the alloy was not observed,
but clear dissolution of pure bismuth was seen. Dissolution of both tin and zinc from
the SnZn alloy seemed to depend on their composition ratios. Dissolution of tin
from the SnAg alloy was accelerated, while no dissolution of silver was seen.
Dissolution of tin from the SnPb alloy was greatly suppressed, and lead dissolved
only slightly.
Time variation in the amounts of dissolution of the components of alloys in 0.1 M
HNO3 are presented in Fig. 6. Pure bismuth easily dissolved in HNO3 , but bismuth
in the alloy accelerated the dissolution of tin instead of dissolving itself. The dissolution behavior of SnZn and SnAg alloys appeared to be similar to that in 0.05 M
H2 SO4 . Lead also dissolved easily, and dissolution of the components of the SnPb
alloy seemed to depend on its composition ratio.
The amounts of dissolution during immersion for 120 h in H2 SO4 and HNO3 of
pH 4.0 are shown in Table 1. The pH of these solutions during the corrosion test

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893

Fig. 5. Time variations in the amounts of dissolution of alloy components in 0.05 M H2 SO4 (). For
comparison, those of the corresponding pure metals are also presented (
).

changed to around 4.4. Dissolution of only zinc and lead in both solutions was
observed.
3.4. Cross-sectional SEM component images of corroded alloys
After corrosion tests in 0.05 M H2 SO4 for 5 h, the cross-sections of alloy samples
were observed with SEM, and the cross-sectional component images are presented in

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Fig. 6. Time variations in the amounts of dissolution of alloy components in 0.05 M HNO3 (). For
comparison, those of the corresponding pure metals are also presented ( ).

Fig. 2. After the corrosion test, only the tin-rich phase of the SnBi alloy (dark area
in the photograph) had dissolved, most of the pure bismuth phase (bright area)
remained. In the case of the SnZn alloy, a porous tin-rich phase of several lm in
thickness, from which zinc had dissolved, was formed on the corroded surface. In the
case of the SnAg alloy, tin preferentially dissolved and the Ag3 Sn phase, which had

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Table 1
Amounts of dissolution of alloy components and pure tin in H2 SO4 and HNO3 of pH 4 in 120 h dipping
tests
Alloy and Sn
SnBi

Component
Sn
Bi
Sn
Zn
Sn
Ag
Sn
Pb
Sn

SnZn
SnAg
SnPb
Pure Sn

Amount of dissolution (mg cm 2 )

0.05 M H2 SO4 , for 120 h

0.1 M HNO3 , for 120 h

0.000
0.000
0.000
0.002
0.000
0.000
0.000
0.016
0.000

0.000
0.000
0.000
0.003
0.000
0.000
0.000
0.025
0.000

Fig. 7. SEM image of the surface of a SnAg alloy after a 5 h corrosion test.

aggregated on the surface, remained. A SEM image of the surface covered with
aggregated Ag3 Sn is shown in Fig. 7. In the case of the SnPb alloy, both the tin-rich
(dark area) and lead-rich (bright area) phases had dissolved and had been covered
with a PbSO4 layer of a few lm in thickness.

4. Discussion
4.1. Corrosion behavior in 0.05 M H2 SO4
Pure tin does not dissolve in practice in acids free from oxidizing agents on account of its large hydrogen overvoltage. However, tin easily dissolves, forming Sn2

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ions, in 0.05 M H2 SO4 saturated with oxygen, as was used in the present study [3].
The Sn2 ions are gradually oxidized by oxygen to form white precipitates, Sn(OH)4
or SnO2
nH2 O, like its formation from Sn(OH)2 by air oxidation [4].
Sn ! Sn2 2e

2Sn2 O2 6H2 O ! 2SnOH4 4H

Sulfuric acid attacks Bi and produces Bi3 as

Bi ! Bi3 3e

A SnBi alloy showed nearly the same corrosion potential as that of pure tin, as
shown in Fig. 3, and only tin dissolved. This means that the Bi-rich phase, which is
composed of almost pure bismuth, was protected by the tin-rich phase and remained
on the surface as shown in Fig. 6. Taking into account the mass% of tin in the alloy,
it is reasonable to consider the dissolution of the tin from the alloy was accelerated
compared with that of pure tin due to galvanic action of bismuth.
Zinc dissolves forming Zn2 ions,
Zn ! Zn2 2e

and the potential of the SnZn alloy in sulfuric acid was nearly the same value as
that of pure zinc at the initial stage of immersion, and it became nearly the same as
that of pure tin after immersion for about 5 min. This suggests that zinc preferentially dissolved and this reaction determined the potential in the initial stage, but zinc
was exhausted shortly in the surface phase, and the potential was determined by the
remaining tin in the next stage as shown in Fig. 3. In Fig. 2, the porous remaining tin
phase on a corroded surface can be seen.
Silver hardly corroded in this solution, and the concentration of silver ions was
too low to be detected. Ag3 Sn was also stable in the solution, and after the tin-rich
phase dissolved, Ag3 Sn agglomerated on the surface as shown in Fig. 7.
Lead corroded, leading to the formation of PbSO4 on the surface,
Pb SO24 ! PbSO4 2e

Lead ions appeared in the solution depending on the solubility of PbSO4 . The dissolution of tin was suppressed by the PbSO4 layer on the surface, and the dissolution
rate of tin from the alloy was relatively low compared with that of pure tin as shown
in Fig. 5.
4.2. Corrosion behavior in 0.1 M HNO3
The color of the test solution for tin and tin alloys gradually turned yellow or
brown.
This can be explained by occurrence of NO2 as follows [5]:
NO3 3H 2e ! HNO2 H2 O

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897

3HNO2 ! NO3 2NO H H2 O

2NO O2 ! 2NO2 :

and
Scherloch and Britton [6] reported that the reduction of nitrate ions accelerated the
dissolution of tin in oxygen free acids, but there was little acceleration eect in the
present experiments, carried out in the presence of oxygen, because the main reduction reaction was probably oxygen reduction.
Bismuth more easily corroded in HNO3 than in H2 SO4 (Figs. 5 and 6), and the
corrosion potential shifted to a more-negative region (Fig. 4). This suggests that
anodic reaction in HNO3 is more active than that in H2 SO4 , coinciding with a report
that the rate constant for the system Bi3
Bi is higher in HNO3 than in H2 SO4
[7,8].
The corrosion rates of lead and SnPb alloy were very large compared with those
in sulfuric acid. This is due to the absence of a barrier layer such as PbSO4 in H2 SO4 .
4.3. Corrosion behavior in H2 SO4 and HNO3 of pH 4
Tin and bismuth were in the passive states in this pH range, and silver was in the
condition of immunity. On the other hand, lead and zinc corroded [911], and only
the dissolution of zinc and lead was observed. It is reasonable to assume that these
results are nearly the same as those in acid rain (of which pH is thought to be about 5).
Since it is thought that zinc does not cause hazardous environmental pollution,
the tin-based alloys investigated in this study are preferable to lead solder.

5. Conclusions
Corrosion behavior of tin-based eutectic alloys, 43Sn57Bi, 91Sn9Zn, and
96.5Sn3.5Ag (wt.%), was investigated in 0.05 M H2 SO4 , 0.1 M HNO3 , and H2 SO4
and HNO3 of pH 4 saturated with oxygen. The following results were obtained.
1. Bismuth did not dissolve from the SnBi alloy in 0.05 M H2 SO4 , whereas pure bismuth dissolved, and the dissolution of tin was slightly accelerated. Pure bismuth
easily dissolved in HNO3 , but bismuth in the alloy greatly accelerated the dissolution of tin instead of dissolving itself.
2. In the initial stage, the dissolution of zinc from the SnZn alloy preferably proceeded, and a porous tin layer remained. In the next stage, both tin and zinc corroded depending on their composition ratios.
3. Dissolution of silver was not observed, and the dissolution of tin from the SnAg
alloy was accelerated by the presence of silver.
4. Dipping tests conducted in H2 SO4 and HNO3 of pH 4 showed that only zinc and
lead had dissolved, suggesting that the tin-based alloys investigated in this study
are preferable to the substitutes for lead solders in terms of corrosion resistance.

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