Trans Indian Inst Met

DOI 10.1007/s12666-015-0517-9

TECHNICAL PAPER

TP 2914

Development and Characterization of SnZnBi Lead Free Solder

S. N. Alam M. K. Mishra M. Padhy
A. N. S. S. Swain Prerna Mishra
Ayan Saha

Received: 8 October 2013 / Accepted: 22 January 2015

The Indian Institute of Metals - IIM 2015

Abstract SnZn based lead free solder is a promising

candidate to replace the SnPb eutectic solder due to its
low cost and melting temperature (198 C) near to the Sn
Pb eutectic solder (183 C). So far eutectic or near eutectic
SnPb alloys have been used as solder material but due to
harmful effect on environment and human health Pb has to
be eliminated from solder and prevent our environment
from being polluted. Here the near eutectic composition of
Sn-8 wt% Zn has been chosen. Apart from Sn-8 wt% Zn
four different alloys containing different wt% of Bi were
considered. They are Sn-8Zn-3Bi, Sn-8Zn-6Bi, Sn-8Zn8Bi and Sn-8Zn-10Bi. The results of the differential
scanning colorimetry (DSC) analysis show that addition of
Bi to the near eutectic composition of Sn-8 wt% Zn lowers
the melting temperature. The microstructure of the alloys
were investigated using a scanning electron microscope
and energy dispersive x-ray spectroscopy analysis. Tensile
test shows that both tensile strength and elongation of the
alloys reduce on addition of high wt% Bi to the Sn8Zn
solder alloy.
Keywords Lead free solder
SnZnBi
Eutectic

Differential scanning colorimetry

S. N. Alam (&)
M. K. Mishra
M. Padhy

A. N. S. S. Swain
P. Mishra
Department of Metallurgical and Materials Engineering,
National Institute of Technology Rourkela, Rourkela Pin769008, Orissa, India
e-mail: nasimulalam@yahoo.com
A. Saha
Center for Nanotechnology, Central University of Jharkhand,
Ranchi 835205, Jharkhand, India

1 Introduction
Pb and its compounds have been found to have the greatest
threat to human life. When Pb comes in contact with the
human body for a long period of time it bonds with the
protein in the body and hampers their normal functioning.
When the level of Pb in the blood cells in the human body
exceeds the normal concentration, Pb poisoning occurs.
During soldering operations Pb does not vaporize and
hence is not a very big health problem however when Pb is
disposed as a waste it can enter human body and can be
dangerous to human health. During wave soldering Pb dust
and Pb vapor may form which can have hazardous effect
on human health. Disposal of Pb in the environment has
been considered to be very harmful to human beings and
proper care has to be taken in disposal of the Pb-containing
waste. Pb has to be slowly eliminated from solder and
prevent our environment from being polluted by these
hazardous materials [13].
Pb is available in plenty and has a very low cost. The
SnPb solder alloys have been studied extensively over
several years. In the electronic industry the solder that is
used primarily is the eutectic composition, Sn-37 wt% Pb
although slight variation could be found in composition.
The presence of Pb in the SnPb solder has been found to
have several advantages. Pb acts as a solvent, allowing Sn
and Cu to form intermetallics by the diffusion process. Cu
is present in the substrate or the electrical component that
is soldered. Pb when present as a constituent in the SnPb
solder prevents the transformation of white Sn to gray Sn
during cooling. This transformation could lead to an increase in the volume and thus affect the structural integrity
of Sn. Pb also reduces the surface tension of pure Sn, which
as a result helps in wetting. These factors make Pb the most
suitable alloying element for solder alloys. However due to

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the harmful effects of Pb on human health the use of Pb is

being slowly eliminated in solder and alternative alloys are
being found [46].
The lead free solder alloys are predominantly Sn based
alloys. The SnZn based solder alloy has been found to
be a promising candidate and one of the best alternatives
to replace the existing SnPb eutectic solder both because
of its low cost and melting temperature which is near to
SnPb eutectic solder. The low melting temperature of the
SnZn eutectic (198 C) is very close to the SnPb eutectic alloy (183 C). Sn is non-toxic and has good corrosion resistance and solderability. This is why using an
alloy of Sn with some other low melting point element
could lead to a desirable solder. SnZn solder has low
cost and good mechanical properties that are suitable for a
solder. SnZn alloys also have a lower cost compared to
SnAg and SnAgCu solders. Both Sn and Zn are cheap
and readily available. The eutectic composition of the Sn
Zn system is Sn-8.8 wt% Zn. The eutectic microstructure
consists of two phases, a body centered tetragonal Sn
matrix and a secondary hexagonal Zn phase. SnZn solders have been found to possess better mechanical properties compared to the SnPb solder. Apart from this Sn
Zn solder alloys are also not hazardous to human health.
However SnZn solder alloy has some limitations like
poor wettability and low oxidation and corrosion resistance. During soldering, Zn reacts to form ZnO which
floats on the surface and hampers the wettability of the
solder. It has been found that addition of Bi near SnZn
eutectic composition improves the wettability of the Sn
Zn system. Bi is a surface active element and its addition
could reduce the surface tension of the molten solder.
Addition of Bi can also reduce the eutectic temperature of
the SnZn system [710].
SnZnBi solder alloys are being widely used. Addition
of Bi with concentration level up to 4 wt% increases the
ultimate tensile strength of the solder but beyond 4wt% Bi
the ultimate tensile strength value slowly decreases. The
elongation of the alloy decreases with increase in Bi addition beyond 4wt%. A small addition of Bi can also
improve the shear strength of the interface of SnZnBi
solder and the Cu substrate. However addition of more
than 4 wt. % Bi decreases the shear strength. The addition
of Bi improves the wettability of the solder by decreasing
the melting temperature of the eutectic alloy. The demerit
of SnZnBi solder is its high oxidation and low reliability. The oxidation is due to the presence of high
percentage of Zn in these alloys which has a very high
tendency to get oxidized. Oxide formation reduces the
wettability of the solder on Cu substrate during soldering
in air. Its major advantage is its very low melting point
and low cost [11, 12].

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2 Experimental
The SnZn and SnZnBi alloys were prepared from
granulated Sn, Bi and Zn powder having purity of 99 %.
The different alloys compositions that were selected are
Sn-8Zn, Sn-8Zn-3Bi, Sn-8Zn-6Bi, Sn-8Zn-8Bi and Sn8Zn-10Bi. Bi powder was procured from Loba Chemie, Sn
granules were procured from Merck and Zn powder was
procured from Rankem. The elements were mixed in the
right proportions and melted in a silica crucible in a frontloading box type muffle furnace and subsequently cooled
in the furnace to produce the solders. The molten alloys
were constantly stirred in order to obtain a homogeneous
composition. The furnace is heated to the desired temperature by electrical resistance heating elements. The
casting temperature is in the range of 400600 C. The
molten alloy was held at this temperature for 2 h. The
morphology and elemental composition of the samples
were analyzed using a JEOL JSM-6480LV scanning electron microscope (SEM) equipped with an INCA PentaFETx3 X-ray microanalysis system with a high-angle ultra-thin
window detector and a 30 mm2Si(Li) crystal for EDX
(energy dispersive x-ray spectroscopy) analysis. The microstructure and various phases formed were analyzed.
Differential scanning colorimetry (DSC) was done in a
Netzsch STA 409C Simultaneous Thermal Analyzer at a
heating rate of 10 C/min in argon atmosphere in order to
determine the melting point of the alloys. X-ray diffraction
(XRD) of the alloys were done in a Panalytical PW 3040
) to
XPert MPD using Cu Ka radiation (k = 1.54056 A
find out if any new phase was formed during their development. The tensile tests of the alloys were performed in a
Instron-1195 in order to find out their mechanical properties. Bulk hardness of all the alloys was measured using a
digital Leco Vickers microhardness tester (LV 700) under a
load of 25 kgf. The electrical resistivity of the solder alloys
were measured by four-point probe method using a
Keithley nanovoltmeter with DC current source.

3 Results and Discussion

Figure 1 below shows the SnZn phase diagram. The eutectic composition is Sn-8.8 wt% Zn. The eutectic temperature is 198 C. This temperature is very close to the
eutectic temperature of SnPb system (183 C) [13].
Sn-8 wt% Zn near eutectic alloy was prepared by
heating Sn and Zn mixture at 500 C for 2 h. This temperature is above the melting point of both Zn (419.5 C)
and Sn (231.9 C). Zn was added to the molten Sn and
mixed thoroughly and held at 500 C for 2 h, after which
the sample was allowed to cool in the furnace. The

Trans Indian Inst Met

Fig. 1 SnZn phase diagram showing the eutectic composition

microstructure of the Sn-8 wt% Zn solder alloy cooled in

furnace is given in Fig. 2ac. The Sn-8Zn near eutectic
alloy exhibits large rod-like Zn-rich regions. The rod
shaped Zn-rich phases are dispersed in the Sn matrix. The
SEM image indicates a typical lamella eutectic microstructure. The EDX analysis in Fig. 2de shows that it
consists of a matrix Sn-phase and a Zn/Sn eutectic mixture.
Dark coloured Zn-rich phases are dispersed in the lighter
coloured Sn matrix.
The large needle or rod-like Zn-rich phase has a thickness of around of 34 lm.The primary Zn phase shows
coarse plate like feature as can be seen in the SEM images
in Fig. 2bc. The lighter coloured Sn matrix is almost
100 % Sn containing no Zn at all whereas the dark
coloured Zn-rich phase contains both Zn and Sn (48.24
wt% Zn and 51.76 wt% Sn). Figure 3 is the DSC curve of
the Sn-8Zn near eutectic solder alloy. The DSC result
shows an endothermic peak at 210.1 C which corresponds
to the melting point of the Sn-8 wt% Zn near eutectic
composition. The melting point of the eutectic Sn-8.8 wt%
Zn composition is 198 C as shown in the binary SnZn
phase diagram in Fig. 1. The difference between the above
two temperatures may be due to the oxide formed during
the development of the near eutectic alloy or any other
impurities in the alloy.
Figure 4ab shows how the Sn-8wt% Zn near eutectic
alloy behaves when it is used as a solder on Cu wires. The
SEM images show that the Sn-8Zn near eutectic alloy
shows good wettability on the Cu substrate.
It has been found that the addition of Bi to the Sn-8 wt%
Zn alloy lowers the eutectic temperature and increases the
pasty region. The pasty region is the region between the
liquidus and the solidus. The melting temperature of the
solder is an important physical property which influences
the behavior of the solder with the substrate. A good solder
alloy should have a low melting temperature and a narrow

pasty region. This is why it is very important to add an

optimum amount of Bi to the SnZn eutectic composition
[1416].
Sn-8Zn-3Bi alloy was developed by adding the desired
wt% of Zn and Bi to molten Sn. After Zn and Bi was added
to the molten Sn it was stirred and held at 450 C for 2 h
after which it was furnace cooled to room temperature. In
the case of the Sn-8Zn-3Bi solder, the microstructure
consists particularly of a Zn/Sn eutectic region with some
dark coloured phase containing Zn and a light coloured Snrich phase containing almost 100 %Sn.
As can be seen from the SEM images in Fig. 5ad the
fine dark coloured phases containing higher wt% of Zn are
dispersed in the lighter coloured Sn matrix. The EDX
analysis in Fig. 5e, f shows the composition of the dark
coloured phase containing Zn and the Sn rich matrix. The
matrix is 99.92 wt% Sn containing negligible amount of Zn
whereas the dark coloured phase contains 93.42 wt% Zn
and 6.58 wt% Sn. The dark coloured phase is rich in Zn
containing also some amount of Sn. It should be noted that
the mutual solubility of Sn and Zn at room temperature is
almost nil (Fig. 1).
Bi could not be traced in the microstructure of Sn-8Zn3Bi. This is due to the very low percentage (3 wt%) of Bi in
the composition. The maximum solubility of Bi in Sn is
around 21 wt% which takes place at the euctetic temperature of 139 C (refer Fig. 6a). The solubility of Bi in
Sn is less than 2 wt% at room temperature and addition of 3
wt% Bi in Sn-8Zn-3Bi composition possibly forms a solid
solution of Bi in Sn. As a result Bi is not visible in the
microstructure. The solubility of Bi in Zn is almost negligible (refer Fig. 6b). It has been reported to be less than 0.1
wt% [17].Therefore all the Bi must be in the Sn-rich region
as solid solution in Sn or remain undissolved. The Sn-Bi
phase diagram in Fig. 6a shows that when Bi is added to Sn
the solubility of Bi is reduced sharply from 21 wt% at the
eutectic temperature to only about 2 wt% at room temperature. In alloys with comppsition of Sn-8Zn-6Bi, Sn8Zn-8Bi and Sn-8Zn-10 Bi where the Bi in the solder alloy
was higher than 2 wt% which is the solid solubility limit of
Bi in Sn at room temperature, Bi could be seen in the Snrich region as bright white spots (Figs. 9ac). The supersaturation of Bi in Sn in alloys where the Bi content in the
alloy is very high it leads to the formation of Bi precipitates
[18, 19].
The projection of the liquidus surface of the ternary Sn
ZnBi system is given in Fig. 6c [19]. For the SnZnBi
system, no experimental data for the isothermal sections
are available and very limited information about the liquidus surface can be found in the literature. However the
calculated liquidus surface in the entire composition range
was presented by Pelton et al. [20], where the calculated
eutectic reaction occurs at about 137 C and the eutectic

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Fig. 2 ac SEM of Sn-8Zn (near eutectic) composition along with d, e EDX analysis

composition is 2.5 at% Zn and 54 at% Sn. The binary phase

diagram of the SnZn (Fig. 1), SnBi (Fig. 6a) and ZnBi
(Fig. 6b) are all simple eutectic systems without any binary
compounds forming between them. There are no intermetallic compounds in this system. The ZnBi system has
a monotectic and a eutectic reaction whereas the SnZn
and SnBi are simple eutectic systems [2123].
Bi addition was found to lower the melting point of the
Sn-8Zn solder alloy. The DSC analysis in Fig. 7 shows that
the peak indicating the melting of the composition Sn-8Zn3Bi is at 203.3 C.The DSC result of Sn-8 wt% Zn eutectic
composition in Fig. 3 showed an endothermic peak at
210.1 C which corresponds to the melting point of the
near eutectic composition Sn-8Zn. Thus there is a significant lowering of the melting point of the near eutectic
composition after adding 3 wt% of Bi. The alloy Sn-8Zn3Bi has been used to solder a Cu wire. SEM images in
Figs. 8ab show that the alloy Sn-8Zn-3Bi has good wettability. The Sn-8Zn-3Bi seems to flow well on the Cu

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substrate. The addition of Bi could improve the wettability

of the SnZn based solder on Cu substrate. Bi is known to
be a surface active element. Surface tension of SnBi eutectic alloy is lower than that of SnPb and SnZn eutectic
alloy in the same state. For this reason the addition of Bi
could reduce the surface tension of the liquid solder and
accelerate their spreading on the Cu substrate [10, 24].
Another composition that was developed and characterized was the Sn-8Zn-6Bi. In the SEM images of the
sample in Figs. 9ac we find that the polyhedral Bi rich
phase and the needle like Zn rich phase precipitates in the
matrix of the Sn-8Zn-6Bi solder alloy. White Bi rich particles could clearly be seen in the Sn rich matrix. Figure 9df is the EDX analysis of the sample. The Sn rich
matrix was found to contain as high as 5.02 wt% Bi. This
suggests that all the Bi is present in the Sn matrix and they
can be seen as white particles in certain areas of the Sn
matrix as the maximum solubility of Bi in Sn is only 2 wt%
and the alloy contains 6 wt% Bi. The light coloured Sn-rich

Trans Indian Inst Met

Fig. 3 DSC of Sn-8Zn (near eutectic) composition

Fig. 4 ab SEM of Sn-8Zn solder on Cu substrate

region contains up to 94.96 wt% Sn and a very low amount

of Zn (0.02 wt% Zn). These are the b-Sn rich regions
devoid of any Zn covering most of the microstructure of
the alloy. A comparatively large amount of Bi is found in
this region. The dark coloured regions contain both Zn
(11.42 wt%) and Sn (87.60 wt%). These regions containing
both Sn and Zn are devoid of Bi (0.98 wt%). The white
coloured small sized particles contain 4.96 wt% Bi.
Wettability between the solder and the substrate determines the reliability of the solder joints in the electronic
packaging and it is an important factor that must be considered. The SEM images in Fig. 10ab does not show very
good wettability between the solder and the Cu wire.
Although SnZnBi has been studied by several groups not

enough information about the wettability of this solder is

available in literature. In order to find out the wettability of
the alloys developed they have been used on a Cu substrate. The SEM images in Figs. 10ab show the solder
joint of the Sn-8Zn-6Bi alloy used on a Cu substrate in
order to find out how they perform. It is clear from the
SEM images in Figs. 10ab that the solder Sn-8Zn-6Bi has
very poor wettability. The SEM images clearly show that
the Sn-8Zn-6Bi solder alloy is not flowing on the Cu
substrate. This has resulted in spherical globules of the
solder on the Cu substrate. This is also indicated by the
large contact angle (h) which leads to poor wettability
(Fig. 10c). As the Bi content in the solder alloy increases it
can be seen from the SEM images in Figs. 8, 10, 15 and 17

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Fig. 5 ad SEM of Sn-8Zn-3Bi composition along with e, f EDX analysis

Fig. 6 Phase diagram of a SnBi and b ZnBi systems, c Calculated projection of liquidus surface of the SnZnBi ternary system [19]

that the contact angles become larger. This suggets that

addition of higher amount of Bi to the Sn-8Zn solder leads
to lower wettability on Cu substrate. Poor wettability is the
major problem of the SnZn solder alloy. The addition of
Bi could improve the wettability of the SnZn based alloys
but the Bi concentration of the SnZnBi alloys should be
controlled. Wettability of typical SnZnBi alloy is not
good enough when soldering is done in air. The major
problem is that of oxidation while soldering in air and it is
mostly used for soldering in N2 atmosphere. Zn is oxidized

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by the atmosphere, resulting in ZnO covering the surface of

the droplet.
With the addition of Bi the wettability of the SnZn
alloys can be improved but, there is a limit to the amount of
Bi that can be added as there can be an unfavorable effect
on the plasticity of the SnZnBi alloy by adding very high
amount of Bi as the solder could become very brittle. So Bi
concentration is usually required below 2 wt% to maintain
the alloys elongation. The SEM images in Fig. 10a, b
suggests that although the Sn-8Zn-6Bi solder is able to wet

Trans Indian Inst Met

Fig. 7 DSC of Sn-8Zn-3Bi composition

Fig. 8 ab SEM images of Sn-8Zn-3Bi alloy used as solder on Cu substrate

the Cu surface and stick to it, it does not have the ability to
spread easily on the Cu surface and as can be seen from
Figs. 15ab and 17ab the ability of the Sn-8Zn eutectic
solder to wet the Cu surface becomes poorer as higher
amount of Bi is added. The poor wettability of SnZnBi
alloys is also reported earlier. This is a major obstacle to
practical applications of the SnZnBi solder alloy
[2527].
The DSC analysis of Sn-8Zn-6Bi alloy is given in
Fig. 11. The melting point of the Sn-8Zn-6Bi alloy has
been found to be 201.24 C. There is a slight decrease in
the melting point with the increase in the wt% of Bi in the
alloy.

The SEM images of Sn-8Zn-8Bi alloy in Fig. 12ac

show a large number of white spots in the Sn rich matrix
region. These are Bi rich particles which have precipitated
in the Sn rich matrix and contains about 7.82 wt% Bi. The
amount of Bi in the light coloured Sn rich matrix is 5.81
wt%. It is known that the solubility of Bi in Zn is less than
0.1 wt%. This can be seen in the ZnBi binary phase
diagram in Fig. 6b. This is the reason why Bi could not be
found in the dark coloured Zn containing region. The dark
coloured Zn containing regions contain 13.49 wt% Zn and
86.51 wt%Sn and no Bi at all.
The DSC analysis of Sn-8Zn-8Bi alloy is given in
Fig. 13. The melting point of the alloy Sn-8Zn-8Bi has

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Fig. 9 ac SEM images of Sn-8Zn-6Bi alloy, df EDX analysis of various regions in Sn8Zn6Bi alloy

Fig. 10 ab SEM images of Sn-8Zn-6Bi alloy used as solder on Cu wire, c Schematic diagram showing the contact angle(h) and wettability of a
liquid on a solid surface

been found to be 201.42 C. There is a slight increase in

the melting point with the increase in the wt% of Bi in the
alloy. Further addition of Bi to the near eutectic compsoiton of Sn-8Zn does not decrease the melting point of the
alloy. The variation of melting point of the near eutectic
coposition Sn-8Zn with addition of Bi is shown in the plot
below in Fig. 14. The graph shows a gradual decrease in

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the melting point of Sn-8Zn up to addition of 6 wt% Bi in

the alloy. Further increase in the wt% of Bi increases the
melting point of the alloy slightly.
Sn-8Zn-8Bi alloy was also used to solder Cu wire to find
out its wettability. The wettability of this alloy seems
poorer than the Sn-8Zn-6Bi alloy. The SnZnBi alloys are
definitely capable to replace SnPb solder due to its low

Trans Indian Inst Met

Fig. 11 DSC of Sn-8Zn-6Bi composition

Fig. 12 ac SEM image of Sn-8Zn-8Bi alloy, df EDX analysis of the various regions in the sample

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melting temperature and low cost but the wettability of this

alloy is not as good as the SnPb alloy when the wt% of Bi
is high. The compositions of the alloy containing higher Bi
wt% has poorer wettability and this is why the Bi content in
the alloy should be maintained below 2 wt% (Fig. 15).
The microstructure of Sn-8Zn-10Bi shown in Fig. 16ac
is similar to the Sn-8Zn-8Bi alloys but the white Bi rich
regions contained a higher wt% of Bi. The Bi wt% is found
to be 25.24 in the white coloured Bi rich particles. A large
number of segregations of massive Bi could be seen in the
microstructure. It should be noted that the content of Zn in
these white coloured particles is negligible (0.14 wt% Zn)
and the content of Sn is very high (69.46 wt% Sn). The EDX
analysis is shown in Fig. 16df. In the SEM image of Sn8Zn-10Bi alloy the light coloured phase is the Sn rich phase
(96.28 wt% Sn) having almost no Zn or Bi in it. The dark
needle or rod like platelet phase is the Zn-rich phase. The
dark areas contain higher wt% of Zn (9.89 wt% Zn) although
they contain significant amount of Sn (71.31 wt%). The
eutectic mixtures are found to be layer type. In the case of
Sn-8Zn-10Bi solder alloys we could see segregation of
massive Bi in the microstructure. The white coloured phase
is the rhombohedral Bi phase. The white spots have been
identified to be Bi rich (25.24 wt% Bi) and having significant
percentage of Sn (69.46 wt% Sn) in it. Due to very high Bi
wt% in the alloy white coloured particles containing very
high amount of Bi could be seen. EDX analysis shows that
there is also some amount of oxygen.

Fig. 13 DSC of Sn-8Zn-8Bi composition

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Fig. 14 Variation of melting point Sn-8Zn with addition of Bi. The

eutectic temperature of Sn-8.8 wt% Zn euetctic compsoition is 198 C

The Sn-8Zn-10Bi alloy was also used as a solder on Cu

wires. Figures 17ab show the SEM images of the use of
Sn-8Zn-10Bi alloy as a solder on Cu wires. There seem to a
less wettability of the alloy on the Cu surface. The wettability of the solder becomes poorer as the Bi wt% in the
solder alloy increases.
The x-ray diffraction plots of the various solder alloys in
Fig. 18 suggest that no new compound has formed. The
phase diagrams of SnZn in Fig. 1 and SnBi and ZnBi in
Figs. 6ab also suggest that no new intermetallic

Trans Indian Inst Met

Fig. 15 ab SEM images of Sn8Zn8Bi alloy used as solder on Cu wire

Fig. 16 ac SEM images of Sn-8Zn-10Bi alloy, df EDX of various regions in the SEM image

compound formation takes place between the three elements Sn, Zn and Bi.
The microstructure and composition at the interface
between the SnZn solder and the Cu substrate was

analyzed using SEM and EDX. The SEM image in Fig. 19a
shows the region near the contact of the Sn-8Zn solder with
the copper substrate. The EDX analysis in Fig. 19b, c of
the Sn-8Zn/Cu interface suggests the formation of CuSn

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Fig. 17 ab SEM images of Sn-8Zn-10Bi alloy used for soldering Cu wires

Fig. 18 XRD plots of the
various SnZnBi alloys

intermetallics. Intermetallics of the CuZn system like

Cu5Zn8 and CuSn system like Cu6Sn5 could form at the
interface between the Sn-8Zn solder and the Cu substrate.
The EDX analysis in Fig. 19c shows that there is complete
absence of Zn in the layer of the Sn-8Zn solder which is in
contact with the copper substrate and contains only
Sn(35.42 wt%) and Cu(46.25 wt%) suggesting the formation of intermetallic CuSn compounds in the contact region between the copper substrate and the solder. The EDX
analysis suggests the possibility of formation of intermetallic Cu6Sn5 at the interface. The intermetallic Cu6Sn5
layer that forms at the interface causes the fracture of the
solder joints and leads to the degradation of the joint
strength. Zn at the solder surface can also be oxidized by
the reaction with H2O and O2. Gibbs free energy for
oxidation of Zn is lower than that of SnO2 and Cu2O. This
could lead to the formation of ZnO thermodynamically. Zn

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very readily oxidizes to ZnO. ZnO is highly brittle and

could lead to the fracture of the solder joint. Soldering is
done in air and the temperature could reach up to 200 C
during soldering. There is a chance of formation of oxide
due the reaction of oxygen in air and the elements present
in the solder. This is one of the major problems of using Zn
in the solder alloy [25, 28, 29]. Figure 19d shows the SEM
image of the contact between the Sn-8Zn solder and the Cu
substrate. Three regions could be clearly identified as the
Cu-substrate, the intermetallic layer and the Sn-8Zn solder.
The relatively fast cooling of the solder in air during solidification of the molten solder alloy on the Cu-substrate
has led to the dendritic grain morphology of the solder.
Figures 20ab show the results of tensile test of the
eutectic SnZn, SnZn-3Bi and SnZn-6Bi samples. The
elongation of the sample decreases with increase in the Bi
content of the sample. The % elongation to failure in the

Trans Indian Inst Met

Fig. 19 a SEM of the contact between the SnZn solder and Cu substrate, bc EDX of the solder near the contact. d SEM images showing the
interface of the solder and Cu substrate

Fig. 20 Variation of a elongation, b ultimate tensile strength and c hardness with increase of Bi content in Sn-8Zn alloy

eutectic Sn-8Zn was found to be 73.46 and the tensile

strength was found to be 37.22 MPa. In the case of Sn-8Zn6Bi the % elongation to failure was found to be 13.37 and
the tensile strength was 24.55 MPa. For Sn-37Pb solder,
the reported stressstrain curve is that of a typical ductile
metal. The total elongation of Sn-37Pb solder is larger than
that of SnZnBi solder. The tensile strength of Sn-37Pb
solder is reported as 38 MPa and elongation of 48 %. The
SnZnBi solders are reported to have higher tensile
strength compared to the Sn-37Pb solder. Other lead free
solders like eutectic Sn-0.7Cu has tensile strength of
28 MPa and elongation of 44 %. Thus the mechanical
properties of the SnZnBi show that it can be a very good
candidate for lead free solder and has the potential to replace the Sn-37Pb solder [1719, 24, 30, 34].

Bi addition leads to decrease in the ultimate tensile

strength value. It can be concluded that addition of small
amount of Bi (\2 wt%) could lead to solid solution
strengthening of the Sn matrix. However when the Bi wt%
is increased in the alloy it leads to precipitation of Bi in the
Sn matrix. When Bi wt% is high in the solder alloy it
cannot completely go into solid solution in Sn as the solid
solubility limit of Bi in Sn is about 2 wt% at room temperature (298 K). This is why white globules of Bi rich
regions could be seen in compositions of solder alloy
containing 6 wt% or more Bi (Figs. 9c, 12c, 16c). The
amount of Bi segregation increases with the increase of Bi
content. It should be noted here that Bi is almost insoluble
in Zn. These Bi rich regions could not be seen in the Sn8Zn-3Bi composition (Fig. 5ad). In the Sn-8Zn-3Bi

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composition although the content of Bi (3 wt%) is slightly

more than the solid solubility limit of Bi in Sn the small
amount of Bi could not be detected in the SEM. With
increasing Bi content in the Sn-8Zn alloy, higher Zn and Bi
precipitations are extracted from the Sn matrix [25, 26].
Addition of Bi to the Sn-8Zn eutectic composition increases the hardness of the solder alloy (Fig. 20c). Addition
of up to 8 wt% of Bi gradually increases the hardness of the
solder alloy but higher addition of Bi leads to decrease in
the hardness value. Hardness of Sn-8Zn-8Bi solder alloy is
about 227.1 MPa. The increase in the hard Bi segregation

in the Sn-8Zn solder alloys is the main cause of the rise in

hardness. The Bi content in the alloy needs to be controlled
because of the brittle nature of the rhombohedral Bi phase
and the strong tendency for segregation. Rise in hardness
on addition of Bi has also been reported earlier [3133].
According to the equilibrium phase diagram of the SnBi system given in Fig. 6a, no intermediate phase is formed
and the maximum solubility of Bi in Sn is about 2 wt% at
room temperature. The maximum solid solubility of Bi in
Sn at the eutectic temperature of 139 C is found to be 21
wt% [17, 19]. On the other hand there is no solubility of Sn

Fig. 21 SEM images of the fracture surfaces of a, b Sn-8Zn, c, d Sn-8Zn-3Bi, e, f Sn-8Zn-6Bi alloys

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in Bi at room temperature, but it is about 1 wt% at the

eutectic temperature. As the solubility of Bi in Sn is about
2 wt% at room temperature so the addition of 3 wt% Bi in
Sn-8Zn-3Bi solder alloy leaves a small amount of Bi
undissolved in Sn. This small amount of Bi is neither seen
in the SEM image of the sample (Fig. 5ad) nor detectable
in the EDX analysis of the sample (Fig. 5e, f). It should be
noted that the solubility of Bi in Zn is almost negligible.
The microstructural analysis of the various alloys in the
SEM images given in Figs. 9, 12, 16 suggests that higher
Bi content in the solder alloy leads to the formation Bi rich
phases in the microstructure and this would lead to lower
strength values as seen from the plots in Fig. 20a, b. It has
been reported that 1 wt% Bi addition enhanced the solid
solution effect and raised the tensile strength of the as-cast
solder alloys but with increasing Bi content Bi does not go
into solid solution in Sn with non-uniform microstructure
of the Sn matrix. Therefore addition of low wt% of Bi
could give better tensile strength of solders and shear
strength of joint with Cu substrate but a large wt% of Bi in
the solder alloy would deteriorate of the tensile properties
of the solder alloys [10, 18, 2325].
Figure 21 shows the fracture morphologies of Sn-8Zn,
Sn-8Zn-3Bi and Sn-8Zn-6Bi alloys. The SEM images of
the fracture surface of Sn-8Zn near eutectic alloy in
Fig. 21a, b show sheared edge pattern and some small
dimples dispersed in the fracture surface. A ductile dimple
pattern can be seen clearly on the fracture surface. This
suggests that it is a ductile fracture. The alloys with lower
Bi content as in Sn-8Zn-3Bi show a ductile fracture with
dimples on the fracture surface as in Fig. 21c, d. The SEM
images of the fracture surface of the Sn-8Zn-6Bi alloy in
Fig. 21e, f show that partially brittle feature has taken
place. The addition of Bi changes the fracture behavior of
the alloys, from ductile to brittle. The alloys with higher Bi
content have brittle fracture. This suggests the lowering of
ductility of the alloy with addition of higher wt% of Bi [24,
30].
The reported values of electrical resistivity of eutectic
Sn-37Pb alloy is 14.5 lX cm and the electrical resistivity
of eutectic Sn-9Zn alloy is 10 -15 lX cm. This suggests
that it is possible to achieve a lower resistivity in the case
of eutectic Sn-9Zn alloy as compared to the eutectic Sn37Pb alloy. Figure 22 shows the variation of electrical
resistivity (q) with addition of Bi to the Sn-8Zn near eutectic composition. The gradual increase of electrical resistivity can be attributed to the increase in content of Bi in
the Sn-8Zn near eutectic solder alloy. Bi has a high electrical resistivity of 115 lX cm. The electrical resistivity of
Sn is 11.5lX cm and Zn is 6 lX cm [31, 34, 35].
Although adding Bi to the near eutectic Sn-8Zn solder
alloy increases its resistivity gradually as the Bi content in
the alloy is increased it also shows a drop in the resistivity

Fig. 22 Variation of electrical resistivity (q) with addition of Bi to

Sn-8Zn solder alloy

value when the concentration of Bi is more than 6 wt%. It

has been reported earlier by Peng and Liu [36] that the
electrical conductivity of solder alloy Sn-3Ag-0.5Cu-6In is
increased when Bi content is proper, for instance, the
electrical resistivity of the alloys can reduce about 10 and
20 %, when the Bi content is 3 and 8 %. Here also we have
seen a reduction in electrical resistivity of the Sn-8Zn near
eutectic alloy when the Bi content of the solder alloy is
above 6 wt%.

4 Conclusions
1.

2.

3.

4.
5.

6.

There is significant lowering of melting temperature

due to addition of Bi (up to 6 wt%) to the Sn-8Zn near
eutectic composition. Further addition of higher wt%
of Bi to the Sn-8Zn near eutectic composition leads to
slight increase in the melting point of the alloy.
SnZnBi alloys does not form any intermetallic
compounds between themselves. No new compound
formation was seen in the alloys.
Bi showed no solid solubility in Zn. Bi could be seen
in Sn rich matrix regions only when the wt% of Bi was
higher than 3 wt%.
Very high wt% of Bi in the alloy led to poor
wettability of the SnZnBi alloy on Cu substrate.
The ultimate tensile strength and percentage elongation of the Sn-8Zn alloy was found to reduce with
addition of high wt% of Bi in the Sn-8Zn near eutectic
alloy. There was a gradual increase in the hardness of
the Sn-8Zn alloy with increase in Bi content up to 8
wt% but addition of higher amount of Bi showed
reduction in hardness of the alloy.
It is possible to achieve a electrical resistivity lower
than the eutectic Sn-37Pb solder alloy in the case of
Sn-8Zn near eutectic solder alloy. The addition of Bi to

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the Sn-8Zn solder alloy leads to a gradual increase in

the electrical resistivity of the solder alloy. Adding
more than 6 wt% of Bi leads to a decrease in the
electrical resistivity of Sn-8Zn solder alloy.
Acknowledgments We would like to thank the staff in the thermal
analysis, SEM and XRD laboratories at the National Institute of
Technology-Rourkela, India. We would also like to thank everyone
involved at the National Institute of Technology- Rourkela for their
useful feedback and help.

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