Journal of ELECTRONIC MATERIALS, Vol. 46, No.

3, 2017
DOI: 10.1007/s11664-016-5225-7
© 2017 The Minerals, Metals Materials Society

Effects of Solidification Thermal Parameters on Microstructure

and Mechanical Properties of Sn-Bi Solder Alloys

BISMARCK LUIZ SILVA,1 VÍTOR COVRE EVANGELISTA DA SILVA,2

AMAURI GARCIA,3 and JOSÉ EDUARDO SPINELLI 2,4

1.—Department of Materials Engineering, Federal University of Rio Grande do Norte, UFRN,

Natal, RN 59078-970, Brazil. 2.—Department of Materials Engineering, Federal University of São
Carlos, UFSCar, São Carlos, SP 13565-905, Brazil. 3.—Department of Manufacturing and
Materials Engineering, University of Campinas, UNICAMP, Campinas, SP 13083-860, Brazil.
4.—e-mail: spinelli@ufscar.br

Samples extracted along the length of directionally solidified (DS) castings of

three Sn-xBi alloys (x = 34 wt.%Bi, 52 wt.%Bi and 58 wt.%Bi) were first
evaluated metallographically and then subjected to scanning electron micro-
scopy and energy-dispersive x-ray spectroscopy analyses. The characteristic
length scale of both eutectic and dendritic phases forming the microstructure
were determined and correlated with solidification thermal parameters
(growth rate V, and cooling rate T˙). Tensile and Vickers hardness tests were
performed to allow strength and ductility to be discussed as a function of both
microstructure features and alloy solute content. The tertiary dendrite arm
spacings along the length of the DS Sn-52 wt.%Bi alloy casting are shown to be
lower than those obtained for the Sn-34 wt.%Bi alloy casting. The results of
mechanical tests show that, with the decrease in the alloy Bi content, both
tensile strength and hardness are improved. This is shown to be mainly at-
tributed to the higher density of Bi precipitates decorating the Sn-rich den-
drites, which are finer than the equivalent phase developed for the Sn-52 wt.%
Bi alloy. However, the ductility is shown to be significantly improved for
specimens associated with regions of more refined microstructure of the Sn-
52 wt.%Bi alloy DS casting. A microstructure combining much branched
dendrites, fine Bi particles within the β-Sn dendritic matrix and an important
proportion of very fine eutectic formed by alternate Bi-rich and Sn-rich phase,
seems to be conducive to this higher ductility. In this case, the fracture surface
is shown to be more finely broken with presence of dimples for this particular
condition, i.e., characteristic of a ductile fracture mode.

Key words: Sn-Bi alloys, solidification, microstructure, Bi precipitates,

tensile strength, fracture surface

INTRODUCTION render this class of alloys particularly suitable for

applications in the electronics industry, where low-
Sn-Bi solder alloys have recently received special
temperature soldering is required. Under such cir-
attention, since they are seen as potential lead-free
cumstances, control of as-soldered Sn-Bi
solder alternatives to traditional Sn-Pb alloys due to
microstructures becomes necessary, especially if
the following inherent characteristics: low melting
reliable final properties are envisaged.
temperature, good wettability, relative low cost and
Appropriate microstructural arrangements of Sn-
excellent creep resistance.1–5 Such characteristics
Bi solder joints may improve the mechanical re-
sponse. It is well known that the mechanical char-
acteristics of the Sn-rich phase are affected by the
(Received July 15, 2016; accepted December 9, 2016;
published online January 10, 2017) combination of solid solution and further precipita-

1754
Effects of Solidification Thermal Parameters on Microstructure and Mechanical Properties of Sn-Bi
Solder Alloys
tion of Bi particles.5 This is one of the metallurgical
aspects to be stressed in as-soldered microstruc-
tures of Sn-Bi alloys. The complexity of the dendritic
network, the sizes of dendritic spacings, the mor-
phology and length scale of the eutectic mixture are
other features to be considered. It is worth noting
that the role of Bi precipitates on the final
mechanical properties, such as ductility and
strength of near-eutectic Sn-Bi alloys, remains
undetermined. The effect of characteristics of Bi
precipitates, for instance morphology and size, as a
function of both alloy solute content and solidifica-
tion thermal parameters deserve deeper investiga-
tions.
In spite of the aforementioned positive charac-
teristics, the poor ductility is still the major problem
restraining the essential processing and industrial
applications of Sn-Bi alloys. This seems to be asso-
ciated with the peculiar characteristics of the
microstructure of these alloys when compared with
those of other Sn-based alloys. Instead of a Sn-rich
matrix with intermetallic compounds or precipitates
distributed in it similar to most Sn-based solders, a
large number of brittle Bi particles throughout the
Sn-rich matrix characterizes the microstructure of
usual Sn-Bi solders. Sn-Bi eutectic or near-eutectic
alloys compositions with or without additions of
alloying elements are considered interesting possi-
bilities.6–9
A number of studies in the literature10–14 have
reported that the microstructure of the Bi-Sn
eutectic alloy is constituted by Bi-rich and Sn-rich
lamellar phases, as well as by Bi precipitates within
the Sn-rich phase. Chen et al.5 affirmed that the
lamellar structure in Sn-Bi alloys is the most
important factor influencing ductility. Two defor-
mation mechanisms are proposed associated with
the strain rate sensitivity of these alloys, that is, a
phase boundary-related mechanism changes to a
dislocation glide mechanism with the increase in
strain rate. The latter phenomenon leads to highly
deteriorated ductility. The phase boundary mecha-
nism is characterized by sliding between the two
phases. Thus, the interaction between Sn-rich and
Bi-rich phases within the eutectic mixture will
strongly affect the deformation behavior of Sn-Bi
alloys.5
Glazer et al.12,15–21 showed that Bi has significant
solid solubility (21.0 wt.%Bi) in Sn at the eutectic
temperature, thus allowing precipitation of Bi in the
Sn-rich phase (solid-state precipitation) at lower
temperatures. The eutectic microstructure that re-
sults from the melt after slow cooling conditions has
been reported as a quasi-regular microstructure,
whereas degenerate material at the boundaries of
the eutectic grains are reported for moderate cooling
rates.15 Faster cooling rates are associated with
even more complex eutectics, which are the so-
called complex-regular eutectics.22 Systematic
studies emphasizing the effects of cooling rate (T˙)
and alloy solute content on the morphology and
1755
evolution of the Sn-Bi eutectic cannot be found in
the literature. Gigliotti and Graham23 established a
zone of coupled growth in Sn-Bi alloys. Such a zone
was shown to be located at the Bi-rich side of the
eutectic, which indicates a typical coupled zone in a
faceted/non-faceted eutectic system. The
microstructures of such areas which nucleated in
the coupled zone were shown to vary with the Bi
content. At the Sn-rich end of the zone, the
microstructure was shown to be mainly irregular,
with some areas in which it was complex-regular.
For compositions higher in Bi, the eutectic was
complex-regular, characterized by trifoils of Bi, with
lamellar-like or fishbone branches.
Over recent years, more investigations have fo-
cused on near-eutectic Sn-Bi solder alloys. Accord-
ing to Lai and Ye,24 non-eutectic Sn-Bi alloys have
better mechanical properties when compared with
those of a eutectic alloy. Furthermore, these authors
reported that the eutectic phase has lower
mechanical strength when compared with that of
the primary -Sn phase. Indeed, mechanical property
parameters of the two phases, calculated by the
Abaqus software, resulted in lower strength for the
eutectic phase. Lai and Ye24 reported that the ulti-
mate tensile strength (UTS) of Sn-10Bi and Sn-20Bi
alloys were slightly above 80 MPa, being higher
than the UTS of a Sn-58Bi alloy. The elongations of
both Sn-10Bi and Sn-20Bi alloys were shown to be
about 50%, which is also higher than the corre-
sponding property of the Sn-58Bi alloy.
It is known that the cooling rate experienced
during liquid-to-solid transformation of a solder fil-
let directly affects the microstructure of Sn-based
solders, having a significant influence on the
resulting mechanical behavior.25–29 For example,
Xiaowu and collaborators14 directionally solidified a
Sn-58Bi eutectic alloy using a Bridgman-type
solidification furnace, and reported the evolution of
lamellar microstructures consisting of Sn and Bi
phases. After proposing inter-relationships between
interphase spacing (λ) and parameters of the pro-
cess, such as the pulling rate (V), experimental
equations relating Vickers hardness (HV) and the
interphase spacing were proposed. It was found that
the microhardness decreases with the increase in
the microstructural spacing. These types of experi-
mental correlations remain unknown when tran-
sient heat flow conditions during solidification of
Sn-Bi eutectic-rich solder alloys are considered.
Gusakova et al.30 compared the microstructural
morphologies associated with the solidification of a
Sn-58 wt.%Bi eutectic alloy under slow (2 K/s) and
fast (105 K/s) cooling conditions. A morphological
transition from lamellar to a microcrystalline pat-
tern was reported to occur with an increase in
cooling rate.
Since results on the microstructures of eutectic-
rich Sn-Bi solder alloys and their dependences on
solidification cooling rate and growth rate are scarce
in the literature, this investigation has focused on
1756
the effects of alloy Bi content (from 34 wt.% to 58 wt.
%) on microstructural features emphasizing den-
dritic and eutectic arrangements, which include
dendritic and eutectic spacings and morphological
characteristics of the Bi-rich phase. The
microstructural evolutions of Sn-Bi alloys solidified
under a transient heat flow regime will be investi-
gated, using a water-cooled directional solidification
system. A comprehensive characterization through
scanning electron microscopy (SEM) and optical
microscopy is envisaged with a view to permitting
experimental growth laws relating microstructural
spacings and solidification thermal parameters to be
derived. In addition, hardness and tensile proper-
ties of Sn-34 wt.%Bi, 52 wt.%Bi and 58 wt.%Bi al-
loys will be investigated with the intention of
establishing correlations between ductility/strength
values and typical length scales of the phases
forming the microstructure along the length of the
directionally solidified (DS) Sn-Bi alloys castings.
EXPERIMENTAL PROCEDURE
In order to promote vertical directional solidifi-
cation, an apparatus designed in such a way that
heat is directionally extracted by the bottom of the
casting (see Fig. 1) was used. The transient direc-
tional solidification experiment results in a range of
as-solidified Sn-Bi microstructures, obtained under
significantly different cooling rates in a single
casting.31–33 The solidification setup used in the
experiments allows heat to be extracted unidirec-
tionally through a water-cooled bottom made of low
carbon steel (SAE 1020), promoting vertical upward
directional solidification. A stainless steel split mold
was used having an internal diameter of 60 mm, a
height of 157 mm and a wall thickness of 5 mm. The
lateral inner mold surface was covered with a layer
of alumina-silica insulating paste to minimize radial
heat losses. The bottom part of the mold was closed
with a thin (3-mm-thick) carbon steel sheet. The
upward solidification experiments were carried out
with Sn-34 wt.%Bi, Sn-52 wt.%Bi and Sn-58 wt.%Bi
solder alloys, which are indicated in the Sn-Bi phase
diagram of Fig. 2. Continuous temperature mea-
surements in the casting were monitored during
solidification via the output of a bank of fine type J
thermocouples sheathed in 1.5-mm outside diame-
ter stainless steel tubes, and positioned at different
positions from the heat-extracting surface at the
bottom of the DS castings. All thermocouples were
connected by coaxial cables to a data logger inter-
faced with a computer and the temperature data
were acquired automatically.
Selected transverse (perpendicular to the growth
direction) and longitudinal samples of the DS alloys
castings were polished (solution of alumina 1 µm
and water) and etched with a solution of 2 mL HCl,
10 mL FeCl3 and 100 mL H2O applied during 5–15 s
to reveal the microstructures. An optical image
processing system, Olympus GX51 (Olympus, Ja-
Silva, da Silva, Garcia, and Spinelli
pan), was used to acquire the images. The primary,
tertiary (λ1, λ3) and secondary dendrite arm spac-
ings (λ2) were measured on transverse and longitu-
dinal sections of the DS castings, respectively. The
triangle method was employed to measure λ1,
whereas λ2 and λ3 were measured by the intercept
method, as reported by Gündüz and Çadirli34 (see
Fig. 3a and b). The eutectic spacings (λc = λcoarse and
λf = λfine) were measured on the transverse sections
by the intercept method, as shown in Fig. 3c. At
least 40 measurements were carried out for each
selected position along the length of the DS cast-
ings.
Furthermore, detailed microstructural charac-
terization was performed using a scanning electron
microscope (SEM–EDS) FEI (Inspect S50L). Cross-
section samples of the three Sn-Bi alloys were
examined by SEM and elemental mapping was
performed to determine the relative distribution of
the elements. The fracture surfaces of the tensile
samples were observed by a field emission gun–
SEM–EDS Philips (XL30 FEG) under secondary
electron mode.
Transverse specimens for tensile tests were ex-
tracted from different positions along the length of
the DS castings. These specimens were prepared
according to specifications of the ASTM Standard E
8 M/04 and tested at a strain rate of about
3 × 103 s−1. Microhardness tests were performed on
transverse sections of the samples of each alloy by
using a test load of 500 g and a dwell time of 15 s. A
Shimadzu HMV-G20 model hardness tester was
used. The adopted Vickers microhardness was the
average of at least 20 measurements on each sam-
ple, which were extracted from the following posi-
tions from the bottom of the casting: 5 mm, 10 mm,
15 mm, 20 mm, 25 mm, 30 mm, 40 mm, 50 mm,
60 mm, 70 mm, and 80 mm.
RESULTS AND DISCUSSION
Directional solidification experiments under
transient heat flow regime, using a water-cooled
solidification setup, were run in order to acquire the
evolutions of temperature versus time along the
length of the Sn-Bi castings, as shown in Fig. 4. The
experimental cooling curves refer to thermocouples
located at specific distances (P) from the cooled
bottom of the castings. Further, such experimental
cooling curves and the liquidus (TL) and eutectic
(TE) temperatures of the alloys of 172.2°C, 150.0°C,
and 136.5°C for the Sn-34 wt.%Bi, Sn-52 wt.%Bi
and Sn-58 wt.%Bi alloys, respectively, have been
used in order to determine the solidification thermal
parameters: growth rate (V), cooling rate (T˙) and
thermal gradient (G = T˙/V).
The cooling curves attained during transient
solidification allowed plots of position (P) versus
time (t), to be generated for all Sn-Bi chemistries
examined. The mentioned time (t) corresponds to
the instant that either the liquidus isotherms of the
Effects of Solidification Thermal Parameters on Microstructure and Mechanical Properties of Sn-Bi
Solder Alloys
Computer and
data acquision
soware
Thermocouples
connected in a
data logger
Fig. 1. Vertical upward directional solidification casting assembly and its devices.
Sn-34 wt.%Bi and Sn-52 wt.%Bi alloys, or the
eutectic front of the Sn-58 wt.%Bi alloy passed by
each thermocouple placed along the length of the DS
castings.
A numerical technique, based on the least squares
method, was used to fit mathematical power func-
tions of the form P(t) = atb (a; b are constants) to
these experimental plots. The derivative of these
functions with respect to time gave values for the
growth rate (V). Moreover, the data acquisition
system permitted accurate determination of the
slope of the experimental cooling curves. Hence, the
cooling rate was determined along the length of the
castings, by considering the thermal data recorded
immediately after the passage of either the liquidus
isotherm (hypoeutectic compositions) or the eutectic
front (eutectic alloy) by each thermocouple.
The experimental points and tendencies of P × t,
V × P, T˙ × P and G × P can be seen in Fig. 5. As the
experimental evolutions for the three Sn-Bi alloys
were inserted jointly in each graph, it is possible to
carry out a direct comparison between them. All
experimental scatters were fitted to power func-
tions, as indicated in Fig. 5. It can be observed that
the experimental V and T˙ values for the eutectic Sn-
58 wt.%Bi solder (dotted lines) are lower than those
found for the other Sn-Bi alloys. A single fit function
has been adopted for the experimental evolutions of
thermal gradient during progress of directional
solidification of the Sn-34 wt.%Bi, Sn-52 wt.%Bi and
Sn-58 wt.%Bi solder alloys.
1757
Mold
Temperature
controller of the
Direconal
Solidificaon furnace
Water flow
meter
The experimental evolution of cooling and growth
rates show that these thermal parameters decrease
with progress of solidification. Microstructural
parameters (dendritic and eutectic spacings) are
expected to be reversely affected by this decrease, as
it will be seen below.
Typical cooling rates during reflow procedures for
solders in industrial practice remain in the range
of 3.0–10.0 °C/s.35 Directional solidification (DS)
experiments as those performed in the present re-
search work allow the same order of magnitude of
cooling rates to be obtained. Final microstructure is
a direct consequence of this solidification thermal
parameter. Hence, DS results have a correspon-
dence with the standard procedures that are used in
industry.
Representative transverse microstructures of the
DS Sn-Bi alloys castings are shown in Fig. 6. Ar-
rows within the images highlight some of their
elements. The solidification cooling rates associated
with the microstructures shown in Fig. 6 are 1.0°C/
s and 0.3°C/s. Tertiary dendritic branches are
clearly seen for the hypoeutectic Sn-34 wt.%Bi and
52 wt.%Bi alloys (see Fig. 6a and b), while large Bi
particles and “fishbone” eutectic can be observed for
the eutectic Sn-58 wt.%Bi specimens, as shown in
Fig. 6c. The fishbone-like eutectic is observed in the
DS Sn-Bi specimens as an isolated structure from
the lamellar eutectic. Similar microstructural as-
pects have been reported by Gigliotti et al.23 who
demonstrated the presence of trifoils of Bi, with
1758 Silva, da Silva, Garcia, and Spinelli

lamellar-like or fishbone branches for alloys of

higher Bi content.
Because the typical non-faceted/faceted growth of
the Sn-Bi eutectic phase, the coupled zone in this
34wt%Bi binary system has been reported to exhibit a skewed
52wt%Bi
shape,23 tending toward the Bi-side of the equilib-
58wt%Bi rium phase diagram. It seems that the primary Bi
phase may nucleate at given undercooling levels or
at given growth velocities (see Fig. 6c), and grow
combined with the eutectic phase.
By comparing the microstructures associated
with the two cooling rate levels, as exhibited in
Fig. 6, it can be seen that the length scale of the
microstructure increases with the decrease in cool-
ing rate, regardless the alloy composition examined.
A complex dendritic array has been identified for
the Sn-34 wt.%Bi and 52 wt.%Bi alloys with the
presence not only of primary dendrite stalks but
also secondary and tertiary dendritic branches in all
cases examined. As expected, the proportion of
eutectic increases with increasing Bi content. The
Fig. 2. Sn-Bi phase diagram highlighting the Sn-Bi alloys examined
in the present investigation.
eutectic mixture is formed by rhombohedral Bi-rich
and body-centered tetragonal Sn-rich phases. No

Fig. 3. Schematic representation of (a, c) transverse and (b) longitudinal sections of methods used to measure dendritic and interphase
spacings: intercept method for λc, λf, λ2 and λ3 and triangle method for λ1. L is the length of the line and n is the number of intercepted branches.
Effects of Solidification Thermal Parameters on Microstructure and Mechanical Properties of Sn-Bi 1759
Solder Alloys

(a) 220 Bi and Sn phases can be seen characterized by light

200 Sn-34wt.%Bi Positions from metal/mold interface:
4mm 9mm 14mm
gray and dark gray regions, respectively. The
19mm 42mm microstructures become finer for higher cooling rates.
180
A large number of fine Bi particles have been formed
160 TL = 172.2°C during cooling, which can be noted particularly in the
Temperature (°C)

140 Sn-34 wt.%Bi alloy specimens through the inset SEM

images. It can be inferred that Bi atoms were firstly
120
dissolved in the Sn phase and secondly precipitated
100 during the cooling stage after solidification. The
80 microstructural spacings between these Bi precipi-
60
tates have been determined for the specimens asso-
ciated with cooling rates of 12°C/s, 1°C/s, and 0.3°C/s,
40 that is, 0.94 μm ± 0.32 μm, 1.45 μm ± 0.30 μm, and
20 2.01 μm ± 0.71 μm, respectively, for the Sn-34 wt.%Bi
0 100 200 300 400 500 600 700 800 alloy. Likewise, λ values of 1.91 μm ± 0.45 μm,
Time (s) 3.42 μm ± 0.40 μm and 2.46 μm ± 0.44 μm were
determined for the Sn-52 wt.%Bi alloy. It can be in-
220
(b) Sn-52wt%Bi Positions from metal/mold interface:
ferred that a higher density of Bi precipitates may
200 5mm 10mm 15mm characterize the Sn-rich dendritic areas in the
59mm 75mm
180 microstructure of the Sn-34 wt.%Bi alloy. Addition-
160 TL = 150°C
ally, the cooling rate affects the distribution of these
Bi particles, since the microstructural spacing in-
Temperature (°C)

140
creased with decrease in cooling rate. These particles
120 have either spherical or ellipsoidal morphologies, as
100 shown in the inset SEM images of Fig. 7.
The Sn-58 wt.%Bi alloy has been reported to have
80
a complex regular eutectic microstructure, in which
60 two types of regions can be observed: zones of a
40 regular repeating pattern and other zones of ran-
20
dom orientation.36 It is worth noting that the two
0 100 200 300 400 500 600 700 800 phases forming the eutectic mixture in the present
Time (s) study are arranged as alternated not-flat plates, as
can be seen in Fig. 7.
(c) 220
Figures 7 and 8 show that the Sn-Bi eutectic-rich
Sn-58wt.%Bi
alloys have two eutectic characteristic sizes: fine
200 Positions from metal/mold interface: (black squares in Fig. 7) and coarse. For Sn-Bi al-
4mm 9mm 14mm
180 19mm 42mm 55mm loys, the transition from lamellar (quasi-regular) to
160 a more complex-regular morphology depends
strongly on the solidification thermal parameters, i.
Temperature (°C)

TE = 136.5°C
140
e., more complex structures are associated with
120 higher cooling rates. It seems that fine eutectic
100 features can be established in certain sites, followed
80
by coarser structures in the surrounding areas, as a
consequence of local thermal instabilities.
60
Fishbone-like eutectic cells and trifoils of Bi can
40 be seen in Fig. 8. These structures have also been
20 reported by Mokhtari and Nishikawa.37 They
0 100 200 300 400 500 600 700 800 stressed that they are formed due to a shift toward
Time (s) the Bi-rich side of the coupled zone diagram, as
established for the Sn-Bi alloy system.23
Fig. 4. Temperature profiles registered during unsteady-state
directional solidification of (a) Sn-34 wt.%Bi, (b) Sn-52 wt.%Bi and (c) Furthermore, Bi particles within the -Sn den-
Sn-58 wt.%Bi solders. dritic matrix are indicated in Fig. 7 by yellow ar-
rows. The morphology of the Bi-rich phase (light
gray) in the eutectic regions remains mainly defined
by the paired growth of trailing and leading phases.
dendrites have been found from the bottom to the As a result, this phase assumes an elongated mor-
top of the DS Sn-58 wt.%Bi (eutectic) alloy casting. phology, as shown in Fig. 7. On the other hand, the
Typical SEM microstructures of the two hypoeu- presence of Bi particles in the -Sn phase is a con-
tectic Sn-Bi alloys are shown in Fig. 7 with a view to sequence of a process of precipitation during cooling
permitting details on the formation of the lamellar after the completion of solidification. In this case,
eutectic structure to be examined. Alternated layers of nucleation and growth are affected by a combination
1760 Silva, da Silva, Garcia, and Spinelli

(a) 90 (b) 1,6

Sn-34wt%Bi Sn-34wt%Bi
80 1,4 Sn-52wt%Bi
Sn-52wt%Bi
0.56 -0.8
P= 2.9 tL VL = 3.7 P
70
1,2
Sn-58wt%Bi

Growth rate, V (mm/s)

Sn-58wt%Bi
60 P= 0.56 tE
0.7
-0.41
VE = 0.3 P
Position (mm)

1,0
50
0,8
40
0,6
30

20 0,4

10 0,2

0
0,0
0 50 100 150 200 250 300 350 400 450 500 550
0 10 20 30 40 50 60 70 80 90
Time corresponding to eutectic/liquidus passage (s) Position (mm)

18
(c)
16 Sn-34wt%Bi
Sn-52wt%Bi
-1.96
14 TL= 345 (P)
Cooling rate, T (°C/s)

12 Sn-58wt%Bi
-1.96
T= 345 (P)
10

0
0 10 20 30 40 50 60 70 80 90
Position (mm)

18
(d)
16 Sn-34wt%Bi
Sn-52wt%Bi
Sn-58wt%Bi
14
Thermal Gradient, G (°C/mm)

-1.04
G = 63 (P)
12

10

0 10 20 30 40 50 60 70 80 90
Position (mm)
Fig. 5. Experimental plots obtained for the Sn-Bi alloys corresponding to: (a) position versus time at which the liquidus/eutectic front reaches
each thermocouple, (b) growth rate, (c) cooling rate and (d) thermal gradient as a function of position.
Effects of Solidification Thermal Parameters on Microstructure and Mechanical Properties of Sn-Bi 1761
Solder Alloys

Fig. 6. Representative optical microstructures and details on the phases and their morphologies considering two distinct levels of cooling rate
(left and right images) for (a) Sn-34 wt.%Bi, (b) Sn-52 wt.%Bi and (c) Sn-58 wt.%Bi solder alloys.

of Bi solid solubility along the Sn-rich phase, which
is affected by the cooling rate imposed under non-
equilibrium solidification and further precipita-
tion/growth of Bi particles.
Figure 9 shows the elemental SEM–EDS maps for
the Sn-52 wt.%Bi and 58 wt.%Bi alloys specimens
corresponding to a cooling rate of 0.2°C/s. Sn con-
trast (in green) is higher in Sn-rich dendrites and in
the eutectic mixture. Bi (in red) also appears con-
centrated in the eutectic mixture, but with less
intensity within the dendrite of the Sn-52 wt.%Bi
alloy. A coarse Bi-rich particle can be seen in the Sn-
58 wt.%Bi alloy specimen. A very low fraction of Sn
spots (in green) can be observed inside this particle.
The eutectic mixture is the main microstructural
component forming the as soldered Sn-Bi joints,
taking into account alloy compositions potentially
able to replace Sn-Pb alloys, i.e., eutectic-rich Sn-Bi
alloys. SEM microstructures as those showed in
Figs. 7 and 8 were examined through an image
analyzer, which allowed the experimental determi-
nation of the eutectic spacing along the length of the
DS castings. Hence, the average λfine and λcoarse
values with their standard deviations are shown in
Fig. 10 for all Sn-Bi alloys examined. The values,
measured from the lamellar eutectic structure, have
been plotted against the growth rate (V). Consider-
ing both fine and coarse eutectic spacings, the
1762 Silva, da Silva, Garcia, and Spinelli

Fig. 7. SEM microstructures of (a) Sn-34 wt.%Bi and (b) Sn-52 wt.%Bi alloys considering cooling rates of 12˚C/s, 1˚C/s and 0.3˚C/s (top to
bottom, respectively). The insets emphasize the distribution of Bi precipitates within the dendritic matrix (Sn-rich phase) of the Sn-34 wt.%Bi
alloy. P is the position from the cooled surface of the DS casting.

experimental evolutions can be represented by the
−1/2 exponent proposed by Jackson and Hunt.38
The experimental fittings encompass the follow-
ing λ ranges during unsteady-state growth of the
eutectic mixture: from 1.7 μm to 3.9 μm (coarse) and
from 0.8 μm to 1.3 μm (fine) for the Sn-34 wt.%Bi
alloy; from 0.9 μm to 3.1 μm (coarse) and from
0.8 μm to 1.8 μm (fine) for the Sn-52 wt.%Bi alloy,
and from 2.2 μm to 3.1 μm (coarse) and from 1.0 μm
to 1.7 μm (fine) for the Sn-58 wt.%Bi alloy. Overall,
if a single growth rate is considered, for example,
0.2 mm/s, the eutectic spacing of the Sn-58 wt.%Bi
alloy is lower than those obtained for the other two
Sn-Bi alloys.
Additional experimental data from Ref. 14 have
been included in Fig. 10b to encompass lower values
of growth rate (V) in order check the range of
applicability of the experimental power law derived
in the present study for the Sn-58 wt.%Bi alloy. The
experimental law, λfine = 0.40 × (V)−1/2, is able to
roughly represent also the inserted points.
Figures 11 shows the evolutions of primary (λ1),
tertiary (λ3) and secondary (λ2) dendritic arm spac-
ings as a function of both cooling rate (T˙) and
Effects of Solidification Thermal Parameters on Microstructure and Mechanical Properties of Sn-Bi
Solder Alloys
Fig. 8. Microstructures features observed in the Sn-58 wt.%Bi alloy. The presence of different sizes of eutectic arrangements (coarse and fine) is
emphasized for two different positions from the cooled surface of the DS casting: 15 and 40 mm.
growth rate (V) for the Sn-34 wt.%Bi and 52 wt.%Bi
solder alloys. The points in the graphs represent the
average experimental microstructural spacing
along with its standard deviation. Linear relation-
ships are shown fitted to the points with a view to
representing experimental power laws of dendritic
growth.
The power function exponents −1/4 and −1/2
characterize the primary/tertiary and secondary
dendrite arm spacings variations with cooling rate
and growth rate, respectively, for the Sn-52 wt.%Bi
alloy. It is worth noting that the Sn-52 wt.%Bi alloy
has a near-eutectic composition with 88% of eutectic
fraction according to Scheil’s equation.39 In this
case, due to this high proportion of eutectic mixture,
the classic Jackson and Hunt growth law for
eutectics37 is expected to apply to this alloy. Thus, λ1
and λ3 may be related to V−1/2. The cooling rate (T˙)
was shown in the literature40,41 to be given for
transient solidification conditions by the following
expression: constant × V2. If such expression is in-
serted into that proposed by Jackson and Hunt, λ1
may be related to the cooling rate according to a
power function exponent of −1/4. This is in agree-
ment with the experimental growth law derived in
the present study for the Sn-52 wt.%Bi solder alloy.
In the case of the Sn-34 wt.%Bi alloy, −0.55 and
−1.1 power laws represent the evolutions of λ1/λ3
and λ2 with the cooling rate and the growth rate,
respectively. The −0.55 exponent is recognized as
the most appropriate based on a number of experi-
mental evidences in recent studies considering the
growth of primary dendrite trunks under transient
solidification conditions.42,43 This kind of experi-
mental law fits well to the experimental scatters of
λ1 and λ3 obtained for the Sn-34 wt.%Bi alloy. It is
worth noting that the theoretical model of Bouchard
and Kirkaldy44 for growth of secondary dendritic
arms predicts a −2/3 exponent for λ2 × V relation-
ships. Nevertheless, such a theoretical exponent
cannot represent the experimental scatters of both
alloys examined, considering λ2 as a function of
growth rate. It is essential to be aware that, despite
the robustness of the experimental and theoretical
1763
approaches for modeling dendritic and cellular
growths, uncertainties associated with different
metallic systems and experimental growth condi-
tions can arise.
Although the primary dendritic spacing, λ1, of the
Sn-34 wt.%Bi alloy is smaller than that determined
for the Sn-52 wt.%Bi alloy, considering any cooling
rate examined, λ3 of the Sn-34 wt.%Bi alloy is sig-
nificantly higher when compared with the experi-
mental values obtained for the Sn-52 wt.%Bi alloy.
In spite of the decrease in λ2 with the increase in
growth rate, it seems that the magnitude of the
secondary spacing is not significantly affected by
the increase in the alloy Bi content from 34 wt.%Bi
to 52 wt.%Bi.
Figure 12 depicts the experimental dependences
of Vickers hardness on the inverse square root of the
eutectic spacing, λfine. The mechanical strength will
be significantly affected not only by dendritic spac-
ings of low and high order but also by the eutectic
mixture and its length scale. Since the Sn-Bi alloys
examined in the present research are considered
eutectic-rich compositions, the length scale of the
eutectic mixture was chosen in order to parame-
terize the experimental inter-relationships of hard-
ness, ultimate tensile strength (σu), yield strength
(σy) and elongation (δ) versus microstructural
spacings.
A decrease in hardness with the increase in the
length scale of the microstructure can be observed
for the hypoeutectic Sn-34 wt.%Bi and 52 wt.%Bi
alloys. However, an opposite experimental tendency
is shown to occur for the eutectic Sn-58 wt.%Bi al-
loy. This indicates that hardness is negatively af-
fected by the growth of trifoils and faceted particles
of Bi, with fishbone branches combined with the
eutectic mixture.
Typical stress–strain curves are plotted consid-
ering tests performed with specimens extracted at
P = 6 mm (black line) and P = 90 mm (gray line)
from the bottom of the DS castings (Fig. 13). Com-
paring the curves obtained for the Sn-34 wt.%Bi and
the Sn-58 wt.%Bi alloys, it can be seen that, with
the increase in the alloy Bi content, both ultimate
1764
Fig. 9. Elemental SEM–EDS maps obtained along the transverse specimens corresponding to a cooling rate of 0.2˚C/s for the DS: (a) Sn-52 wt.
%Bi and (b) Sn-58 wt.%Bi alloys castings.
tensile strength and elongation-to-fracture de-
crease. For the alloy with higher Bi content, the
necking stage seems to be shortened, which means
that the toughness has deteriorated. Such differ-
ences may be explained by the fact that both
strength and plasticity of the primary Sn-rich phase
are recognized as being better than those of the
eutectic phase.24 The Sn-34 wt.%Bi alloy has been
characterized by a significant fraction of Sn-rich
dendrites (see Fig. 6) whilst the microstructure of
Silva, da Silva, Garcia, and Spinelli
the eutectic composition does not reveal the pres-
ence of Sn-rich areas.
The stress–strain curves obtained for the differ-
ent positions in the Sn-52 wt.%Bi alloy DS casting
reveal an evident contrast between them, which can
be explained with basis on microstructure features.
In this case, a brittle behavior is associated with
P = 90 mm, with the corresponding stress–strain
curves exhibiting low ductility. The coarse eutectic
lamellar structure may be the responsible for such
Effects of Solidification Thermal Parameters on Microstructure and Mechanical Properties of Sn-Bi 1765
Solder Alloys

(a) function of the fine eutectic spacing along the length

of the DS castings. Most of the experimental scatters
λcoarse (μm)

have been fitted by Hall–Petch type correlations.

10
1 Considering the Sn-34 wt.%Bi and 52 wt.%Bi al-
loys, σu, σy and δ increase with decreasing λfine. The
tensile strengths, represented by σu and σy, of the
Coarse eutectic spacing,

Sn-34 wt.%Bi alloy casting are higher than the

corresponding values of the Sn-58 wt.%Bi alloy.
Sn-34wt%Bi
This is due to the combination of a higher proportion
0
λcoarse = 1.45 (V)
-1/2 2
- R =0.88 of areas of Sn-rich phase and a higher density of Bi
10
Sn-52wt%Bi precipitates inside those areas in the Sn-34 wt.%Bi
λcoarse = 1.1 (V)
-1/2 2
- R =0.93 alloy, as demonstrated by the smaller spacings be-
Sn-58wt%Bi tween the precipitates of this alloy when compared
-1/2 2
λcoarse = 0.75 (V) - R =0.81
with those determined for the Sn-52 wt.%Bi alloy. A
-2 -1 0
decrease in the eutectic spacing means a reduction
10 10 10
in size and more homogeneous distribution of the
Growth rate, V (mm/s) Bi-rich and Sn-rich phases throughout the
microstructure and this seems to enhance the
(b) mechanical strength of the mentioned alloys. In
Sn-52wt%Bi contrast, the values of elongation-to-fracture con-
sidering 1/λ1/2
fine > 0.9 (see Fig. 14c) are higher for
-1/2 2
λfine = 0.67 (V)
λfine (μm)

- R =0.79

Sn-34wt%Bi the Sn-52 wt.%Bi alloy when compared with those

Sn-58wt%Bi
1
10 λfine = 0.40 (V)
-1/2 2
- R =0.85
found for the Sn-34 wt.%Bi alloy.
As mentioned before, the best balance of strength
Fine eutectic spacing,

and ductility is that obtained with 1/λ1/2 fine = 1.23,

0
10
Results on Bridgman-type furnace
Sn-58wt%Bi [ref 31]
-3
10
Growth rate, V (mm/s)
Fig. 10. (a) Coarse and (b) fine lamellar spacing as a function of the
growth rate (V) for the Sn-Bi alloys. R2 is the coefficient of determi-
nation.
behavior. In contrast, an arrangement of much
branched dendrites with growth of high-ordered λ3
arms, fine Bi phase precipitates within the β-Sn
dendritic matrix, and an important proportion of
very fine eutectic formed by alternate Bi-rich and
Sn-rich phase (λfine = 0.8 μm and λcoarse = 0.9 μm)
characterizes the microstructure associated with
the relative position of 6 mm of the Sn-52 wt.%Bi
alloy DS casting. The combined reinforcement roles
of lower values of λfine, λcoarse and high density of Bi
precipitates inside the Sn-rich phase were shown to
induce beneficial effects on the tensile properties
with both strength and ductility increasing when
compared with the corresponding values obtained
for P = 90 mm, as shown in Fig. 13b.
Figure 14 synthesizes the results of tensile prop-
erties of all the three Sn-Bi alloys experimentally
examined. The ultimate tensile strength (σu), yield
tensile strength (σy) and elongation-to-fracture (δ)
are plotted with their standard deviations as a
which represents samples extracted from the posi-
tion that is closest to the cooled bottom of the DS Sn-
52 wt.%Bi alloy casting. For values of 1/λ1/2 fine lower
than 0.85, a recovery in strength is noted by the
lines representing the results of the Sn-52 wt.%Bi
alloy (see Fig. 14a and b). As discussed in a previous
article,38 this can be attributed to both an increase
-2 -1 0 in the eutectic fraction from this point and a
10 10 10
homogeneous distribution of this eutectic mixture
due to the more complex dendritic network caused
by the presence of tertiary dendrite arms.
Lower tensile properties are associated with the
Sn-58 wt.%Bi alloy casting, with an opposite ten-
dency when compared with the other alloys, con-
sidering σu and σy. Bi is considered a brittle phase
and this seems to contribute to this particular
behavior since the microstructure of the eutectic Sn-
58 wt.%Bi alloy is constituted by a predominance of
the eutectic mixture and by trifoils and faceted Bi
particles. The ductility deteriorates when compared
with the corresponding results of the two other al-
loys examined. It is worth noting that open and solid
circle values of strength representing the Sn-58 wt.
%Bi and the Sn-52 wt.%Bi alloys samples, respec-
tively, remain very close regardless ofr the alloy Bi
content for 1/λ1/2
fine < 0.8. This is due to the very high
area fraction of coarse lamellar eutectic in the Sn-
52 wt.%Bi alloy samples (>85%), which approxi-
mates both alloys regarding their microstructures.
Figure 15 shows SEM fracture surfaces of tensile
specimens of the Sn-34 wt.%Bi, Sn-52 wt.%Bi and
Sn-58 wt.%Bi alloys from positions in the DS cast-
ings corresponding to higher values of ductility, as
shown in Fig. 14c. Two SEM images with different
magnifications (×1000 and ×4000) are depicted for
each alloy examined.
1766 Silva, da Silva, Garcia, and Spinelli

3
(a) (b) 10
3
10 Sn-34wt%Bi

Secondary dendritic spacing, λ2 (μm)

-1.1 2
Primary dendritic spacing, λ1 (μm)

λ2 = 8.8 (VL) - R =0.99

Sn-52wt%Bi
-1/2 2
2 λ2 = 15.4 (VL) - R =0.91
10
2
10

Sn-34wt%Bi 1
-0.55 2 10
1
10 λ1 = 64 (T) - R =0.96

Sn-52wt%Bi
-1/4 2
λ1 = 310 (T) - R =0.98

0
0
10 10
-1 0
-1
10 10
0 1
10 10 10
Growth rate, VL (mm/s)
Cooling rate, T (°C/s)

(c)
Sn-34wt%Bi
-0.55 2
λ3 = 17 (T) - R =0.99
Tertiary dendritic spacing, λ3 (μm)

Sn-52wt%Bi
-1/4 2
λ3 = 10.5 (T) - R =0.97

1
10

-1 0 1
10 10 10

Cooling rate, T (°C/s)

Fig. 11. (a) Primary (b) secondary and (c) tertiary dendrite arm spacing as a function of cooling rate and growth rate for the DS Sn-34 wt.%Bi and
52 wt.%Bi alloys castings.

The fracture surfaces for the Sn-34 wt.%Bi and 30

Sn-58 wt.%Bi alloys are characterized by the pres-
ence of faceted Bi particles as indicated by black 27
arrows. These cleavage facets may induce the
occurrence of fracture throughout such phase.
Vickers Hardness (HV)

24
Overall, a brittle or faceted fracture type may be
indicated in these cases, which means that the 21
failure mode is basically the same for such Sn-Bi
alloys. Despite the presence of brittle fracture as- 18
pects in the Sn-34 wt.%Bi alloy, the presence of
ductile fracture bulges can be noted on the surface, 15 Sn-34%Bi
as can be seen in Fig. 15a. Sn-52%Bi
Sn-58%Bi
In the case of the Sn-52 wt.%Bi alloy, a particular 12
behavior is observed as compared with the other
aforementioned fractures. A typical ductile fracture 9
0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5
mode is associated with the stress–strain curve of
1/2 -1/2
high toughness (black line in Fig. 13b). As shown in 1/(λfine) (μm)
Fig. 15b, the fracture surface appears to be very fi- Fig. 12. Evolution of Vickers hardness as a function of the inverse of
nely broken, showing a large number of dimples the square root of the fine eutectic spacing for Sn-Bi solder alloys.
Effects of Solidification Thermal Parameters on Microstructure and Mechanical Properties of Sn-Bi 1767
Solder Alloys

(a) 70 (a) 70
65 Sn34wt.%Bi

Ultimate Tensile Strength (MPa)

68
60
66
55
50 64 0.5
σu = 51.5 + 7.1 (1/λfine )
45 62
Stress (MPa)

40 60
35 58
30 56
0.5
25 54 σu = 70 - 20.7 (1/λfine )
0.5
20 52 σu = 61.5 - 7.0 (1/λfine )
15 - Positions from 50
metal/mold interface (P): Sn-34wt%Bi
10 48
6mm 90mm Sn-52wt%Bi
5 Sn-58wt%Bi

σu,
46
0 44
0 3 6 9 12 15 18 21 24 27 30 0,4 0,5 0,6 0,7 0,8 0,9 1,0 1,1 1,2 1,3 1,4
Strain (%) 0.5 - 0.5
1/(λfine) ( µm )
(b) 70
(b) 60
65 Sn-34wt%Bi

Yield Tensile Strength (MPa)

Sn52wt.%Bi 58
60 Sn-52wt%Bi 0.5
σy = 43.2 + 8.3 (1/λfine )
55
56 Sn-58wt%Bi

50 54
45 52
Stress (MPa)

40 50
35 48 0.5
σy = 39.5 + 9.8 (1/λfine )
30
46
25
44 0.5
20 σy = 54.0 - 9.5 (1/λfine ) 0.5
σy = 62 - 21.2 (1/λfine )
15 42
- Positions from metal/mold interface (P):
10 40
σy,

6mm 90mm
5 38
0 36
0 4 8 12 16 20 24 28 32 36 40 44 48 52 56 60 0,4 0,5 0,6 0,7 0,8 0,9 1,0 1,1 1,2 1,3 1,4
Strain (%) 0.5 - 0.5
1/(λfine) ( µm )
(c) 70
(c) 70
65 65 Sn-34wt%Bi
Sn58wt.%Bi
60 Sn-52wt%Bi
Elogantion-to-fracture (%)

60
Sn-58wt%Bi
55 55
50 50 0.5
δ = -43 + 75 (1/λfine )
45 45
Stress (MPa)

40 40
35 35 0.5
δ = 9.9 + 9.9 (1/λfine )
30 30
25 25
20 20
15 15
δ,

10 - Positions from metal/mold interface (P): 10 0.5

6mm 90mm δ = -5 + 20.5 (1/λfine )
5 5
0 0
0 3 6 9 12 15 18 21 24 27 30 0,4 0,5 0,6 0,7 0,8 0,9 1,0 1,1 1,2 1,3 1,4
0.5 - 0.5
Strain (%) 1/(λfine) ( µm )
Fig. 13. Typical stress–strain curves of specimens extracted from Fig. 14. (a) Ultimate tensile strength-σu, (b) yield tensile strength-σy
two regions; close to the cooled bottom of the DS castings and (c) elongation-to-fracture-δ as a function of fine (λfine) eutectic
(P = 6 mm) and close to the top of the castings (P = 90 mm): (a) Sn- spacing for the Sn-34 wt.%Bi, 52 wt.%Bi and 58 wt.%Bi alloys.
52 wt.%Bi, (b) Sn-52 wt.%Bi and (c) Sn-58 wt.%Bi alloys castings.

that may lead to enhancement of toughness. As a sliding of the interfaces between adjacent phases is
very fine eutectic structure is formed by alternate attained due to the increase in contact area between
Bi-rich and Sn-rich phases (λfine = 0.8 μm and the phases.45 Such a complex interaction may occur
λcoarse = 0.9 μm), an enhancement effect on the especially during necking, with a direct beneficial
1768
Fig. 15. SEM fracture surfaces of the Sn-Bi alloys corresponding to tensile specimens extracted at different positions from the cooled surface of
the DS castings: (a) Sn-34 wt.%Bi; (b) Sn-52 wt.%Bi and (c) Sn-58 wt.%Bi.
effect to toughness as can be seen in the corre-
sponding stress–strain curve of Fig. 13b.
CONCLUSIONS
The following conclusions can be drawn from the
present experimental study:
1. The DS hypoeutectic Sn-Bi alloys castings were
shown to be characterized by a Sn-rich matrix
having a complex dendritic array formed not only
by primary dendrite stalks but also secondary
and tertiary dendritic branches with a lamellar
eutectic mixture in the interdendritic regions
formed by rhombohedral Bi-rich and body-cen-
tered tetragonal Sn-rich phases. In contrast,
Silva, da Silva, Garcia, and Spinelli
despite the non-equilibrium solidification condi-
tions, the eutectic DS Sn-58 wt.%Bi alloy casting
has no evidence of dendritic regions, being
characterized by a complex regular eutectic
microstructure typified by coarse and fine re-
gions, fishbone-like eutectic cells and trifoils of
Bi.
2. Experimental power–function growth laws were
shown to characterize the growth of primary,
secondary and tertiary dendritic branches, as a
function of solidification cooling rate and growth
rate. The evolution of the lamellar eutectic
spacing versus the growth rate was shown to be
represented by the −1/2 exponent proposed by the
classical Jackson and Hunt eutectic growth law.
Effects of Solidification Thermal Parameters on Microstructure and Mechanical Properties of Sn-Bi
Solder Alloys
3. A decrease in hardness was shown to occur with
the increase in the length scale of the eutectic
mixture considering the hypoeutectic Sn-34 wt.%
Bi and 52 wt.%Bi alloys. However, an opposite
experimental trend was derived for the eutectic
Sn-58 wt.%Bi alloy, indicating that hardness has
been negatively affected by the growth of trifoils
and faceted particles of Bi (with fishbone
branches) associated with the eutectic mixture.
4. Hall–Petch type equations have been proposed
relating σu; σy and δ with λfine. For the Sn-34 wt.
%Bi and 52 wt.%Bi alloys, σu, σy and δ increase
with decreasing λfine. A decrease in the eutectic
spacing induced a more homogeneous distribu-
tion of the Bi-rich and Sn-rich phases throughout
the microstructure, with beneficial effects on the
mechanical strength. The lowest tensile proper-
ties were shown to be associated with the Sn-
58 wt.%Bi alloy with an opposite tendency when
compared with the corresponding results of the
hypoeutectic alloys. This particular behavior has
been attributed to the microstructure of the
eutectic Sn-58 wt.%Bi alloy, which was shown
to be formed by predominance of eutectic mixture
and by trifoils and faceted Bi particles.
ACKNOWLEDGEMENTS
The authors acknowledge the financial support
provided by FAPESP (São Paulo Research Founda-
tion, Brazil: Grants 2015/11863-5 and 2013/08259-
3), CNPq and CAPES-COFECUB (Grant 857/15).
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