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Procedia Materials Science 1 (2012) 80 – 86

11th International Congress on Metallurgy & Materials SAM/CONAMET 2011.

Microstructure evolution during the aging at elevated

temperature of Sn-Ag-Cu solder alloys
C. Morando(a,b) *, O. Fornaro(a,b), O. Garbellini(a,c) and H. Palacio(a,c)
a
IFIMAT- Instituto de Física de Materiales Tandil, FCE - CICPBA - MT. Universidad Nacional del Centro de la Provincia de Buenos
Aires. Pinto 399 (B7000GHG) Tandil-Argentina
b
Consejo Nacional de Investigaciones Científicas y Técnicas CONICET
c
Comisión Investigaciones Científicas Provincia de Buenos Aires

Abstract

In this work, binary Sn-3.5%Ag and Sn-0.7%Cu and ternary Sn-3.5%Ag-0.9%Cu eutectic alloys has been used to
investigate the dynamic of microstructure transformation during isothermal artificial aging process at 180ºC. The
microstructure was investigated using optical microscopy (OM), scanning electron micrograph (SEM) and EDX (energy
dispersive X-ray microanalysis) and followed by Differential Scanning Calorimetry technique (DSC). In the as-cast
condition the binary eutectic alloys have a structure composed of Sn primary phase crystals surrounded by an irregular
eutectic structure composed of intermetallic sheets of Ag3Sn and Cu6Sn5 in an Sn matrix while the microstructure of the
ternary alloy shows the following phase -Sn surrounded by Sn-Ag binary eutectic and Sn-Ag-Cu ternary eutectic. After
48 hours of isothermal aging at 180°C both alloys show a noticeable change in their microstructures. In binary alloys a
larger grain structure is formed, Sn dendrites coarsen, and in the ternary alloy the intermetallic phases Ag3Sn Cu6Sn5 are
randomly distributed in a Sn matrix. There is a coarsening of Sn dendrites and Ag 3Sn phase produced by the growth
mechanism of Ostwald (Ostwald Ripening).

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Keywords: SnAgCu alloys; differential scanning calorimetry (DSC); lead free solder; eutectic solder alloys, microstructural changes.

* Corresponding author. Tel.: +54-249-4439670; fax: +54-249-4439679.

E-mail address: cmorando@exa.unicen.edu.ar, carinamorando@yahoo.com.ar.

2211-8128 © 2012 Published by Elsevier Ltd. Selection and/or peer-review under responsibility of SAM/CONAMET 2011, Rosario, Argentina.
Open access under CC BY-NC-ND license. doi:10.1016/j.mspro.2012.06.011
 C. Morando et al. / Procedia Materials Science 1 (2012) 80 – 86 81

1. Introduction

The operating environment temperature of many new electronic systems could be as high as 150ºC, for
example in the automotive industry or in aviation. These demanding conditions of use, together with the need
for greater reliability of all electronic systems motivate further research on the effects of high temperature
aging of solder materials (Anderson and Harringa, 2004). Microstructural changes can significantly modify
the mechanical properties of the joint and influence the behavior of the material during thermal fatigue (Wu
and Huang, 2005). The natural and artificial agings and their effect on the microstructure and mechanical
properties have been studied extensively in Pb-free alloys (LFS) used as input solder electronic processes,
particularly the system Sn-Ag-Cu (SAC) as a candidate to replace eutectic Sn-Pb alloy (Islam et. al., 2005;
Hsuan and Lin, 2007; Wei et. al, 2009; Seo et. al., 2009).
For this reason, it is important to know the initial microstructure of the solder joint and to understand how
the microstructural evolution occurs. This information will help in the development of physical models of the
phenomenon and thus anticipate the changes that will occur over time. Furthermore, this knowledge may be
taken into account to design standards to improve the reliability of Pb-free solder joints and to predict their
useful life. Research has shown that the characteristic lifetime due to fatigue of solder joints depends on the
microstructural evolution, assume that during the process occurs recrystallization and coarsening of the
microstructure. Less change of the microstructure in solder joints would imply that mechanical properties
remain stable and therefore the reliability and life time prediction will be more accurate using initial material
data (Fix et. al., 2008).
In a previous work performed by the authors (Morando et. al., 2010), microstructural and microhardness
changes of binary SnAg, SnCu and ternary SnAgCu eutectic alloys were studied as a function of aging time
during a heat treatment at 180°C, from the as-cast condition up to 500 hours. In all cases we have observed a
reduction of up to 20% in the microhardness compared with the as-cast alloy, reaching a minimum after 48
hours of heat treatment. This softening is related to the coarsening of Sn dendrites and Ag3Sn phase. As the
aging time exceeds 48 hours, the microhardness begings to increase and remains constant after the 100 hours.
This effect corresponds to the dispersion of the Ag3Sn particles into Sn rich crystals wich previously didn´t
contain intermetallic precipitates. In this work, binary Sn-3.5%Ag and Sn-0.7%Cu and ternary
Sn-3.5%Ag-0.9%Cu eutectic alloys have been used to investigate the dynamic of microstructure
transformation during isothermal artificial aging process at 180ºC with Differential Scanning Calorimetry
technique (DSC). The corresponding evolution of the microstructure with different times has been
investigated and discussed.

2. Experimental

Binary Sn-3.5%Ag, Sn-0.7%Cu and ternary Sn-3.5%Ag-0.9%Cu eutectic alloys were prepared by melting
pure elements (4N) in an electric resistance-type furnace under inert Ar gas atmosphere, stirred for adequate
homogeneization and cast into a refractory sand mold with a heat transfer coefficient in the metal-mold
interface: hi = 0.2 x103 J/m2.s.K. This procedure ensures the correct application of the equilibrium diagram in
the system studied. Rectangular specimens, 20 mm long by 10 mm wide, were cut. The nominal compositions
of the alloys are expressed as weight % of solute.
The as-cast and thermal aged solder samples were polished for testing of microhardness and observations
of the microstructure. Both optical microscopy (OM) and scanning electron microscopy (SEM) were used to
characterize the microstructure. Energy dispersive X-ray microanalysis (EDX) was used to characterize the
compositions of the compounds formed due to aging. Microstructural analysis of as-cast and thermal aged
solder samples was performed on metallographic specimens that were polished by following standard
82 C. Morando et al. / Procedia Materials Science 1 (2012) 80 – 86

metallographic procedures and etched with a solution of 2 of HCl in alcohol for several seconds. The
microstructure was recorded by photomicrographs at regular 24 hours intervals. The observation was started
one hour after the casting. The observation area was carefully selected in order to observe the microstructural
change. After the photomicrographs were taken, the various specimens were aged and at the end of each 24
hours ageing stage, the specimen was polished slightly and re-etched. For calorimetric analysis, we used a
differential scanning calorimeter DSC Heat Flux Rheometric Scientific SP, with a stability of line better than
1mW in the measurement range used. The samples used are 6mm in diameter and 20mg of weight. The curves
were obtained for scan rates of 5 and 10K/min.
3. Results and Discussion
From the microstructure examination, it was found that Sn-rich crystals are the basic microstructure of the
Sn-3.5%Ag and Sn-0.7%Cu binary eutectic alloys in as-cast condition, there are intermetallic particles around
the Sn-rich phase as shown in Figure 1a and 2a). From EDX microanalysis, the intermetallic compounds
found were mainly Ag3Sn and Cu6Sn5 respectively. Some coarsening of Sn-rich crystals with random
orientations is observed in the annealed after 48 hours, Figures 1b and 2b). Figures 1c and 2c) show that in
both binary alloys the microstructure changes significantly after 100 hours of heat treatment, showing an
intermetallic particle dispersion of Ag3Sn and Cu6Sn5 in Sn-rich crystals which initially did not contain these
precipitates. Figure 1d and 2d) shows detailed views of SEM images where the precipitation of 1: -Sn, and 2:
Ag3Sn y Cu6Sn5 phases are marked. The composition of these phases was determined by EDX.
Figure 3a) shows an optical micrography of the Sn-3.5%Ag-0.9%Cu as-cast alloy. The microstructure
shows -Sn surrounded by Sn-Ag binary eutectic and Sn-Ag-Cu ternary eutectic. Figure 3b) shows the
microstructural evolution after 48 hours of isothermal heat treatment at 180°C. Intermetallic phases Ag3Sn
and Cu6Sn5 are randomly distributed in a matrix of Sn, there is a coarsening of the Sn dendrites and Ag 3Sn
phase produced by the growth mechanism of Ostwald (Ostwald Ripening) (Snugovsky et. al., 2004). After
100 hours of heat treatment at this temperature, samples exhibit a more dispersed precipitated structure,
indicating that at this aging temperature Ag rapidly diffuses from the eutectic region to Sn-rich crystals
forming new precipitates, Figures 3c). The detail of this microstructure is shown in SEM micrograph of
Figure 3d) in which different phases are marked whose compositions were determined by X-ray scattering
-Sn, phase 2: Ag3Sn and phase 3: Sn-Ag3Sn-Cu6Sn5. In every studied case there was a
decrease in microhardness of up to 20% in the (Morando et. al., 2010) of that of the as-cast alloy, reaching a
minimum value after 48 hours of heat treatment. This softening is related to the coarsening of Sn dendrites
and Ag3Sn and Cu6Sn5 intermetallic phases. As the aging time exceeds 48 hours, the microhardness begings
to increase and remains constant after the 100 hours.
Calorimetry charts are shown in Figures 4 a, b and c) for all the studied alloys and for each aging time.
Figure 4a) corresponds to the Sn-Cu eutectic alloy in as-cast condition, and with artificial aging of 24, 48 and
96 hours at T = 180ºC, whilst Figure 4b) to Sn-Ag eutectic alloy and 4c) to Sn-Ag-Cu ternary eutectic alloy
for similar aging time. As previously reported (Morando et. al., 2010), for aging in the range of 24 to 48 hours
the samples showed a decrease in the Vickers microhardness and then an increasing starting from 96 hours of
aging, reaching the original values of the as-cast condition. However, this behavior does not correlate with the
data extracted from calorimetry curves of Figure 4, where there are no signs of dissolution or precipitation of
new phases in the range of the studied temperatures from 40-205ºC. From the point of view of this analysis
technique, the mechanism compatible with this behavior is the coarsening of existent phases and the stress
relaxation during the first hour of aging.
 C. Morando et al. / Procedia Materials Science 1 (2012) 80 – 86 83

a) b)

c) d)

Figure 1. Microstructure of Sn-3.5% Ag eutectic alloy, a) as-cast, subjected to aging heat treatment at 180° C for b) 48 hours c) 100
hours, d) SEM micrograph, for 100hs of aging, -Sn, phase 2: Ag3Sn.

a) b)
84 C. Morando et al. / Procedia Materials Science 1 (2012) 80 – 86

c) d)

Figure 2. Microstructure of Sn-0.7% Cu eutectic alloy, a) as-cast, subjected to aging heat treatment at 180° C for b) 48 hours c) 100
hours, d) SEM micrograph, for 100hs of aging, in which are marked different phases: phase 1 -Sn, phase 2: Cu6Sn5.

a) b)

c) d)

Figure 3. Microstructure of Sn-3.5% Ag-0.9%Cu eutectic alloy, a) as-cast, subjected to aging heat treatment at 180° C for b) 48 hours
c) 100 hours, d) SEM micrograph, for 100hs of aging, in which are marked different phases: phase 1 -Sn, phase 2: Ag3Sn and phase 3:
Sn-Ag3Sn-Cu6Sn5.
 C. Morando et al. / Procedia Materials Science 1 (2012) 80 – 86 85

0,4
a) As Cast
24 hs
48 hs
96 hs
0,3

Q (J/gK)
0,2

0,1
40 60 80 100 120 140 160 180 200
T (°C)

0,4

b) As Cast
24 hs
48 hs
96 hs
0,3
Q (J/gK)

0,2

0,1
40 60 80 100 120 140 160 180 200
T (°C)

0,4

As Cast
c) 24 hs
48 hs
96 hs
0,3
Q (J/gK)

0,2

0,1
40 60 80 100 120 140 160 180 200
T (°C)

Figure 4. Normalized heat flux per unit mass at the rate 10 K/min, for binary eutectic a) Sn-Cu, b) Sn-Ag and c) Sn-Ag-Cu ternary
eutectic alloy, during artificial aging at T=180°C, at time 0 (as-cast), 24, 48 and 96 hs.
86 C. Morando et al. / Procedia Materials Science 1 (2012) 80 – 86

4. Conclusions
In this work we studied the dynamic of microstructure transformation of binary eutectic alloys Sn-3.5% Ag
and Sn-0.7% Cu and ternary Sn-3.5%Ag-0.9% Cu during artificial aging at 180ºC at different times of heat
treatment. The evolution of the microstructure was investigated using optical microscopy (OM) and scanning
electron microscopy (SEM) and followed by Differential Scanning Calorimetry technique (DSC). In the
as-cast condition the binary eutectic alloys has a structure composed of Sn-rich crystals surrounded by an
irregular eutectic structure composed of intermetallic sheets of Ag3Sn and Cu6Sn5 in an Sn matrix. The
microstructure of the ternary alloy shows -Sn surrounded by Sn-Ag binary eutectic and Sn-Ag-Cu ternary
eutectic. After 48 hours of isothermal aging at 180° C noticeable changes in the microstructures were
observed. In binary alloys a larger grain structure is formed, and Sn dendrites coarsen. In the ternary alloy the
intermetallic phases Ag3Sn Cu6Sn5 are randomly distributed in a Sn matrix. There is a coarsening of Sn
dendrites and Ag3Sn phase produced by the growth mechanism of Ostwald (Ostwald Ripening).
There is no evidence of disolution or precipitation of new phases in the range of studied temperatures that
can be detected by DSC calorimetry technique.As a result the acting mechanisms could be the coarsening of
Sn dendrites and the relaxation of residual stresses during the first stages of isothermal aging. By means of
these mechanisms the behavior of Vickers microhardness can be interpretated.

Acknowledgements

This work was carried out at IFIMAT (Instituto Física de Materiales de Tandil) and has been partially
supported by CICPBA (Comisión de Investigaciones Científicas de la Provincia de Buenos Aires), CONICET
(Consejo Nacional de Investigaciones Científicas y Técnicas) and SeCyT-UNCPBA (Secretaría de Ciencia,
Arte y Tecnología de la Universidad Nacional del Centro de la Provincia de Buenos Aires).

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