Accepted Manuscript

Separation of Sn, Bi, Cu from Pb-free solder paste by ammonia

leaching followed by hydrochloric acid leaching

Sang-Hee Jeon, Kyoungkeun Yoo, Richard Diaz Alorro

PII: S0304-386X(16)30623-5
DOI: doi: 10.1016/j.hydromet.2016.12.004
Reference: HYDROM 4482
To appear in: Hydrometallurgy
Received date: 4 September 2016
Revised date: 23 November 2016
Accepted date: 8 December 2016

Please cite this article as: Sang-Hee Jeon, Kyoungkeun Yoo, Richard Diaz Alorro ,
Separation of Sn, Bi, Cu from Pb-free solder paste by ammonia leaching followed by
hydrochloric acid leaching. The address for the corresponding author was captured as
affiliation for all authors. Please check if appropriate. Hydrom(2016), doi: 10.1016/
j.hydromet.2016.12.004

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 ACCEPTED MANUSCRIPT

Separation of Sn, Bi, Cu from Pb-free solder paste by ammonia leaching followed by
hydrochloric acid leaching

Sang-Hee Jeon1, Kyoungkeun Yoo1*, Richard Diaz Alorro2

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Department of Energy & Resources Engineering, Korea Maritime and Ocean University,
Busan, 606-791, Korea
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Department of Mining Engineering and Metallurgical Engineering, Western Australian
School of Mines, Curtin University, Kalgoorlie, WA 6430, Australia

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* Corresponding author: kyoo@kmou.ac.kr

Abstract

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A recycling process consisting of swelling, ammonia leaching and hydrochloric acid
leaching was developed to recover Sn, Bi, Cu, and resin from Pb-free Sn-Bi-Cu solder paste.
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The resin was separated from metal powder by swelling the solder paste in methyl ethyl
ketone at 30°C, 200 rpm and 5% pulp density. The addition of distilled water precipitated the
resin from methyl ethyl ketone. The recovered resin was confirmed to be epoxy resin by FT-
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IR analysis. Ammonia leaching followed by hydrochloric acid leaching was performed to

separate Cu, Sn, Bi sequentially from metal powder. Copper was solubilized easily with
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leaching efficiency reaching 100 % within 15 min under the following conditions: 5 M NH3
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solution, 1 M (NH4)2CO3, 0.1 M CuCO3, 50 °C, and 1 % pulp density. Tin and bismuth were
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recovered as leach residue in the ammonia leaching. Tin was selectively leached in 0.5 M
HCl solution with 10000 mg/L Sn4+ and 1 % pulp density at 50 °C and 400 rpm, while Bi was
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not detected in the leach solution. The recycling process has successfully separated Sn, Cu,
Bi and resin.
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Key words: lead-free solder; ammonia leaching; hydrochloric acid leaching; recycling

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1. Introduction
The recovery of valuable metals from secondary resources such as E-wastes and
wastewater is vital in resource-scarce countries (Kim et al., 2015; Nakamura, 2014). Solders
are important components of electronic products. Solder alloys are used as interconnecting
materials in electronic packaging for the production of electric and electronic equipment (Yoo
et al., 2012). Lead (Pb) used to be main component of solder alloys but, due to its toxicity,

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Pb-free solders have been developed as alternative using tin (Sn), silver (Ag), copper (Cu),
bismuth (Bi), antimony (Sb), and zinc (Zn) (Ma and Suhling, 2009; Yoo et al., 2012). Sn-Bi-

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Cu series has several advantages compared to Pb-Sn solder including lower temperature
requirement for soldering, better creep resistance, and higher tensile strength (Miao et al.,

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2000; Miao and Duh, 2001). There is a need to recycle waste solder alloys as they contain
both valuable and heavy metals.
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Waste Pb-free solder can be recycled into solder bars by simple melting processes,
which could pose serious environmental problems due to hazardous gas emissions from the
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combustion of organic flux in the Pb-free solder (Yoo et al., 2012). Hydrometallurgical
processes have been alternatively researched for the recycling of waste Pb-free solder. Tin
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can be recovered as stannic acid from Sn-Ag-Cu and Sn-Bi solders by nitric acid leaching
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(Jeon et al., 2015; Yoo et al., 2012). However, due to concerns regarding NOx emission in
these processes, recycling techniques using HCl leaching with H2O2 and Fe3+ were proposed
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to recover Sn, Ag, and Cu from waste Pb-free solder (Kim et al., 2014; Lee et al., 2015).
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Research on Sn-Bi-Cu solder recycling is limited. To date, very few studies reported
investigations on recycling processes for the new solder. Therefore, the present study is
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aimed at developing a new recycling process consisting of swelling, ammonia leaching

followed by hydrochloric acid leaching with cupric and stannic ions as oxidants. The effects
of the parameters, such as agitation speed, oxidant concentration, leaching media and pulp
density, on the leaching behavior of Sn, Bi, and Cu were investigated and the results are
discussed in this paper.

2. Experimental

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2.1. Materials
The Pb-free solder paste containing 20 % Bi, 17 % Sn, 47 % Cu and 16 % resin was
obtained from a solder company in Korea. The solder paste sample is still in the middle of
development and this explains the higher Cu content compared to other commercialized Sn-
Bi-Cu solders. All chemical properties of the paste sample other than Cu content are
comparable to the commercial ones. All chemicals used in this study are of reagent-grade.

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2.2. Swelling and leaching procedures

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When a resin is swollen by some organic solvents, the resin behaves like solution or
suspension with the solvents. Swelling tests with methyl ethyl ketone (MEK) were conducted

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to separate the resin from metal components, using a 250 cm3 Pyrex glass reactor equipped
with water jacket. After 100 cm3 of MEK was placed in the reactor, the temperature was set at
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30°C with water jacket system, and then 5 g of the solder paste was added. A magnetic bar
was used for stirring at 200 rpm, and after 1 hour, metal powders/precipitates and MEK-resin
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suspension were separated using a Mega 17R centrifugal separator (Hanil Science Inc., Korea)
at 3820 ×g for 30 minutes. A 100 cm3 of distilled water was added to the supernatant solution,
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to separate the resin from MEK.

Leaching tests were performed in a 500 cm3 three-necked Pyrex glass reactor using a
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heating mantle to maintain temperature. During the tests, nitrogen gas was introduced into the
leach solution at 100 cc/min. The reactor was fitted with a stirrer and a reflux condenser to
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avoid solution loss at high temperatures. Ammonia leach solution was prepared by adding
CuCO3 and (NH4)2CO3, CuCl2 and NH4Cl, or CuSO4 and (NH4)2SO4 to ammonia solution,
respectively, where the concentration of NH4+ was adjusted to 2M. The hydrochloric acid
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leach solution was prepared by adding SnCl4 to hydrochloric acid solution. A 200 cm3 of
ammonia leach solution or hydrochloric acid leach solution was fed into the reactor and
allowed to reach thermal equilibrium at 50°C. The metal powder collected from swelling test
or the leach residue obtained from ammonia leaching test was added to ammonia leach
solution or hydrochloric acid leach solution, respectively, and stirred at 200−600 rpm. During
the tests, 3 cm3 of the solution sample was withdrawn at a desired time interval.

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2.3. Analytical methods

The resin separated from swelling test was analyzed with FT/IR 4100 (Jasco Analytical
Instrument, Inc., Japan), and then digested using Start D microwave digestion system
(Milestone Inc., Italy). The metal powder collected from swelling test and the leach residue
obtained from ammonia leaching test were analyzed with SmartLab X-ray diffractometer

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(XRD) (Rigaku Co., Japan). The metal powder and the solder paste were examined with
MIRA 3 FE-SEM (Field emission scanning electron microscope) (TESCAN Inc., Czech

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Republic).
The leaching residue was digested with HNO3 and HF solution. The resulting solution

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was filtered with a 0.45-µm membrane filter and then diluted with 5% HNO3 solution for Cu
and Bi analyses and 15% HCl solution for Sn analysis. Metal concentrations were then
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measured with AA7000 atomic absorption spectrometry (Shimadzu Co. Ltd., Japan) and
OPTIMA 8300 DV inductively coupled plasma-atomic emission spectrometry (ICP-AES,
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PerkinElmer Inc., USA).

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3. Results and discussion

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The Sn-Bi-Cu solder paste contains resin, so swelling test with MEK was conducted to
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remove the resin components. MEK was found to be an effective solvent to dissolve resin
(Mauerer, 2005). Fig. 1 shows the SEM images of solder paste (as-received) (Fig. 1(a)) and
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metal powder (Fig. 1(b)) collected from the swelling test. The metal powder is more visible
and defined in Fig. 1(b) than in Fig. 1(a). The flat and spherical particles observed in the
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micrograph were confirmed to be Cu and Sn/Bi by energy-dispersive X-ray spectroscopy.

Leaching tests with solder paste and metal powder were performed in 1 M HCl at 50 °C and
400 rpm with 1 % pulp density. Fig. 2 shows that the leaching efficiencies of Sn, Cu, Bi
increased after swelling, which could be attributed to the enhanced contact between leach
solution and metal. The supernatant solution obtained from swelling followed by
centrifugation consists of MEK and resin. In the conventional Vinyloop Process (Lindahl and
Winsnes, 2005), it was reported that the resin (PVC) was successfully recovered because the

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water addition decreased the solubility of resin (PVC) in MEK (Lindahl and Winsnes, 2005).
When distilled water was added to the supernatant solution, floating resin was observed in the
solution. As shown in Fig. 3, the resin was determined to be epoxy resin by FT-IR analysis,
and no metal was detected from the digested epoxy solution. Therefore, epoxy was
successfully separated and recovered from metal powder by MEK swelling followed by water
addition.

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A leaching process was designed to separate Sn, Bi, Cu, respectively, from metal powder,
using ammonia leaching with cupric ion (Cu2+) followed by hydrochloric acid leaching with

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stannic ion (Sn4+). Cupric ammonia complex ion (Cu(NH3)42+) could oxidize Cu metal as
follows (Bari et al., 2009; Koyama et al., 2006; Oishi et al., 2007);

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This reaction could be achieved in the pH range of 9 – 11 (Meng and Han, 1996) where
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the solubilities of bismuth (Bi) and tin (Sn) are low (Jeon et al., 2015). Fig. 4 shows the
effects of leaching media (prepared by adding CuSO4 and (NH4)2SO4, CuCl2 and NH4Cl, or
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CuCO3 and (NH4)2CO3 to 5 M NH3 solution) on the leaching efficiency of Cu. The leaching
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efficiency of Cu reached 100 % within 15 min in carbonate and sulfate media, while within
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60 min in chloride medium. Similar results were reported by Bari et al. (2009), but the
mechanism is still not clear and further study is required.
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Fig. 5 shows the effects of agitation speed on the leaching efficiency of Cu in 5 M NH3
solution with 1 M (NH4)2CO3 and 0.1 M CuCO3 at 50°C and 1 % pulp density. The leaching
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efficiency initially increased rapidly to over 80% at 200 rpm and then gradual increments
were observed reaching about 90% at 60 min. When the agitation speed was increased to
more than 400 rpm, 100% leaching efficiency was achieved within 15 min. Therefore, in all
subsequent leaching tests, a working agitation speed of 400 rpm was selected to ensure
effective particle suspension in the solution. Since cupric ion acts as an oxidant, the effect of
cupric ion concentration on the leaching efficiency of Cu was investigated in 5M NH3
solution with 1M (NH4)2CO3 at 50°C, 400 rpm and 1% pulp density. As shown in Fig. 6, the

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leaching efficiency increased with increasing cupric ion concentration at the initial leaching
stage, and the difference became negligible with more than 0.05M Cu 2+ within 60 min.
Sn and Bi were not detected in leach solution in all ammonia leaching tests. The XRD
results of as-received solder paste and ammonia leach residue are shown in Fig. 7. It can be
observed that the peaks of Cu disappeared in the leach residue. Digesting the leach residue
obtained from leaching test in 5M NH3 solution with 1M (NH4)2CO3 and 0.1M CuCO3 at

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50 °C and 1% pulp density, confirmed that Cu was not present in the leach residue. These
results indicate that Cu could be separated successfully from Sn and Bi.

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Kim et al. (2016) reported that stannic ion (Sn4+) could oxidize tin metal in hydrochloric
acid solution as follows:

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The leaching behaviors of Sn and Bi were investigated in 0.5M HCl solution with stannic ion
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to separate Sn and Bi from leach residue. Fig. 8 shows the effects of agitation speed on the
leaching efficiency of Sn in 0.5M HCl solution with 10000 mg/L Sn4+ at 50°C and 1% pulp
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density. The leaching efficiency increased rapidly and reached 100 % within 60 min at more
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than 300 rpm.

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The ammonia leach residue contains 46% Sn and 54% Bi. Given this concentration,
more than 4600 mg/L Sn4+ will be required to dissolve Sn in the leach residue at 1% pulp
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density condition. Fig. 9 shows the effects of Sn4+ concentration on the leaching efficiency of
Sn in 0.5M HCl solution at 50°C, 400 rpm and 1% pulp density. The leaching efficiency
increased to 100 % within 60 min at 10000 mg/L Sn4+ and within 120 min at 5000 mg/L Sn4+,
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respectively. At 2500 mg/L Sn4+, only about 50% of leaching efficiency was observed and
this could be explained by the insufficient concentration of Sn4+ available for Sn dissolution.
The effect of pulp density on the leaching efficiency of Sn was investigated in 0.5M HCl
solution with 10000 mg/L Sn4+ at 50°C and 400 rpm. As shown in Fig. 10, the leaching
efficiency increased to 100% within 60 min for pulp densities of 1-2%, while only 66% at a
pulp density of 3%. The decrease in the leaching efficiency at higher pulp density can be

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attributed to the insufficient amount of oxidant (Sn4+). About 20g/L tin solution was obtained
from the leaching test performed under the leaching conditions: 0.5M HCl, 10000 mg/L Sn4+,
50°C, 400 rpm and 2 % pulp density. In all HCl leaching tests with stannic ion, Bi was not
detected in the solution. These results indicate that Sn can be separated successfully from Bi
in the leach residue.
Based on the results discussed above, a recycling process for the waste Pb-free solder

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paste of Sn-Bi-Cu series is proposed. The process, as shown in Fig. 11, consists of the
following: (1) epoxy resin is separated by swelling the solder paste with MEK; (2) Cu ion is

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recovered from metal powder collected from swelling test, by NH3 leaching with (NH4)2CO3
and CuCO3; and (3) Sn ion is separated from Bi by HCl leaching with SnCl4. Oishi et al

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(2007) and Kim et al (2016) reported that Cu+ and Sn2+ ions could be electrochemically
oxidized into Cu2+ and Sn4+, respectively, and could then be reused in the leaching processe.
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This couldenhance the economic viability of the process. Further study is required to
investigate the effect of this re-circulation process.
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4. Conclusion
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A hydrometallurgical route was investigated to separate resin, Cu, Sn and Bi,

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respectively, from Sn-Bi-Cu solder paste. The swelling test with MEK, ammonia leaching
with Cu2+, followed by hydrochloric acid leaching with Sn4+ were sequentially tested to
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examine various leaching parameters, such as oxidant concentration, leaching media, pulp
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density, and agitation speed.

The removal of resin enhanced the leaching efficiency of metals and the resin was
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determined to be epoxy resin by FT-IR analysis. The copper component can be selectively
leached from metal powders in ammonia solution with cupric ion. in can be separated from
Bi in the ammonia leaching residue by hydrochloric acid leaching with stannic ions.
Consequently, these hydrometallurgical processes could separate resin, Cu, Sn, and Bi from
Pb-free solder paste and could eliminiate the hazardous gas emission associated with
conventional recycling processes, such as melting. .

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Acknowledgement

This study was supported by the R&D Center for Valuable Recycling (Global-Top
R&BD Program) of the Ministry of Environment.

References

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the leaching behaviors of tin and bismuth spent lead free solder in nitric acid leach solution.
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from waste Pb-free solder using hydrochloric acid leaching with hydrogen peroxide. Mater.
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Trans. 55, 1885-1889.

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Kim, S., Lee, J.C., Yoo, K., 2016. Leaching of tin from waste Pb-free solder in hydrochloric
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Koyama, K., Tanaka, M., Lee, J., 2006. Copper leaching behavior from waste printed circuit
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electronic packaging. J. Mater. Sci. 44, 1141-1158.

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joints under thermal aging. Mater. Chem. Phys. 71, 255-271.
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Yoo, K., Lee, J.C., Lee, K.S., Kim, B.S., Kim, M.S., Kim, S.K., Pandey, B.D., 2012.
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Fig. 1. SEM images of (a) as-received solder paste (before swelling test) and (b) metal
powder separated from swollen resin.
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Fig. 2. The comparison of leaching efficiencies of Sn, Cu, Bi before and after swelling tests.
Leaching conditions: 1 M HCl, 400 rpm, 1 % pulp density, 50 °C and 180-minute leaching
time.
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Fig. 3. The FT-IR analysis result of resin collected from swelling test
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Fig. 4. The effects of leach media on the leaching efficiency of Cu in 5 M NH3 solution with
2M NH4+ and 0.1M Cu2+ at 50°C, 400 rpm and 1% pulp density.
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Fig. 5. The effects of agitation speed on the leaching efficiency of Cu in 5M NH3 solution
with 1M (NH4)2CO3 and 0.1M CuCO3 at 50°C and 1 % pulp density.
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Fig. 6. The effects of cupric ion concentration on the leaching efficiency of Cu in 5M NH3
solution with 1M (NH4)2CO3 at 50°C, 400 rpm and 1% pulp density.
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Fig. 7. XRD patterns of solder paste (before leaching) and leach residue (after leaching).
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Fig. 8. The effects of agitation speed on the leaching efficiency of Sn in 0.5M HCl solution
with 10000 mg/L Sn4+ at 50°C and 1% pulp density.
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Fig. 9. The effects of Sn4+ concentration on the leaching efficiency of Sn in 0.5M HCl
solution at 50°C, 400 rpm and 1% pulp density.
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Fig. 10. The effects of pulp density on the leaching efficiency of Sn in 0.5M HCl solution
with 10000 mg/L Sn4+ at 50°C and 400 rpm.
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Fig. 11. The recycling process of Pb-free solder paste proposed in this study.
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Highlights

 A new Sn-Bi-Cu solder paste recycling process was proposed using

swelling and leaching processes to separate resin, Sn, Bi, and Cu,
respectively.

 Epoxy resin could be recovered by swelling with methyl ethyl ketone

followed by distilled water addition.

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 Cu could be dissolved by ammonia leaching leaving Sn and Bi as leach
residue from metal powders obtained from the swelling process

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 Sn could be selectively leached from Sn and Bi powder using HCl

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solution with SnCl4.
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