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High temperature investigations on optimising the recovery of copper from

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Article  in  Waste Management · January 2017

DOI: 10.1016/j.wasman.2017.01.001

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 Waste Management xxx (2017) xxx–xxx

Contents lists available at ScienceDirect

Waste Management
journal homepage: www.elsevier.com/locate/wasman

High temperature investigations on optimising the recovery of copper

from waste printed circuit boards
R. Cayumil a, M. Ikram-Ul-Haq a, R. Khanna a,⇑, R. Saini a, P.S. Mukherjee b, B.K. Mishra b, V. Sahajwalla a
a
Centre for Sustainable Materials Research and Technology (SMaRT), School of Materials Science and Engineering, The University of New South Wales, Sydney, NSW 2052, Australia
b
CSIR – Institute of Minerals and Material Technology, Advanced Materials Technology Department, Bhubaneshwar, Orissa 751013, India

a r t i c l e i n f o a b s t r a c t

Article history: High temperature pyrolysis investigations were carried out on waste printed circuit boards (PCBs) in the
Received 23 October 2016 temperature range 800–1000 °C under inert conditions, with an aim to determine optimal operating con-
Revised 2 January 2017 ditions for the recovery of copper. Pyrolysis residues were characterized using ICP-OES analysis, SEM/EDS
Accepted 2 January 2017
and XRD investigations. Copper foils were successfully recovered after pyrolysis at 800 °C for 10–20 min;
Available online xxxx
the levels of Pb and Sn present were found to be quite low and these were generally present near the foil
edges. The relative proportions of Pb and Sn became progressively higher at longer heating times due to
Keywords:
enhanced diffusion of these molten metals in solid copper. While a similar behaviour was observed at
E-waste
PCBs
900 °C, the pyrolysis at 1000 °C resulted in copper forming Cu-Sn-Pb alloys; copper foils could no longer
Pyrolysis be recovered. Optimal conditions were identified for the direct recovery of copper from waste PCBs with
Copper recovery minimal processing. This approach is expected to make significant contributions towards enhancing
Pollution material recovery, process efficiency and the environmental sustainability of recycling e-waste.
Energy efficiency Pyrolysis at lower temperatures, short heating times, coupled with reductions in process steps are
expected to significantly reduce energy consumption and pollution associated with the handling and pro-
cessing of waste PCBs.
Ó 2017 Elsevier Ltd. All rights reserved.

1. Introduction
High consumption of electronic and electrical equipment (EEE),
their short life-spans and subsequent obsolescence has resulted in
the accumulation of large volumes of electronic waste (e-waste)
worldwide. Rapid technological advancements followed by regular
upgrades of electronic items such as mobile phones, computers,
TVs, laptops, notebooks etc. are playing a significant role in the
generation of such waste. With e-waste volumes increasing at
the rate of 4–5% per year, it is one of the fastest growing solid
waste streams in the world. Nearly 41.8 million tons of e-waste
was generated globally in 2014; and the global generation of e-
waste in 2018 is expected to be 49.8 Mt (Baldé et al., 2015).
The central components of EEE are printed circuit boards (PCBs),
which contain a mixture of polymers, ceramics and metals as part
of the boards, circuitry, components, solders, and connectors
(Lister et al., 2014). With increasing demands for metals, declining
mineral resources, costs and environmental impacts associated
with mining and the exploitation of natural resources, there is
immense potential in transforming e-waste from a waste product
⇑ Corresponding author.
E-mail address: ritakhanna@unsw.edu.au (R. Khanna).
to a materials resource. While the rates for recycling are still quite
low, there is an urgent need to take a critical look at the current e-
waste recycling techniques and to optimise the recovery of metals
and other valuable products.
This article is focussed primarily on optimising the recovery of
copper from e-waste, one of the main metallic constituents (up to
20 wt%) of waste PCBs. Along with the key aspects of material
recovery, associated waste management perspectives including
the volumes of wastes processed, energy consumption, secondary
waste generation, and the environmental impact of PCB recycling
will be discussed. The recovery of copper from e-waste has been
investigated extensively using hydrometallurgical and pyro-
metallurgical techniques (Cui and Zhang, 2008; Schluep et al.,
2009). We first present a brief overview of the current status of
research in the field including techniques/approaches used along
with details such as the nature/form of copper recovered, the num-
ber of process steps, and process efficiency.
1.1. Commercial approaches
Commercial recycling of e-waste is currently carried out in two
industrial operations, namely Noranda and Rönnskar as a part of
primary copper processing (Veldhuizen and Sippel, 1994). Up to

http://dx.doi.org/10.1016/j.wasman.2017.01.001
0956-053X/Ó 2017 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Cayumil, R., et al. High temperature investigations on optimising the recovery of copper from waste printed circuit
boards. Waste Management (2017), http://dx.doi.org/10.1016/j.wasman.2017.01.001
2 R. Cayumil et al. / Waste Management xxx (2017) xxx–xxx
14 wt% crushed e-waste is added as an additive/impurity to the
copper ore; the levels of e-waste being recycled are limited by their
influence on furnace operations. Copper present in PCBs is heated
at 1250 °C in oxygen-rich atmosphere, converted to copper matte;
high purity copper is then recovered through electro-refining. Umi-
core process uses e-waste (up to 10 wt%) as feedstock for recover-
ing copper and precious metals in the metallic phase, followed by
subsequent purification in a leach–electrowinning plant (Schluep
et al., 2009). While these processes can be used to recycle large vol-
umes of e-waste without producing significant levels of secondary
wastes, these multi-stage techniques recover copper in an indirect
manner. It is important to note that the copper present initially in
waste PCBs generally has quite high purity. These processes how-
ever treat e-waste as an impurity/copper ore and carry out high
temperature oxidation of pure copper followed by its reduction
and purification in order to extract copper. Some of these processes
were developed nearly 20 years ago, have low energy efficiency/
productivity and do not represent the state-of-the art recycling
technology.
1.2. Hydrometallurgical techniques
Hydrometallurgy has been used widely to extract copper from
e-waste; these techniques generally include mechanical process-
ing/size reduction followed by extraction through chemical leach-
ing/reactions. Behnamfard et al. (2013) size reduced waste PCBs in
a hammer crusher followed by pulverisation to particles sizes
300 lm. These powders were then leached in a sulphuric acid
solution in the presence of hydrogen peroxide for 3 h/200 rpm/-
room temperature. Up to 85.76 wt% copper was extracted as Cu2+
ions in solution; remaining copper could also be recovered through
repeated leachings. However, these solutions contained other
metallic ions such as Zn2+, Sn2+, Fe2+ and Ni2+ in addition to copper
ions. Silvas et al. (2015) used a number of process steps including
size reduction, magnetic separation and two chemical leachings
with H2SO4 and H2SO4/H2O2 to recover copper. Recovered copper
solution contained Al and Zn as impurities and required further
purification/electrowinning steps. Secondary wastes produced
included magnetic fractions, chemical effluents and residual solids.
Zhang and Zhang (2014) used an eight-step process for the
recovery of copper; waste PCBs were first heat treated at 270 °C
to improve their crushing efficiency. The material was then
crushed in a hammer mill, followed by air separation. The metallic
fraction obtained in the separation step was mechanically pro-
cessed in a cutting mill to obtain 0.25 mm particle sizes. The mate-
rial was then leached in a solution of CuSO4
5H2O and NaCl at
60 °C. After two filtration processes, copper was recovered in the
form of cupreous chloride. Although 98.5% copper recovery was
achieved, this approach used a number of process steps, producing
significant amounts of residual chemicals, spent acids, non-
metallic fractions, etc. Ou and Li (2015) used mechano-chemistry
to recover copper, an approach involving the grinding and mixing
of waste PCB samples with sulphur powder. The mixture was
ground in a ball mill for 20 min to form copper sulphide; followed
by leaching into a 3 M sulphuric acid solution containing 30 wt%
hydrogen peroxide. While up to 95% copper could be recovered
in a solution form, other impurities were also present in this solu-
tion; additional steps were required to recover metallic copper.
Spent acids and resin residues were generated as secondary waste.
While successful in recovering copper, these techniques are
severely limited by the volumes of waste processed, significant
levels of waste handling/initial processing and by the amounts of
secondary wastes produced, thereby making large scale e-waste
recycling and copper recovery economically and environmentally
unviable.
Please cite this article in press as: Cayumil, R., et al. High temperature investigations on optimising the recovery of copper from waste printed circuit
boards. Waste Management (2017), http://dx.doi.org/10.1016/j.wasman.2017.01.001
1.3. Pyro-metallurgical techniques
Long et al. (2010) heated waste PCBs to 550 °C at a heating rate
of 10 °C/min under vacuum, kept these at 550 °C for 2 h followed
by quenching. Solid pyrolysis residues containing glass fibres, cop-
per and carbon were then crushed to fine powders and separated
into heavy and light fractions using gravity separation. While up
to 99 wt% of copper could be recovered in the heavy fraction, this
approach required four process steps, and produced secondary
waste in the form of oils and light fractions. Zhou et al. (2007) used
a multi-stage pyro-metallurgical approach to recover copper and
other metals. Waste PCBs were mixed with 12 wt% NaOH and heat
treated at 1200 °C under reducing atmosphere to produce two
types of solid fractions: a metallic fraction containing Fe, Cu, Pb
and precious metals, and a slag phase containing SiO2, Al2O3 and
CaO. The Cu concentrations in the metallic and the slag phase were
determined to be 82 wt% and 0.15 wt% respectively. The metallic
fraction was then heat treated at 1200 °C under air; the Cu2O thus
generated was reduced with pyrolysis gas to obtain metallic cop-
per; secondary wastes produced included up to 30% copper as
Cu2O slag.
Zhan and Xu (2011) crushed waste PCBs in a high speed shear-
ing machine, followed by hammer grinding, sieving and the sepa-
ration of metallic and non-metallic fractions using a corona
electrostatic separator, followed by vacuum pyrolysis of these
powders at 850 °C. Most of the copper was recovered in the form
of (Cu, Pb, Sn) alloys containing up to 92.93 wt% Cu, 2.38 wt% Pb,
3.57 wt% Sn, and small amounts of non-metallic fractions.
Cayumil et al. (2014) carried out high temperature pyrolysis of
waste PCB chips in the temperature range 1150–1550 °C for times
up to 20 min under argon atmosphere; copper was recovered in
the form of copper rich and lead rich alloys. While pyro-
metallurgical approaches do not produce much residual waste
such as spent acids etc. and can significantly reduce the volumes
of waste after processing, careful attention needs to be paid to
the gaseous emissions from PCBs during exposure to high temper-
atures. The generation of harmful brominated compounds, dioxins,
furans from polymer degradation can be a serious issue for pro-
cessing at low temperatures. However, the generation of dioxins/-
furans is known to become negligible at temperatures above
800 °C (Mckay, 2002).
1.4. Other approaches
Xiu and Zhang (2009) investigated the recovery of copper from
waste PCBs using supercritical water oxidation and an electroki-
netic process. PCBs were size reduced in a cutting mill to get par-
ticles sizes  0.1 mm. The material was then dissolved in solution
of distilled water and hydrogen peroxide; and inserted in a reactor
consisting of two electrodes and kept at 713 K and 30 MPa for
60 min. Electrodes were then leached in a 5 M HNO3 solution for
several hours (overnight). The recovery of copper achieved was
84.2%, of which 74% was deposited on the cathode. In this four-
step process, other impurities were present in the spent solutions,
and solid residues were generated as secondary waste. Fogarasi
et al. (2014) investigated the recovery of copper and the concentra-
tion of gold from waste PCBs by using electrochemical oxidation
without any mechanical processing. The process consisted of
leaching the samples into an acidic ferric chloride solution (0.3 M
HCl + FeCl3) and electrowinning at 4 mA/cm2 density. Up to 99%
copper was recovered in the form of a deposit, along with a gold
rich residue. The process was improved further by adjusting the
flow rate in the leaching step and in the deposit of copper in the
EW process (Fogarasi et al., 2015). Bioleaching has been also used
as an alternative process to recover copper from waste PCBs. How-
ever, the process took a very long time to leach the metal (Wang
 R. Cayumil et al. / Waste Management xxx (2017) xxx–xxx 3

et al., 2009; Yamane et al., 2011), and required an additional pre-
cipitation step to recover copper from the solution (Chenglong
et al., 2010).
While a number of techniques have been successful in recover-
ing most of the copper present in waste PCBs, these are still limited
by too much initial handling/mechanical processing, number of
process steps involved, quality/form of copper recovered, sec-
ondary waste generation, emissions as well as environmental con-
tamination. Waste PCBs being a valuable/extensive copper
resource, there is an urgent need for developing optimal process/
s for efficient copper recovery with minimal side effects or local
area contamination. In an previous study by our group (Cayumil
et al., 2014), waste PCB pieces (1 cm2) were heat treated at high
temperatures (P1150 °C) for 10–20 min in argon atmosphere. As
these temperatures were above the melting point of copper
(1085 °C), this study was an attempt to melt copper out of the
PCB matrix. While most of the copper could indeed be extracted,
it was recovered in the form of copper rich and tin-lead rich metal-
lic droplets. The use of inert atmosphere prevented the re-
oxidation of metals and the burning of carbons. This single step
process did not produce any secondary waste, as the carbonaceous
slag phase produced as a side product, was transformed into
value–added carbon foams and fibres (Khanna et al., 2015).
However, these pyrolysis temperatures were higher than the
melting points of both lead (327.5 °C) and tin (231.9 °C), other
two key metals present in waste PCBs; these molten metals tended
to diffuse into molten copper and form Cu-Pb-Sn alloys. As the
kinetics of diffusion of Pb and Sn is likely to be much slower in
solid copper, we carried out in-depth investigations on waste PCBs
at temperatures below the melting point of copper. In this article,
we report on the high temperature pyrolysis of waste PCBs in the
temperature range 800–1000 °C for 10–60 min in argon atmo-
sphere. These temperatures are also high enough to either destroy
or stop the formation of hazardous emissions such as poly-
halogenated dioxins (PCDDs/PBDDs) and furans (McKay, 2002;
Striebich et al., 1991). Detailed characterization of pyrolysis resi-

Fig. 1. A schematic representation of the experimental arrangement.

Fig. 2. Representative examples of copper rich products generated after 10, 20, 30 and 60 min of heat treatment of waste PCBs at 800 °C, 900 °C and 1000 °C.

Please cite this article in press as: Cayumil, R., et al. High temperature investigations on optimising the recovery of copper from waste printed circuit
boards. Waste Management (2017), http://dx.doi.org/10.1016/j.wasman.2017.01.001
4 R. Cayumil et al. / Waste Management xxx (2017) xxx–xxx
Fig. 3. Relative concentrations of Cu, Pb and Sn in: (A) Copper rich metallic fraction,
(B) Tin/lead rich metallic residue (C) Carbonaceous/slag residue after 10 min of heat
treatment.
Fig. 4A. Influence of heating times on copper concentrations in the copper rich
fractions generated at 800 °C, 900 °C and 1000 °C.
dues was carried out using a variety of analytical techniques. The
aim of the present investigation is to enhance the quality of copper
recovered from waste PCBs, while optimising the process efficiency
and the environmental sustainability of the overall process.
Please cite this article in press as: Cayumil, R., et al. High temperature investigations on optimising the recovery of copper from waste printed circuit
boards. Waste Management (2017), http://dx.doi.org/10.1016/j.wasman.2017.01.001
Fig. 4B. Influence of heating times on lead and tin concentrations in the copper rich
fractions generated at 800 °C, 900 °C and 1000 °C.
2. Experimental
Waste PCB specimens in this study were taken from a variety of
waste boards such as computers/mobiles/mother boards etc. and
represent a generic e-waste mix. These were size reduced by cut-
ting and manual crushing to typical sizes  1 cm2 and
weights  2 g. Average concentrations of key metals in these raw
PCBs were  13.3% Cu, 4.8% Pb and 3.1% Sn. High temperature
investigations were carried out in a horizontal tube furnace with
inner dimensions as: 1 m length, 5 cm internal diameter, wall
thickness 5 mm (Fig. 1). The temperature near the edges of the fur-
nace (20 cm; the cold zone) was generally  200–300 °C;
whereas the experimental temperatures were maintained in the
central region, (15 cm; the hot zone) with the help of thermocou-
ples. The furnace tube was purged with 99.99% pure argon
throughout the duration of the experiment with a flow rate of
1.0 L/min. The PCB specimens (1 cm2) were placed on an alumina
tray (1 cm  2 cm) and mounted on a sample holder. The assembly
 R. Cayumil et al. / Waste Management xxx (2017) xxx–xxx 5

was held in the cold zone for  10 min to avoid thermal shock, and
was then inserted into the hot zone of the furnace preventing any
reactions occurring at lower temperatures. The temperatures in the
cold zone were below typical polymer degradation temperatures;
the direct insertion of PCB specimens into the hot zone (800–
1000 °C) therefore prevented emissions associated with low tem-
perature polymer degradation as well as the diffusion of Pb and
Sn into copper during the heating process. The assembly was
quenched after fixed periods of reaction time (10–60 min) by with-
drawing the tray into the cold zone of the furnace. Studies were
carried out at a range of temperatures/time for sake of optimiza-
tion. Experiments were repeated at least three times at each tem-
perature/time to enhance the reproducibility of results, and to
compensate for the initial variability in raw waste specimens.
The deviation on the results could be up to ±5%. Solid products
obtained after various heat treatments had phase separated into
a metallic fractions: copper rich red foils/wires/droplets, lead &
tin rich white droplets/wires and a dark carbonaceous slag phase.
Detailed investigations carried out on metallic phases using tech-
niques such as Scanning Electron Microscopy (SEM)/Energy Dis-
persive Spectroscopy (EDS) on model Hitachi 3400X SEM;
elemental analysis using Inductively Coupled Plasma Optical Emis-
sion Spectrometry (ICP-OES) using model Perkin Elmer Optima
7300DV; X-ray diffraction (XRD) on PANanalytical Xpert Multipur-
pose X-ray Diffraction System. Detailed results on metallic prod-
ucts recovered from waste PCBs heat treated at 800–1000 °C for
10–60 min, are presented in the following section.
3. Results
Solid residues recovered after pyrolysis were in the form of red
and white metallic fractions and a dark carbonaceous slag residue.
A full characterization of the carbonaceous/slag residue has been
reported previously (Sahajwalla et al., 2015). Representative exam-
ples of copper rich metallic phases recovered after various heat
treatments are shown in Fig. 2. While most of the foils recovered
at 800 °C were coppery red in colour, fractions recovered at higher
temperatures and longer times had additional dark coloured
deposits on the foil surfaces. The relative concentration of these
deposits was highest after pyrolysis at 1000 °C for 30 and 60 min.
Further results are given below.
3.1. Chemical composition of pyrolysis residues
Detailed elemental analysis of various fractions was carried out
using ICP-OES. Relative proportions of three main metals, i.e, Cu, Sn
and Pb in the copper rich, lead/tin and carbonaceous residues are
presented in Fig. 3 for a range of pyrolysis temperatures after
10 min of heat treatment. Corresponding results from pyrolysis
at 1250 °C, typical temperature used during commercial recycling
of e-waste, have also been included for sake of comparison. The
copper rich fraction (Cu: 87.5%) contained low levels of Pb (0.3%)
and Sn (3.1%) after pyrolysis at 800 °C (Fig. 3A). While the corre-
sponding concentrations of Pb and Sn had increased somewhat at
900 °C and 1000 °C, significantly higher levels of Pb (6.4%) and Sn

Fig. 5. SEM-EDS analysis of copper-rich foils after 20 min of heat treatment at 800 °C.

Please cite this article in press as: Cayumil, R., et al. High temperature investigations on optimising the recovery of copper from waste printed circuit
boards. Waste Management (2017), http://dx.doi.org/10.1016/j.wasman.2017.01.001
6 R. Cayumil et al. / Waste Management xxx (2017) xxx–xxx
(9.9%) were observed after pyrolysis at 1250 °C. While the pyroly-
sis temperature did not have much influence on the loss of copper
in the white Pb/Sn rich metal fraction (Fig. 3B), the presence of cop-
per in the carbonaceous residue had reduced significantly at lower
temperatures: 0.2% at 800 °C as compared to 1.5% at 1250 °C
(Fig. 3C). Fig. 4A shows the influence of pyrolysis time on the cop-
per recovery in the temperature range 800–1000 °C. These results
point towards two specific features. There was a marginal influ-
ence of heating time on the extent of copper recovered; variations
observed were typically within statistical errors. It is quite likely
that most of the copper had already precipitated out of waste PCBs
within the first 10 ten minutes; additional heating for up to 60 min
did not serve much purpose. Extended heating at 800 °C was actu-
ally detrimental to the quality of copper recovered due to increased
levels of Pb and Sn in the copper foils. Corresponding levels of Pb
and Sn present in copper rich fractions are shown in Fig. 4B. At
800 °C, the concentration/diffusion of lead and tin into copper were
found to increase with time. While the extent of such an increase
was quite small at 900 °C, the corresponding results at 1000 °C
showed an increase till 20 min followed by a rapid decrease at
longer times. This behaviour was attributed to the enhanced
volatility of both lead and tin at high temperatures, and their loss
in the vapour phase. In addition to these two metals, other metals
such as Ni, Zn, Fe, Al, Mg and precious metals Ag, Au, Pt, Pd were
also present in trace quantities. A detailed report on the behaviour
of precious metals under these operating conditions has been pre-
sented elsewhere (Cayumil et al., 2015).
Fig. 6. SEM-EDS analysis of copper-rich foils after 20 min of heat treatment at 900 °C.
Please cite this article in press as: Cayumil, R., et al. High temperature investigations on optimising the recovery of copper from waste printed circuit
boards. Waste Management (2017), http://dx.doi.org/10.1016/j.wasman.2017.01.001
3.2. Electron microscopy investigations
In-depth SEM-EDS investigations were carried out on the cop-
per rich fractions recovered after various heat treatments. Fig. 5
shows a microscopic analysis of a copper rich foil recovered after
20 min of heat treatment at 800 °C. Fig. 5a shows a relatively pla-
nar but somewhat granular sheet composed mainly of copper
(Fig. 5a; ‘A’) along with trace amounts of Sn and Zn. The regions
near the edge of the foil showed a lamellar structure; the elemental
composition of this region was very similar to the bulk copper foil.
However, a few bright deposits containing small amounts of Pb, Zn,
Cu, C and O could also be seen in these areas (Fig. 5b; ‘B’). In addi-
tion, a small number of bright droplets (Fig. 5c; ‘C’), representing
molten Cu-Sb alloys were also detected as well; their sizes were
found to typically range between 1 and 2 lm. The SEM-EDS analy-
ses of copper rich fractions obtained after 20 min of heat treatment
at 900 °C are presented in Fig. 6. Instead of the lamellar structure
observed at 800 °C, the copper foil (Fig. 6a; ‘A’) was overlaid with
a number of metallic droplets (Fig. 6b; ‘B’) and locally melted
regions (Fig. 6c; ‘C’). While the region ‘A’ was almost pure copper,
the EDS analysis of the region ‘B’ showed Sb-Sn droplets embedded
on the surface of the copper foil. Partially molten and lamellar
region ‘C’ was predominantly composed of Pb with trace amounts
of C and O. In addition, several carbonaceous deposits were also
recorded near the edge of copper foils (see top left region in
Fig. 6a). These regions represent some of the carbonaceous residue
adhering to the copper foils after pyrolysis. A closer look at these
 R. Cayumil et al. / Waste Management xxx (2017) xxx–xxx 7

Fig. 7. SEM-EDS images of carbonaceous regions on copper-rich foils after heat treatment at 900 °C.

dark deposits is presented in Fig. 7. These regions contained a large addition, several lead rich partially melted deposits (Fig. 9b; ‘B’)
concentration of Cu-Sb metallic droplets (Fig. 7b; ‘B’), with sizes were also observed on the droplet surface. The composition of
ranging from 2 to 16 lm; these sizes are much larger than corre- the copper recovered was found to evolve with pyrolysis
sponding droplets observed after 800 °C pyrolysis. There were temperature.
additional bright deposits (Fig. 7c; ‘C’) on the surfaces of these dro-
plets; these were primarily composed of Pb, C and O.
3.3. X-ray diffraction investigations
While the copper rich foils were the main product after heat
treatment at 1000 °C, a few copper rich droplets were also pro-
X-ray diffraction analysis was carried out on copper foils recov-
duced indicating the molten state of these alloys at this tempera-
ered after heat treatments at 800 °C and 900 °C for 20 min. The
ture. The SEM-EDS analyses of copper-rich foils and droplets
focus here was on identifying any loss of structural order and pre-
have been presented in Figs. 8 and 9 respectively. The SEM-EDS
ferred orientation, if any, in the copper foils recovered after pyrol-
images of copper foils recovered after pyrolysis at 1000 °C are
ysis. Detailed X-ray diffraction patterns are presented in Fig. 10.
shown in Fig. 8; the results in Fig. 8a–c are shown with increasing
These results show the well-known diffraction pattern for FCC cop-
levels of magnification. Fig. 8a clearly shows the presence of mol-
per; the peak positions and relative intensities of different peaks
ten lead in the grain boundaries on the top surface of the copper
were as per the standard pattern. Except for the presence of a small
foil. Several other deposits could also be seen across the surface;
peak corresponding to PbSb2O6, these results identify the copper
three distinct regions ‘A’, ‘B’, and ‘C’ could clearly be identified.
foils recovered from waste PCBs as being crystalline copper. No
The top surface of the foil (Fig. 8a; ‘A’) was a predominantly Cu-
preferred orientation was observed, thereby indicating the absence
Pb alloy; this result is a significant variation from the pure copper
of localised melting and subsequent solidification of partially
foils recovered at 800 °C and 900 °C. The droplets ‘B’ (Fig. 8b) seen
melted copper in these foils. These X-ray diffraction results are in
on the surface were much depleted in copper and were determined
good agreement, and consistent with ICP and SEM-EDS results on
to be a mixed alloy of Pb and Sn. Deposits of Pb (Fig. 8c; ‘C’) on the
these copper foils, and are indicative of the high quality of copper
top of these droplets appear to represent the precipitation of lead
recovered.
vapour upon quenching. The SEM-EDS images of the copper rich
droplets recovered after 1000 °C pyrolysis are shown in Fig. 9.
The surface region of these primarily Cu-Sn droplets (Fig. 9a; ‘A’) 4. Discussion
was not smooth and appeared to contain several bulges, channels
that appeared to be partially melted regions. A very large number The temperature range (800–1000 °C) used in this investigation
of small droplets were also recorded on the droplet surface. In resulted in the phase separation of pyrolysis products from waste

Please cite this article in press as: Cayumil, R., et al. High temperature investigations on optimising the recovery of copper from waste printed circuit
boards. Waste Management (2017), http://dx.doi.org/10.1016/j.wasman.2017.01.001
8 R. Cayumil et al. / Waste Management xxx (2017) xxx–xxx

Fig. 8. SEM-EDS analysis of copper-rich foils after 20 min of heat treatment at 1000 °C.

Fig. 9. SEM-EDS images for copper-rich droplets after 20 min of heat treatment at 1000 °C.

Please cite this article in press as: Cayumil, R., et al. High temperature investigations on optimising the recovery of copper from waste printed circuit
boards. Waste Management (2017), http://dx.doi.org/10.1016/j.wasman.2017.01.001
 R. Cayumil et al. / Waste Management xxx (2017) xxx–xxx
Fig. 10. X-ray diffraction analysis of copper-rich foils obtained after heat treatment
at 800 °C and 900 °C.
PCBs into metallic and non-metallic fractions. The metallic phase
was generated in the form of ‘red’ foils/droplets and ‘white’ dro-
plets, while the non-metallic fraction was in the form of a carbona-
ceous/slag residue. The elemental analysis of the resulting ‘red’,
‘white’ and carbonaceous/slag fractions showed that the concen-
tration of Pb and Sn in the copper rich fractions was significantly
lower than the corresponding results from pyrolysis at 1250 °C
(Fig. 2). Due to their limited solubility in solid copper, the physical
state of copper (solid vs molten) was found to play an important
role in the pickup of Pb and Sn by copper during pyrolysis. The
ICP-OES analysis results in the present investigation were found
to be consistent with these observations. The presence of lead in
the copper rich fractions, detected only at 1000 °C is more likely
to have been caused by the precipitation of lead vapours than solid
state diffusion. Tin on the other hand has a higher affinity for cop-
per and was present in higher concentrations in copper fractions. A
small loss of copper was found to occur in the white droplets that
could be attributed to a localised/partial melting of copper or to the
difficulty of its separation from Sn at lower temperatures and short
heating times. Higher levels of localised copper melting were
observed at 1000 °C as indicated by the formation of Cu-rich dro-
plets. The Pb-Sn solders are a likely source of small amounts of
Sb present that is known to form solid solution with copper at
these temperatures (Predel, 2012). As antimony is molten at the
operating temperatures (M.P. 630.6 °C), it showed a tendency to
accumulate and concentrate in the copper fraction (Haynes, 2014).
The focus of earlier research on managing e-waste was primar-
ily on developing recycling approaches as alternatives to landfilling
and incineration. Key issues for these studies were managing large
volumes of waste being produced, reducing their volumes to
manageable proportions and to recover materials wherever possi-
ble. E-waste was generally regarded as being too complex for a
Please cite this article in press as: Cayumil, R., et al. High temperature investigations on optimising the recovery of copper from waste printed circuit
boards. Waste Management (2017), http://dx.doi.org/10.1016/j.wasman.2017.01.001
9
complete physical/chemical separation, and was seen as contain-
ing far too many constituents. Recent developments in the field
are however making consistent efforts towards recovering pre-
cious and other materials, along with reductions in secondary
waste generation and environmental impact. One of the key find-
ings in our earlier study on high temperature pyrolysis of waste
PCBs at P1150 °C (Cayumil et al., 2014), was that the thermal
degradation of polymers, metals and ceramics occurred in different
temperature regimes and that the degradation of these con-
stituents did not interfere much with each other. While the poly-
mer degradation was more or less complete by 600–700 °C; the
segregation of metals from waste PCBs occurred predominantly
in the temperature regime: 700–1400 °C; ceramics and other oxi-
des were still stable at these temperatures and tended to separate
out as residual fractions. Low melting point metals such as Pb and
Sn continued to remain in the metallic phase to a certain extent
and their loss as volatiles became significant only at high temper-
atures. These observations suggest that it may be possible to
untangle the overall complexity of waste PCBs to a great extent
by choosing appropriate operating temperatures and their well-
known material characteristics/behaviour could be exploited
towards optimal material recovery.
There were several key features of this study, which played an
important role in the recovery of copper from waste PCBs in a
single step. The operating temperatures for the pyrolysis of PCBs
under inert atmosphere were chosen in the range 800–1000 °C.
Low temperature (up to 700 °C) pyro-metallurgical approaches
including open burning, incineration, and pyrolysis are known
to have a significant environmental impact in terms of hazardous
and/or toxic emissions and secondary wastes generated. While
most of the polymer degradation would have been completed
by 800 °C; this temperature and operating time (P10 min) is suf-
ficient to completely stop the generation of dioxins/furans from
degrading polymer. However copper, the main metal present in
waste PCBs, will still be solid at 800 °C (M.P. 1085 °C); the diffu-
sion of molten Pb and Sn into solid copper is likely to be much
slower than their corresponding diffusion in molten copper (e.g.
at 1250 °C; typical temperatures used for copper recovery). The
upper temperature bound of 1000 °C was chosen to lie below
the melting point of copper. However our results show that there
was a significant diffusion of both Pb and Sn at this temperature
and for longer times at lower temperatures. In this study, PCBs
were inserted directly in the hot temperature zone from the cold
zone (200–300 °C) and did not spend any time at intermediate
temperatures. This approach slowed down the diffusion of Pb
and Sn and the generation of dioxins/furans at lower tempera-
tures. In typical furnaces, it is a common practice to insert spec-
imens in the furnace at room temperature and heat these to the
set temperatures at certain heating rates. The PCBs are thus
exposed to a wide temperature range and extended heating times
making the segregation of different constituents difficult to
control.
Our results from ICP-OES analysis, SEM-EDS and X-ray diffrac-
tion have clearly shown that copper foils could be recovered from
waste PCBs in a single step of pyrolysis at 800–900 °C for times
between 10 and 20 min. It was also noticed that the mechanical
crushing or powdering of PCBs was not really necessary. Although
small PCB pieces (1–2 cm) were used in these laboratory investiga-
tions, these limitations were due to the small size of the furnace
used. We have carried out a few studies in larger furnaces where
an entire PCB or larger pieces of 10 cm  10 cm could be directly
inserted into high temperatures. Sheets of copper were recovered
easily from these scaling studies without any difficulty. We also
carried out on some experiments on powdered PCBs; however
the overall phase separation and copper extraction was not very
successful in this scenario.
10 R. Cayumil et al. / Waste Management xxx (2017) xxx–xxx
5. Conclusions
A number of key results were obtained on optimising the recov-
ery of copper from waste PCBs in the temperature range 800–
1000 °C for 10–60 min under inert atmosphere. These are sum-
marised below:
1. This study has shown that it may be possible to optimise the
recovery of copper from waste PCBs through a judicious choice
of operating temperatures and heating times. Pyrolysis temper-
atures below the melting point of copper and short heating
times were found to play an important role in limiting the dif-
fusion/pickup of lead and tin in the copper rich fractions.
2. Copper foils with lead and tin levels as low as 0.3% and 3.1%
were recovered directly in a single step from the pyrolysis of
waste PCBs (800 °C, 10 min). Results from the pyrolysis at
900 °C were also quite promising. However, the impurity levels
in the recovered copper were found to increase with increasing
temperatures and heating times. Low levels of impurities pre-
sent in recovered copper are likely to reduce its further refin-
ing/processing for commercial applications.
3. While the loss of copper in Pb-Sn rich white metallic phase was
unaffected by the pyrolysis temperature, the corresponding loss
of copper in the carbonaceous phase was significantly lower in
the temperature range 800–1000 °C as compared to the corre-
sponding loss at 1250 °C, typical temperature used for recycling
e-waste.
4. As the temperatures proposed here are much lower than typical
temperatures currently being used, these coupled with short
operating times could significantly reduce the overall energy
consumption during e-waste recycling, enhance copper recov-
ery, process efficiency and the environmental sustainability of
e-waste management.
Acknowledgments
Romina Cayumil gratefully acknowledges the support from
CONICYT PhD scholarship from Chile. The authors would like to
express their gratitude to the Mark Wainwright Analytical Centre
Electron Microscope and Solid State & Elemental Analysis Units,
the University of New South Wales. Special thanks are due to
Rabeya Akter from ICP Laboratory for her help.
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