Surface & Coatings Technology 224 (2013) 71–76

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Surface & Coatings Technology

journal homepage: www.elsevier.com/locate/surfcoat

A simple method for acrylonitrile butadiene styrene metallization

M. Bazzaoui a, b,⁎, 1, J.I. Martins a, E.A. Bazzaoui c, A. Albourine b, R. Wang d, Po-Da. Hong e
a
Equipe de Chimie de Coordination, Laboratoire des Matériaux et Environnement, Département de Chimie, Faculté des Sciences, Université Ibnou Zohr, B.P. 8106, Agadir, Morocco
b
Faculdade de Engenharia, Departamento de Engenharia Química, Universidade do Porto, Rua Roberto Frias, 4200-465 Porto, Portugal
c
Faculté des Sciences, Département de Chimie, Université Mohammed Ier, 60000 Oujda, Morocco
d
Department of Mechanical Systems Engineering, Faculty of Engineering, Hiroshima Institute of Technology, 2-1-1 Miyake, Saeki-ku, Hiroshima 731-5193, Japan
e
Department of Materials Science and Engineering, National Taiwan University of Science and Technology, Taipei 10607, Taiwan

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

Article history: The metallization of acrylonitrile butadiene styrene (ABS) has been achieved using a new direct plating
Received 16 April 2012 process that consisted of a previous treatment by polypyrrole (PPy) to transform the plastic conductor
Accepted in revised form 27 February 2013 followed by direct copper electroplating. The deposition of PPy on ABS samples is reached chemically in a
Available online 15 March 2013
solution of pyrrole and iron(III) chloride as oxidant. The PPy synthesized is adherent to the plastic surfaces.
Adherent copper layers with different thicknesses have been obtained on PPy/ABS at different electrolysis
Keywords:
Metallization
time. Energy dispersive X-ray spectroscopy (EDS) analysis revealed that copper is deposited on PPy/ABS
ABS surface. SEM analysis shows that increasing the electrolysis time increases the copper coating thickness.
Polypyrrole © 2013 Elsevier B.V. All rights reserved.
Electroplating
Polymerization

1. Introduction Afterwards, the conventional metal plating process on plastic has

Metal plating on non-conductor substrates has been widely used for
more than 20 years in many industrial fields, aiming to bring about me-
tallic properties on the surfaces. In particular, the metallization of plas-
tics has various manufacturing applications on automotive components,
cosmetic packaging, computers, toys, cell phones, clocks, watches and
various plastic appliances [1–4].
The conventional metal plating process generally starts after etch-
ing the plastic in a sulfuric–chromic acid bath and activation by tin/
palladium colloidal. After the activation of the surface, the electroless
metallization of copper or nickel is applied to achieve an electrical
conductivity on the plastic surface. At the last step, copper is directly
plated on the above pre-treated surfaces [5–7].
This process is generally expensive, toxic and necessitates
several complex steps [8–11]. Chromium is known as a human
carcinogen and a hazardous air contaminant. Moreover, the use
of precious metals such as palladium to activate the plastic sur-
face before the electroless procedure to produce the first conduc-
tive metallic layer usually makes the plating process expensive
and more complicated.
certain impact from an economic and environmental standpoint.
Thus, a method of simple, environment friendly and direct metalliza-
tion is required.
The treatment of non-conductive substrate for metallization from
chromic free etching solution has been reported in some researches
[12–14]. In these researches, the traditional chromic acid etching bath
was substituted by an etching solution containing sodium permanga-
nate and a mineral acid. The process included an activation solution of
palladium salt and an amine complexor. Comparable to the convention-
al method, this method is relatively friendly to the environment [15].
Recently, the metal plating on plastic is also carried out using mild
etch process, in which roughened plastic surface with individual cav-
ities allows a high degree of adhesion of metal deposit. The mild etch
can improve the high percentage of hydroxyl groups chemically
linked by atomic bridges composed of sulfur atoms [12].
Table 1
Electrolytic conditions for copper electroplating on PPy/ABS.

CuSO4, 5H2O 215 g/l

H2SO4 60 g/l
CUFLEX 500 MU BASE 1.6 ml/l
⁎ Corresponding author at: Faculdade de Engenharia, Departamento de Engenharia CUFLEX 500 brightness 0.8 ml/l
Química, Universidade do Porto, Rua Roberto Frias, 4200-465 Porto, Portugal. Temperature of the bath 23–26 °C
Tel.: + 351 225081779; fax: + 351 225081449. Anode Copper plate
E-mail address: bazzaoui@fe.up.pt (M. Bazzaoui). Cathode PPy/ABS sample
1
ISE member. Current density 33 mA/cm2

0257-8972/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.surfcoat.2013.02.050
72 M. Bazzaoui et al. / Surface & Coatings Technology 224 (2013) 71–76

A new surface activation for electroless plating on ABS was also
reported recently. The authors used biopolymer chitosan to fix
catalyst metal on the substrate by chemical sorption instead of
the physical sorption used in conventional techniques [13,14].
This method enhanced the adhesion of the film on the ABS sub-
strate at low-cost and environment-friendly surface activation
process.
Here in this paper, we show a new process free from chromium
and precious metal baths and no electroless method is required.
The chemical deposition of PPy on ABS is the key of this process. Ef-
fectively, the polypyrrole coating ensures the electric conductivity
of plastic sample [16–18], which allow its electroplating. This pro-
cess is achieved with only one step instead of many bath steps of
plastic chemical pre-treatment used in conventional methods.

Fig. 1. PPy synthesized on ABS electrode after 2 h stirring. a) SEM micrograph and b) EDS analysis spectrum.
 M. Bazzaoui et al. / Surface & Coatings Technology 224 (2013) 71–76
Fig. 2. Cyclic voltammograms in copper plating solution at 100 mV s−1 scanning rate.
a) PPy/ABS modified by slight amount of Cu and b) Cu bare.
2. Experimental
2.1. Chemicals
Pyrrole (98%) was purchased from Sigma, sulfuric acid (H2SO4, 96%)
from Riedel-deHaën and CuSO4, 5H2O (99.5%) from Panreac Quimica.
Bath additives of CUFLEX 500 MU BASE and CUFLEX 500 brightness
were imported from IMASA, (Industria de Maquínas Salvator, Porto,
Portugal). The products were used as received and water was distilled
before use. ABS was a commercial polymer (Novodur P2M Grade).
2.2. Polypyrrole deposition on ABS
The polypyrrole deposition on ABS substrates at room tempera-
ture was carried out as follows: Samples of ABS were immersed in a
solution of 0.3 M pyrrole (75 ml). After 1 h another solution of
0.9 M FeCl3 (25 ml) was slowly added drop wise into the stirred
monomer medium. The polymerization was achieved for 2 h with
constant mechanical stirring. The synthesized PPy/ABS was rinsed
several times with distilled water and ethanol.
2.3. Copper electroplating
The electrolysis was performed in a beaker of 200 ml, with copper
as anode and the PPy/ABS as cathode. The working electrode (4 cm 2)
was fixed to a copper wire and wholly exposed to electrolyte
73
medium. The electrolytic conditions of copper electroplating bath
are gathered in Table 1.
2.4. Electrochemical experiments
The electrochemical experiments were performed in a one-
compartment cell with three electrodes connected to Voltalab 80
Model PGZ potentiostat/galvanostat with pilot integration con-
trolled by Voltamaster 4 software. The PPy/ABS rectangular sheet
(1 cm 2 of surface) constitutes the working electrode. The behavior
was achieved in copper sulfate solution. The electrodes were rinsed
in water and ethanol and dried before each electrochemical exper-
iment. A stainless-steel plate was used as auxiliary electrode. All the
potentials were measured versus an Ag/AgCl (0.1 M KCl) reference
electrode.
2.5. Adherence test and characterization techniques
Adherence measurements were based on the standard sellotape
test (TESA-4204 BDF), which consists of cutting the film into small
squares, sticking the tape and then stripping it. The ratio between
the number of adherent film squares remaining and their total num-
ber gives the percentage of adherence.
Scanning electron microscopy (SEM) micrographs and energy
dispersive X-ray spectroscopy (EDS) analysis were performed in the Cen-
tre of Materials of Porto University (CEMUP), Portugal. The analysis was
obtained on high-resolution (Schottky) environmental scanning electron
microscope (ESEM) with X-ray microanalysis and backscattered electron
diffraction pattern analysis (FEI Quanta 400FEG/EDAX Genesis X4M).
3. Result and discussion
3.1. Pyrrole polymerization on ABS substrates
After 1 h of continuously stirring of ABS samples in 0.3 M pyrrole
(Py) solution, 0.9 M of FeCl3 is added. The polymerization is achieved
at the ABS surface and is maintained during 2 h following the reaction
þ0:33 −
nPy þ 2:33nFeCl3 →ðPy þ 0:33Cl Þn þ 2:33nFeCl2 þ 2nHCl:
The pyrrole oxidation is occurred and a black, homogeneous and ad-
herent PPy film is deposited on the ABS. SEM image shows that PPy coat-
ing is a globular structure with a grain diameter size of 0.3 to 0.5 μm
(Fig. 1a). The adherence was estimated at 100% by the normal sellotape
test. This result could be explained by the oxidation of adsorbed Py mol-
ecules on the ABS surface to produce nucleus of polypyrrole bonded to
ABS surface. Effectively, the pyrrole monomer reacts with ABS and
causes surface roughness in which crack and melting are observed on
the plastic. This behavior turns more aggressive and the ABS sample be-
comes sticky and viscous when the surface is immersed in pure pyrrole
during several minutes. This shows that concentration of pyrrole solu-
tion constitutes an important key to control the absorption of pyrrole
on ABS. Similar results have been reported by Patil et al. in the case of
polyaniline coated ABS [19]. They show that the interaction of aniline
with ABS is achieved with C`N group from acrylonitrile and acts as nu-
cleation sites for further polymerization process. In our case we think
that the pyrrole is fixed into the rubber by impregnation.
The EDS analysis (Fig. 1b) revealed the presence of carbon, oxygen
and chlorine from the polypyrrole and doping anion.
3.2. Copper electroplating on ABS substrates
3.2.1. Electrochemical behavior of PPy/ABS in copper plating solution
The voltammetric curves of PPy/ABS sample in copper plating
solution exhibits ohmic behavior during the potential range. The
74 M. Bazzaoui et al. / Surface & Coatings Technology 224 (2013) 71–76
Fig. 3. Photography of copper electroplated ABS. a) uncoated ABS, b) PPy/ABS and c) Cu/PPy/ABS.
obtained cyclic curves present very low current density, which con-
firms the low conductivity of the synthesized doped PPy coating. To
approve the conductivity, the electrode of PPy/ABS was polarized as
cathode in copper plating solution by applying a cathodic current
density of 33 mA cm −2 during 1 min. This step allows a partial re-
duction dedoping of PPy and a deposition of copper nucleus which in-
crease the PPy/ABS conductivity. The sample is then polarized
potentiodynamically in the same solution at scanning rate of
100 mV s −1. The voltamperometric curves revealed an oxidation
peak at E = 0.42 V which increased with an increasing number of
scans (Fig. 2a). This anodic peak didn't appear in the cyclic
voltammetric curves of Cu bare polarized in the same conditions
(Fig. 2b). These confirm that probably the observed oxidation peak
is attributed to PPy oxidation. The polypyrrole is oxidized doped
with sulfate counter anion from plating copper bath.
3.2.2. Electrodeposition of copper on PPy/ABS
Fig. 3 presents the result of different steps of the plating process.
The PPy film obtained chemically on ABS during 2 h, and copper coat-
ing deposited on PPy/ABS at 33 mA cm −2 during 15 min are homo-
geneous as is observed from the macroscopic images.
The electrodeposition of copper on PPy/ABS samples was investi-
gated galvanostatically by applying 33 mA cm −2 at different times.
The adherence test applied to different deposition time coating was
estimated at 100% leading to normal sellotape test and could be the
result of the copper bonding to PPy/ABS nucleus. SEM micrographs
(Fig. 4) show that during 30 min and 45 min electrolysis time copper
coating becomes compact, well-spread on the PPy/ABS without any
cracks. The copper coating obtained during 15 min is thin character-
ized by globular structure with grain size of 4 μm diameter. This mor-
phology is relatively like the PPy texture which shows that during the
first stage, copper deposition is formed following the PPy shape. The
longer electrolysis time influences the texture that changes to com-
pact structure as is observed with 30 min and 45 min of electrolysis
time. EDS characterization of this layer proved that the coating is
composed mostly of copper.
The thickness of the deposited Cu film was estimated by the fol-
lowing Eq. (1) [20]
Δm
θ¼ : ð1Þ
Sρ
The thickness average reached at 33 mA cm −2 is readily con-
trolled by the time of electrolysis. The longer is the electrolysis time,
the thicker is the copper thickness.
Where ρ is the metal density (in the case of copper, ρ =
8.92 g cm − 3), Δm is the experimental mass difference between the
blank and the coated PPy/ABS electrode and S is the coated electrode
area.
Table 2 summarizes the thickness calculated by the formula above
and the experimental thickness estimated from SEM cross section im-
ages of Fig. 4. The data show that the theoretical and the experimental
thickness averages are generally in line.
4. Conclusions
The copper metallization of ABS free from chromium and palladi-
um baths is successfully achieved after pre-treatment with PPy. Only
one step is required before direct electroplating that consists of PPy
polymerization on ABS, while, several and complex steps are required
in the conventional method of ABS electroplating.
 M. Bazzaoui et al. / Surface & Coatings Technology 224 (2013) 71–76 75

Fig. 4. SEM micrographs of copper electroplating on ABS previously treated by PPy at 33 mA cm−2 during a) 15 min, b) 30 min and c) 45 min.

The copper coating obtained is homogeneous and adherent with that the coating is compact without any cracks. The adherence of
controlled thickness from thin to thick coating. The EDS analysis con- the copper electroplated was estimated at 100% according to normal
firms the presence of copper on the ABS electrode and SEM reveals sellotape test. This simple procedure for metal plating on ABS shows
a promising feature in several industrial applications.
Table 2
Experimental and calculated thickness of copper plating on PPy/ABS.
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