J. Coat. Technol. Res.
, 15 (6) 1433–1442, 2018
https://doi.org/10.1007/s11998-018-0075-2
Direct electroplating of nickel on ABS plastic using polyaniline–
silver surface composite synthesized using different acids
Maryam Mehdizadeh, Mehdi Khorasanian , Seyyed Mohammad Lari Baghal
 American Coatings Association 2018
Abstract Nickel coating was directly electroplated on
acrylonitrile butadiene styrene (ABS) plastic substrate
using a new method. The substrate surface was first
coated by thin polyaniline film, then silver particles
were deposited on the surface in order to improve the
electrical conductivity. Three different acids (perchlo-
ric, nitric, and sulfuric acid) were used to synthesize the
primary polyaniline film. The method adopted in the
present study was not based on incorporation of silver
particles within the polyaniline matrix; rather, the
silver was deposited on the substrate surface. The
electrical conductivity of the samples was increased to
a level high enough for direct electroplating of nickel.
The sample synthesized using nitric acid showed the
finest grain size (1.57 lm) and greatest thickness of the
final nickel coating (57 lm). The sample synthesized
using sulfuric acid exhibited the lowest electrical
resistance (0.008 X). In addition, the nickel coating
deposited on the surface of the sample synthesized
using perchloric acid exhibited the strongest adhesion
to the substrate (5B according to ASTM standard).
Keywords Polyaniline, ABS plastic, Silver particles,
Nickel, Direct electroplating
Introduction
Metallization of plastics has been developed to obtain
materials that show the benefits of both plastics and
M. Mehdizadeh, M. Khorasanian (&),
S. M. Lari Baghal
Department of Materials Science and Engineering, Faculty
of Engineering, Shahid Chamran University of Ahvaz,
Ahvaz, Iran
e-mail: m.khorasanian@scu.ac.ir;
mehdikhorasanian@gmail.com
metals. Although plastics are low-cost materials with
high plasticity, their mechanical properties are not
comparable to those of metals. Metals however exhibit
good mechanical behavior and bright appearance,
while their density is higher than that of polymers.1
Various types of plastics can be metallized, amongst
which ABS is one of the most important and widely
used. It is a thermoplastic polymer with acrylonitrile
styrene base phase and dispersed butadiene phase.
This plastic is suitable for metallization because of the
selective dissolution ability of the dispersed butadiene
particles. Various organic solvents can be used to
dissolve the dispersed phase. The resulting pores can
act as good sites for formation of bonds between the
substrate and metallic coating.2
One of the most popular methods for metalizing the
surface of ABS is electroless plating, which creates a
thin conductive layer with thickness of 0.5–2 lm on the
substrate surface, resulting in electrical conductivity
adequate for electroplating. Before electroless plating,
the surface of the substrate should be treated using an
activator to produce active electrical sites. The most
practical activator used on industrial scale is palladium
(in the form of palladium chloride). Electroplating
using palladium is a very sensitive process consisting of
many different complicated steps. Another disadvan-
tage of this method is high materials and processing
costs and the problem of environmental pollution.3
The aforesaid disadvantages explain why scientists
have sought other methods for activating and metal-
lizing plastics. Ma et al.4 used gold nanoparticles for
ABS plating. In research by Xu et al.,5,6 electroless
plating of copper on the surface of ABS was carried
out with the aid of copper as an activator. Shi et al.7
carried out electroless plating on polyethylene tereph-
thalate using iron ions as activator. In another study by
Dechasit et al.,8 electroless plating of nickel on the
surface of ABS was carried out with the aid of nickel
and cobalt as activators.
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J. Coat. Technol. Res., 15 (6) 1433–1442, 2018
Conductive polymers can be categorized within the
group of intelligent materials because of their complex
dynamic structure. Polyaniline (PANI), polypyrrole,
and polythiophene are the most popular conductive
polymers. These polymers can be produced with a wide
range of properties.9
Polyaniline is one of the main conductive polymers,
also being the oldest. It was discovered in 1834 by
Runge and is known as aniline black.10 In 1912, Green
and Woodhead11 discovered that polyaniline can be
produced in various forms, ranging from insulator to
conductor. The importance of conductive polymers
became clear when the Nobel Prize in Chemistry was
awarded to Alan J. Heeger, Alan G. MacDiarmid, and
Hideki Shirakawa in 2000 for the discovery and
development of conductive polymers.12
The zigzag pattern of polyaniline is composed of
nitrogen groups and phenyl rings surrounded by p-
electron clouds (Fig. 1). Although polyaniline has
some structural similarities to other conductive poly-
mers, the presence of dual bonds, p bonds, and more
importantly, nitrogen atoms in the structure, results in
a different conductivity mechanism compared with
other conductive polymers.10,13
The method used in the present study is not based
on surface activation for electroless plating. By pro-
ducing a conductive polymer–metal surface composite
on the plastic substrate, the surface can be electro-
plated without the need to carry out the intermediate
electroless stage. It is important to note that the term
‘‘composite’’ in the present work does not have the
classic meaning. In the present work, a primary
polyaniline thin film was polymerized on the surface
of the substrate. After polymerization, deposition of
dispersed silver metal particles was performed on the
conductive polymer surface using hydrazine hydrate as
reducing agent; therefore, the substrate surface was
composed of silver particles nucleated on the polyani-
line substrate but not embedded within it, thus
providing the highest possible conductivity.
Experimental
Materials
ABS plastic from Tabriz Petrochemical Company was
used as substrate. To prepare PANI thin film, the
following materials were used: ethanol 96% (Zakaria
H
N N
N N
n nickel plating bath to improve the brightness and to
H
X 1– x
Fig. 1: Zigzag pattern of polyaniline
1434
Jahrom Co.), sulfuric acid 98%, hydrogen peroxide
30%, freshly distilled aniline monomer, perchloric
acid, and nitric acid (all from Merck), deionized water
and ammonium persulfate (Sinachemiran Co.). For
deposition of silver particles on the primary film, silver
nitrate and hydrazine hydrate (Merck) were used.
Boric acid, nickel chloride, nickel sulfate (Samchun
Chemical), and saccharine (C7H5NO3S) (Merck) were
used for nickel electroplating.
Procedures
Sample preparation
An ABS plate (2 mm thickness) was cut into
20 9 20 mm2 specimens. The samples were cleaned
by ethanol and etched using solution composed of
40 ml H2SO4 98% and 10 ml H2O2 30% for 5 min at
50C. Such etching forms microscopic holes on the
surface of ABS by dissolving the butadiene phase.
These holes increase the effective surface of ABS and
enhance the mechanical adhesion between the PANI
film and ABS surface.14
PANI synthesis on ABS surface
Freshly distilled aniline (2 ml) and acid (35 ml, 3
molar) were added to a flask and stirred until complete
dissolution. The specimens were soaked in the pre-
pared solution. Perchloric acid, nitric acid, and sulfuric
acid were used to prepare three different samples.
Then, fresh aqueous solution of ammonium persulfate
(APS) was added to the former solution. The samples
were left in the solution to extend polymerization for
about 6 h at 4–8C.
PANI–Ag surface composite synthesis
PANI-coated ABS specimens were soaked in aqueous
solutions of 5 g/l AgNO3 for 1 h, then dipped into 2%
vol. hydrazine hydrate solution. Therefore, the PANI-
Ag composite layer was prepared on the surface of the
ABS specimens.
Nickel electroplating
Nickel electroplating solution was prepared using 40 g/
l H3BO3, 40 g/l NiCl2, 300 g/l NiSO4, and 1 g/l
C7H5NO3S. Boric acid was used as buffer to control
the acidity, nickel chloride to increase the solution
conductivity and coating uniformity, and nickel sulfate
as source of nickel ions. Saccharine was added to the
refine the grains.15 The conductive ABS specimens
were finally placed in the nickel electroplating bath for
1 h at 50C under current density of 5 A/dm2.
 J. Coat. Technol. Res., 15 (6) 1433–1442, 2018

Surface characterization (B: benzene ring). C–N stretching caused a peak at

FTIR spectra
Fourier-transform infrared (FTIR) spectra of polyani-
line were obtained using a PerkinElmer RXI device.
Scanning electron microscopy (SEM)
SEM images were taken using a VEGA TESCAN
device equipped with an energy-dispersive x-ray spec-
troscopy (EDS) detector. The specimens were coated
by thin gold film prior to characterization.
Conductivity test
A four-point probe conductivity test setup was used for
measurement of the electrical resistivity of PANI and
PANI–Ag surface composites.
Adhesion testing
The TQC cross-cut adhesion test kit (master paint
plate) was used to measure the resistance of the nickel
coatings to separation from the substrate when a right-
angle lattice pattern was cut onto the coating.
Results and discussion
FTIR spectra
Figure 2 shows the FTIR spectra of the three kinds of
polyaniline synthesized using the different acids.
The peaks at around 1250 cm 1 correspond to
stretching of the amine bond. One of the major peaks
at around 1550 cm 1 is assigned to N=Q=N vibrations
(Q: quinoid ring). Other major peaks were located at
around 1480 cm 1 and assigned to N–B–N stretching
Perchloric acid
1555 1485 1238
1307
Transition %
1108 cm 1 for the specimens synthesized using per-
chloric acid and at around 1134 cm 1 for the other two
samples. The presence of a peak at about 1300 cm 1
indicates the protonation process. Finally, the presence
of a peak at around 800 cm 1 is assigned to C–H out-
of-plane vibrations during protonation.16
There are also some other, minor peaks. The peaks
at about 850 cm 1 correspond to vibration of C–H in
quinoid ring and N–H wagging of amine. The presence
of the peaks at around 880 cm 1 indicates C–H
vibration in the benzene ring. There are also some
peaks between 400 and 600 cm 1. HSO4 and SO24
anions were created during aniline polymerization by
APS. The peak at around 600 cm 1 indicates these
anions. There are also some other peaks due to sample
preparation for FTIR using KBr.
When sulfuric acid was used in the PANI synthesis
process, PANI protonation became more uniform than
when using the other acids. This explains the higher
conductivity of PANI synthesized using sulfuric acid.
On the other hand, PANI synthesized using sulfuric
acid showed the highest degree of protonation, leading
to red-shift of the quinoid and benzene peaks.17
The ratio of the peak intensity of the quinoid ring
(IQ) to that of the benzene ring (IB) is a measure of the
polyaniline oxidation state.18 As shown in Table 1, this
ratio was approximately 1 for all samples, indicating
formation of polyaniline in emeraldine salt state. In
summary, a thin film of (emeraldine) polyaniline was
formed on the surface of all three specimens. The
oxidation state of the thin films showed that the
conductive type of polyaniline was formed on the
surface of the specimens, as confirmed below by the
conductivity results.
Scanning electron microscopy (SEM)
Primary polyaniline thin film
As shown in Fig. 3, use of different acids in the
chemical synthesis process led to formation of polyani-
line with different morphology. The specimen synthe-
sized using perchloric acid (Figs. 3a and 3b) exhibited
the most uniform, most compact, flake-like morphol-
801 ogy. The polyaniline film synthesized using nitric

Nitric acid
1108 (Figs. 3c and 3d) or sulfuric acid (Figs. 3e and 3f)
showed granular morphology. Polyaniline synthesized
802
using nitric acid showed finer clusters and was more
1560 1485 1296 1241
Sulfuric acid
1134
Table 1: Oxidation state of polyaniline in different
798 samples
1554 1470
1300 1241
1134 IQ/IB IB IQ Type of sample
2000 1600 1200 800 400
Wave length (cm –1) 1.02 57 58 PANI synthesized using perchloric acid
0.87 64 56 PANI synthesized using nitric acid
Fig. 2: FTIR spectra of polyaniline synthesized on ABS 1.08 49 53 PANI synthesized using sulfuric acid
surface using (a) HClO4, (b) HNO3, and (c) H2SO4

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J. Coat. Technol. Res., 15 (6) 1433–1442, 2018
Fig. 3: SEM images at two different magnifications of polyaniline synthesized on ABS surface using (a), (b) HClO4, (c), (d)
HNO3, and (e), (f) H2SO4
uniform than that synthesized using sulfuric acid.
There were larger pores in the specimen synthesized
using sulfuric acid. It is predicted that the morphology
of the final nickel coating may be a direct function of
the morphology of the primary polyaniline thin film. If
the PANI thin film has a uniform and smooth surface
1436
without too many pores, the final nickel coating will
probably have smooth and uniform microstructure, as
well. It therefore seems reasonable to predict that the
nickel coating deposited on the specimen synthesized
using perchloric acid will show the most uniform
morphology with lowest concentration of imperfec-
 J. Coat. Technol. Res., 15 (6) 1433–1442, 2018

tions. The other two specimens showed less smooth

surface with some degree of imperfections such as
porosities. It seems that the specimen synthesized using
sulfuric acid will show the lowest uniformity and
highest concentration of imperfections. This is dis-
cussed in more detail below.

Polyaniline–silver surface composite

The SEM morphology of the polyaniline–silver surface

composites is shown in Fig. 4.
Table 2 presents the results of elemental composi-
tion analysis by EDS.
The silver content on the surface was obtained using
MIP image analysis software, being about 50% for all
three samples, an optimal concentration to provide
conductivity sufficient for direct electroplating. For all
three samples, there was a relatively uniform distribu-
tion of Ag particles on the surface of the primary PANI
film. It is evident that the surface morphology of the
primary PANI film could influence the size and
distribution of Ag particles. For the specimen synthe-
sized using HClO4 (Fig. 4a), the smooth surface of the
PANI film will have limited sites suitable for deposi-
tion of silver particles, so the silver particles showed
agglomerated appearance and a vertical growth pat-
tern was observed in some areas of the surface. On the
other hand, on the surface of the other two samples
with higher degree of nonuniformity and imperfec-
tions, there are many sites suitable for deposition of
silver; therefore, the Ag particles were more uniformly
distributed across the surface of the primary PANI
film. Use of sulfuric acid resulted in formation of the
highest concentration of surface porosities on the
PANI film and the most uniform distribution of silver
particles among the three samples. This is because of
the higher probability of mechanical interlocking
between the Ag particles and PANI surface.

Nickel coatings

Figure 5 shows the surface morphology of the three

samples after nickel electroplating.
Table 3 presents the results of grain size measure-
ments for the nickel coatings.
As predicted above, the surface morphology of the
primary PANI film indeed influenced the morphology
of the final nickel coating. The specimen synthesized
using nitric acid exhibited cauliflower morphology,
while the morphology of the nickel coating on the
other two samples was granular. As shown in Fig. 3
(lower-magnification images), the latter two samples
exhibited compact structure, while the polyaniline
layer treated using nitric acid showed a porous nature, Fig. 4: SEM images of polyaniline-silver synthesized on
indicating a large amount of high-energy area on the ABS surface using (a) HClO4, (b) HNO3, and (c) H2SO4

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J. Coat. Technol. Res., 15 (6) 1433–1442, 2018
Table 2: Results of chemical composition analysis by EDS at point A
Sample synthesized using HClO4 Sample synthesized using HNO3
wt.% at.% wt.%
C 2.62 19.34 5.87
N 0.12 0.73 3.02
Ag 97.26 79.93 91.12
surface appropriate for initiating nickel nucleation.
This sample showed smaller nickel grain size with
different morphology.
In addition, the size and distribution of Ag particles
can alter the growth behavior of the nickel coating.
The nickel coating created on the specimen treated
using perchloric acid exhibited large grains with
smooth surface, while the Ag particles agglomerated
on the surface with lower surface coverage compared
with the other two samples, indicating fewer nickel
nucleation sites with a higher degree of dispersion. The
result will be a granular surface of nickel with large
grains.
The higher amount of porosities on the surface leads
to a more uniform distribution of Ag particles for the
other samples. As a result, the deposited nickel coating
will show finer grain size due to the higher concentra-
tion of nucleation sites.
Figure 6 shows cross-sectional views of the samples
after nickel electrodeposition.
It is evident that the nickel coating on the specimen
treated with perchloric acid was thinner than for the
other two specimens. Coating growth occurred at a
slower rate for this specimen. There are few nucleation
sites with low growth rate, leading to a surface with
smooth coating and low thickness. The specimen
obtained using nitric acid showed the highest thickness
due to the higher rates of nucleation and growth of the
nickel coating on the surface of the sample. The third
sample showed a nickel coating with moderate thick-
ness due to the dual morphology of its surface, with
some parts being highly compact, surrounded by some
porosities.
Electrical conductivity
As the electrical conductivity is a fundamental variable
in the present study, the conductivity of the samples
was measured by a four-point probe method at each
stage of the production process. The results are
presented in Fig. 7.
According to Fig. 7, the polyaniline films synthe-
sized using sulfuric and nitric acid showed the lowest
and highest electrical resistance, respectively. Forma-
tion of the PANI–Ag surface composite increased the
conductivity by approximately tenfold. The electrical
conductivity is a direct function of the size and
distribution of conductive Ag particles. It is important
to note that polyaniline itself exhibits considerable
1438
Sample synthesized using H2SO4
at.% wt.% at.%
31.54 7.87 39.28
13.91 2.56 10.95
54.56 89.57 49.76
electrical conductivity, but insufficient for direct elec-
troplating of nickel. Deposition of silver on the PANI
surface can increase the conductivity to a higher level,
suitable for direct nickel deposition. As explained
above, the conductivity of the composite layer is a
function of the deposition pattern of Ag particles.
Nitric acid created a significant concentration of pores
on the PANI film, thus the PANI film treated using
nitric acid showed the lowest conductivity due to the
high fraction of discontinuities on the surface. After
deposition of Ag particles, this specimen showed the
least conductivity, again because of the presence of the
discontinuities. The PANI and PANI–Ag layers
treated using sulfuric acid showed the highest conduc-
tivity values. The surface of the PANI film showed
some compact and smooth areas, with a fraction of
pores around them. The surface discontinuities are less
apparent compared with the specimen synthesized
using nitric acid. The simultaneous absorption of a
significant volume of Ag particles by these pores
explains why this specimen showed the best electrical
behavior. In the case of the specimen treated using
perchloric acid, the smoothness of the surface was very
high, but this led to an agglomerated pattern of Ag
particles and reduced the electrical conductivity.
The data in Table 1 indicate that the oxidation state
was emeraldine based with approximately equal
amounts of amine and imine groups. However, proto-
nation leads to emeraldine salt formation, and the
percentage of protonation controls the conductivity.
When sulfuric acid was used in the PANI synthesis
process, the protonation of PANI was more uniform
than when using the other acids, representing a reason
for the higher conductivity of the PANI synthesized
using sulfuric acid.17 Another reason for the difference
between the magnitudes of the conductivity of the
coatings is their morphology, as the more compact the
morphology, the higher the conductivity. Therefore,
the PANI synthesized using nitric acid showed the
lowest conductivity because it lacks the above features.
Adhesion
The adhesion of the electroplated nickel coating to the
substrate was examined by cross-cut test. The results of
the cross-cut test were compared with the ASTM
D3359-09 standard. Images of the nickel coating
surface after the cross-cut test are shown in Fig. 8.

Fig. 5: SEM images showing morphology of nickel coating
for the samples synthesized using (a) perchloric, (b) nitric,
and (c) phosphoric acid
J. Coat. Technol. Res., 15 (6) 1433–1442, 2018
Table 3: Grain size and thickness of final nickel coating
on the three samples
Grain size Thickness
(lm) (lm)
Sample treated using 6.65 20
perchloric acid
Sample treated using nitric 1.57 57
acid
Sample treated using sulfuric 3.92 38
acid
The specimen synthesized using perchloric acid with
the highest adhesion was placed in category 5B
according to the relevant ASTM standard, while the
specimen synthesized using sulfuric acid exhibited very
poor adhesion, and was placed in class 0B. The
specimen synthesized using nitric acid exhibited rela-
tively good adhesion, being placed in class 3B. The
high adhesion of the specimen treated using perchloric
acid was expected because of its high degree of
uniformity and compactness. The Ni coating on the
surface was well bonded to the polyaniline–Ag com-
posite layer without considerable defects. The speci-
men treated using nitric acid showed a nonuniform
surface, but again the bonding to the substrate was
good, though not comparable to the former one. In the
case of the specimen treated using sulfuric acid, it
seems that the dual structure of the PANI film led to
low bonding strength to the substrate, resulting in the
weakest adhesion among the samples.
The nickel coating was formed on an uneven and
nonuniform surface. Thus, under the compressive
stress applied during the cross-cut test, the pores under
the nickel coating played a stress concentration role
and led to cracking and fracture of the nickel coating.
The main mechanism of adhesion between the
electroplated nickel coating and the PANI-Ag surface
composite is mechanical anchoring. Any feature
increasing the probability of mechanical interlocking
between the coating and PANI-Ag layer will enhance
the adhesion strength between them. The etching and
acid treatment in the PANI formation stage will
increase the roughness of the surface of the ABS
substrate, forming a large amount of pores that can
play the role of anchor points.2,19
In the case of using perchloric acid, the surface of
the PANI was compact and smooth. After deposition
of silver, a uniform spatial distribution of silver
particles formed on the PANI surface, resulting in
many suitable sites for nucleation of the nickel coating.
The final coating grew uniformly on a smooth and
uniform surface, resulting in high adhesion strength.
When using the other two acids, the roughness of the
resulting PANI-Ag surface composite showed a less
uniform distribution (with some regions of the surface
covered by large Ag particles and other points by tiny
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J. Coat. Technol. Res., 15 (6) 1433–1442, 2018

0.5 Polyaniline
0.437
0.45
Polyaniline-Ag comp.

Electrical resistivity (Ω)

0.4
0.35
0.3
0.25
0.2 0.174
0.15
0.096
0.1 0.063
0.05 0.017 0.008
0
1 2 3
Type of acid used in synthesis process

Fig. 7: Results of electrical resistance measurements on

samples treated using (1) perchloric, (2) nitric, and (3)
sulfuric acid

Ag deposits), causing the growth rate of the Ni coating

to vary. The final Ni coating was therefore formed on a
nonuniform base, resulting in reduced adhesion
strength.

Conclusions

• A new method was applied for direct electroplating

of nickel on ABS plastic.
• The method was performed in three stages, includ-
ing formation of a primary polyaniline thin film,
deposition of silver particles on the primary PANI
surface, and electroplating of nickel.
• The primary PANI thin film was produced via a
chemical synthesis route using three different acids:
perchloric, nitric, and sulfuric acid.
• The PANI thin film treated using perchloric acid
exhibited a flaky morphology with smooth and
compact surface. The other two samples showed
granular morphology full of pores and imperfec-
tions.
• The size and distribution of Ag particles deposited
on the primary PANI surface were quite different
depending on the acid applied. Perchloric acid
produced colonies of columnar Ag deposits dis-
persed nonuniformly on the surface. The uniformity
of the Ag particles was better for the other two
specimens.
• The electrical conductivity of the PANI thin films
and the PANI–Ag surface composites varied
depending on the acid applied. Sulfuric acid pro-
duced a more conductive surface on the ABS
substrate.
• The morphology of the final nickel coating was a
direct function of the morphology of the primary
Fig. 6: SEM images showing cross-sectional views of
PANI film and the size and distribution of Ag
nickel coating on samples synthesized using (a) particles. The nickel coating on the specimen
perchloric, (b) nitric, and (c) phosphoric acid treated using perchloric acid showed granular

1440

Fig. 8: Results of cross-cut test on nickel coating
deposited on specimens treated using (a) perchloric, (b)
nitric, and (c) sulfuric acid
microstructure with smooth surface, while the
morphology of the nickel coating on the other two
specimens was granular.
• The nickel coating produced on the specimen
treated using perchloric acid showed the highest
adhesive strength, while that treated using sulfuric
acid showed the lowest strength.
J. Coat. Technol. Res., 15 (6) 1433–1442, 2018
Acknowledgment The authors kindly appreciate
financial support from Shahid Chamran University of
Ahvaz (Grant No. 96/3/02/16670). In addition, useful
comments by Dr. M. Yeganeh are sincerely respected.
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