Environmentally friendly process for nickel electroplating of ABS

Abstract

Nickel electroplating of acrylonitrile butadiene styrene (ABS) plastic has been achieved
successfully without any chromium or palladium pretreatment. Once the ABS is coated
with polypyrrole (PPy), the sample may be electroplated. The process is fast, economic
and involves three stages. Firstly, chemical deposition of PPy on ABS, secondly, copper
deposition and finally nickel electroplating. A homogenous and adherent PPy has been
synthesized chemically on ABS plate by using pyrrole as monomer and iron (III) chloride as
oxidant. Cooper and nickel were deposited galvanostatically from industrial plating baths.
The metallic coatings were homogenous and the adherence was estimated at 100%. The
thickness of copper and nickel depend on the electrolysis time. As the current density
increases, the Cu and Ni thickness raises. This result was confirmed from SEM
characterization and RX map. The Ni coating is characterized by a globular structure with
globules of different sizes. Energy dispersive X-ray spectroscopy (EDS) analysis shows the
presence of Ni with some amount of carbon and oxygen due to the nickel oxides and
contaminant from the bath solution.

1. INTRODUCTION:
Acrylonitrile butadiene styrene (ABS) is the most common plateable plastic.
Copper and nickel plated ABS is used in almost all decorative planting processes.
For industrial applications, plastic metallization serves to make toys, automotive
and computer body parts, electronic housings, wheel covers, lamp housings,
ventilation, air condition parts, pipes and fittings and many more things [1-4].
The available plating process of ABS involves many steeps and baths [5-8]: (1)
etching the plastic surface in strong acidic oxidizing solutions by a combination of
sulphuric acid, chromic acid, phosphoric acid and permanganate solutions. These
baths usually operate at temperature between 50°C and 70°C, and are hazardous
waste and highly corrosive. (2) Sensitizing the etched plastic by immersion of
samples in stannous chloride solution. This steep allows the sensitizer to be
absorbed into the surface (3) Activating the ABS surface in an aqueous solution of
precious metal catalyst, like palladium and gold for depositing metallic nucleus
particles in the selected plastic are following the chemical reaction:
Sn2++ Pd2+  Sn4+ + Pd0 or Sn2++ 2Au+  Sn4+ + 2Au0.
The palladium or gold are deposited onto modified ABS surface. (4) Electroless
copper deposition on the activated samples. After this pre-treatment the ABS acts
as a conductor and are ready for subsequent electroplating systems.
However, this conventional technique requires multiples and complex
manufacturing steps and suffer numerous drawbacks. High costs of precious
 metals such Pd and Au increase manufacturing costs. Involving, chromium in
etching tank is undesirable due to the environmental impact. In addition,
electroless plating solution is not easily controlled and involves a relatively large
number of steps that increase the processing time and water consumption.
Direct metallization is required to substitute the conventional process. In this
context, several works have been reported [9-13]. Blandon et.al. [9] proposed the
model of stepwise propagation with continuous conduction. They showed that
palladium-tin colloid is adsorbed onto an epoxy substrate and serves as a catalyst
for the subsequent electroless deposition of copper in nonconductive supports and
directly followed by a thick layer of electrolytic ally deposited copper. This process
has been developed to replace the electroless step with a sulphide-containing
solution which alters the adsorbed palladium-tin colloid and make it resistant to
acidic solutions and electrolytic deposition of copper.
Another process, named laser direct structuring (LDS) [13-14] based on mixing
some laser compatible particles with the polymer material before is moulded.
After moulding, a laser beam is directed to the area to be plated and reach these
particles. This selective technique is advantageous since it does not provide toxic
chemicals in the treatment of the article to be metallized.
In this paper we report a direct metal electroplating process on ABS, an
environment friendly coating method that reduces steeps and costs of the
conventional metallization process largely used in plating industries.
2. EXPERIMENTAL
Pyrrole (98%) was purchased from Sigma, Sulphuric acid (H2SO4) 96% from Riedel-
deHaen and (CuSO4.5H2O) 95%, (NiSO4.6H2O), (NiCl2.6H2O), H3BO3, NIVELIX
EUROLYTE AM, NIVELIX EUROLYTE BASE, NIVELIX UROLYTE from Panreac Quimica,
Spain, Bath additives CUFLEX 500 MU BASE and CUFLEX 500 brightness were
imported from IMASA (Industria de Maquinas Salvator, Porto, Portugal). The
products were used as received and water was distilled before use. ABS was a
commercial polymer (Novodur P2 M Grade).
The polypyrrole deposition on ABS substrates at room temperature was carried
out as follows: samples of ABS were immersed in a solution of 0.30 M pyrrole (75
ml). After 1h another solution of 0.9 M FeCl3 (25 ml) was slowly added drop wise
into the stirred monomer medium. The polymerization was achieved for 2h with
constant magnetic stirring. The synthesized PPy/ABS was rinsed several times with
distilled water and methanol.
The electrolysis was performed in beaker of 200 ml, with copper as anode in the
case of Cu electroplating and nickel in the case of Ni electroplating. The PPy/ABS
 constitutes the cathode. The electrolytic conditions for the two baths are gathered
in the Table 1.
The electrochemical experiments were performed in a one-compartment cell with
three electrodes connected to Volta lab 80 Model PGZ potentiostat/galvanostat
with pilot integration controlled by Voltamaster 4 software. The PPy/ABS
rectangular sheet constitutes the working electrode. The electrodes were rinsed in
water and ethanol before each electrochemical experiment. A stainless-steel plate
was the auxiliary electrode. All the potentials were measured versus an Ag/AgCl
(0.1 M KCl) reference electrode.
Adherence measurements were based on the standard sellotape test, which
consists of cutting the film into small squares, sticking the tape and then stripping
it. The ration between the number of adherent film squares remaining and their
total number gives the percentages of adherence.
Scanning electron microscopy (SEM) micrographs, RX maps and electron dispersion
spectroscopy (EDS) analysis were performed in Centre 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 Nickel electrplating of ABS

Nickel electroplating of ABS process is successfully achieved in three steps: firstly, the chemical
deposition of PPy on ABS to transform plastic into conductive surface, secondly, copper
electroplating and finally the nickel electrodeposition.

(a) Step 1: PPypretreatment of ABS subtrates.

The behaviour of ABS after 1 h of continuously stirring in 0.3 M pyrrole solution shows a swelling
and melting of ABS surface. Effectively, the texture becomes a fish scale like when the plastic is
treated in pyrrole solution (Fig. 1 a) in comparison with ABS without treatment (Fig.1 b). Pyrrole
solution is adsorbed on the ABS and cause surface roughness in which cracks and melting appear
in the plastic. It can be speculated that this behavior is likely due to interaction between the ABS
surface and the monomer, which causes a slight dissolution of ABS. This stage approves the
coating adhesion since the polypyrrole could be bonded strongly to the crake nucleus during
polymerization reaction. After addition of FeCl3, the oxidation occurs and a black, homogeneous
and adherent PPy film is deposited on the ABS surface.

SEM image (Fig.1 c) shows that the PPy coating is a globular structure with a grain of 0.3-0.5 um
diameter size. The adherence was estimated at 100% by the normal sellotape test. The chemical
polymerization reaction achieved in the ABS substrates between pyrrole and FeCl3 is as follows:
From the reaction we can conclude that synthesized PPy is no more doped than 33% with chlorine
anion. Otherwise, one chlorine atom accepts one electron from three pyrrole monomer units to
become a doping anion. The EDS analysis reveals the presence of carbon, nitrogen, oxygen and
chlorine from the polypyrrole and chlorine doping anion.

(b) Step 2: copper electroplating of PPy/ABS

The electrodeposition of homogeneous copper on ABS samples was successfully achieved

galvanostatically. The adherence was estimated at 100% and could be the result of the copper
bonding to PPy/ABS nucleus. SEM micrographs (Fig. 2) show that the grain size of the copper film
increased with increasing electrolysis time and the cooper coating become compact, well-spread
on the PPy/ABS without any cracks and the apparent copper crystal geometry on the SEM
micrographs. The copper coating obtained during 15 min is thin characterized by globular
structure with grain size of 4 um diameter. This morphology is relatively like 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 compact grains of cubic form in agreement
with the copper crystallography geometry. EDS characterization of this layer proved that it
contained mostly copper.

The copper thickness reached at 33 mA cm-2 is readily controlled by the time of electrolysis and
was estimated by the following equation:

Where ƿ is the metal density (in the case of copper, ƿ= 8.92 gcm-3) Δm the experimental mass
difference between the blank and the coated PPy/ABS electrode. S is the coated electrode area.
Table 2 summarizes the data of the thickness estimated by the formula above. The longer is the
electrolysis time, the higher is the copper thickness.

(c) Step 3: nickel electroplating.

Electroplating of Ni on ABS substrates was investigated at 20 mA cm-2 during different

electroplating time. The Ni was applied like a top coating of Cu/PPy/ABS as is schematized in Fig. 3.
The electrodeposition of Ni from industrial bath cited in the experimental section is achieved
easily since the surface of ABS is already coated with uniform copper film. The obtained nickel
coating is homogeneous. Table 3 summarizes the thickness estimated from equation (1) (with
ƿ=8.90 g cm-3 is the nickel density). The results show that thickness increases with increasing time
of electroplating.

SEM images of the nickel electroplated ABS samples are presented in Fig. 4. The micrographs
disclose a homogeneous nickel coating with globular structure. The time of electrolysis has a great
effect on the coating morphology. The globule size increases with increasing electrolysis time, and
the texture become compact and smoother. No crakes are seen in the deposit and the adherence
is estimated at 100% from standard sellotape test, which confirms a high quality nickel coating.

X-ray mapping of cross-section of Ni coated Cu 38 µm/PPy/ABS electroplated during different time

(Fig. 5) shows that nickel and copper are uniform and consistent. Moreover, a larger in time will
result in a thicker metallic bilayer coating of PPy/ABS electrode surface. Table 4 summarizes the
coating thicknesses of Ni obtained by SEM and X-ray mapping. The nickel thicknesses estimated
experimentally are similar to those estimated theoretically already reported in Table 3.
Nickel peak is observed in energy dispersive X-ray spectroscopy (EDS) spectra, indicating the
presence of nickel in the deposit samples. The coating samples also contained a small amount of
carbon and oxygen, which may have originated from the impurities and bath solutions. However,
it is interesting that no copper was detected for all samples with different deposition times, which
gives an idea that the ABS electrodes were entirely covered with homogeneous and compact
nickel coating.

3.2. Electrochemical behaviour of Cu/PPy/ABS and Ni/Cu/PPy/ABS.

The cyclic voltammograms for metalized PPy/ABS samples as well as for copper bare in NiSO4
solution are shown in Fig. 6. During the first scan of pure copper bare (Fig. 6a) an oxidation wave
appears at ca. 0 V and is attributed to the copper oxidation. In the following cycles this wave
shifted to ca. -0.1 V and it is associated with the Ni and Cu oxidation. During the reverse scan a
broad cathodic peak starting at ca. 0 V and ending at ca. -0.9 V is observed.

This complex cathodic peak that increases with number of cycles is related with the reduction of
copper anodically dissolved and nickel ions from solution. Mattisson et al.[15] and Schumacher et
al.[16] show that the copper in acidic sulphate solution is dissolved into the cationic species Cu+
and Cu2+, which means that the reduction proceeds in two steeps: the first one is the reduction of
Cu2+ to Cu+ and the second one is Cu+ to Cu.

The potentiodynamic curves recorded to Cu8um/PPy/ABS in the same condition as above are
represented in Fig. 6b. No differences are observed in the first scanning cycle of the voltammetric
shape of Cu bare and Cu8um/PPy/ABS. However, from the second scan appears an oxidation peak
at ca -0.2 V that was not observed in the Cu bare. This behaviour must be related with the
oxidation of PPy. Effectively, the thickness of copper is thin (around 8 um), and during the
oxidation wave the copper coating is partially dissolved.

Thus, the micro holes formed on the copper layer allow a direct contact between the electrolytic
solution and the polypyrrole film during the following successive potential sweeping. In the
cathodic sweep, a complex peak become progressively broader and shift to more negative
potentials. The PPy is reduced, which means an expulsion of anions such as Cl- and SO42- and
insertion of metallic cations (Ni2+ and Cu2+) from solution, as well as the metallic ions from
solution. It should be noted that during the oxidation of polypyrrole the metallic cations adsorbed
are expulsed and the anions are inserted[17,18].

The polarization of nickel electrode under the same conditions is shown in Fig. 7a. The passivation
of Ni surface occurs at the potential domain between -0.7 V and -0.3 V, and this potential domain
is due to adsorbed species such as SO42- and OH- at Ni surface[16]. Oxidation starts at -0.3 V
followed by an anodic peak of nickel dissolution at ca. 0 V. It has been reported that in acidic
solution, beyond the oxidation of nickel metal, the dissolution of nickel may involve a contribution
of H+ to active anodic region according to the following reactions[19]:

Ni(OH)-ad + H+ → Ni2+ + H2O + 2e (3)

Ni(OH)2 + 2H+ → Ni2+ + 2H2O. (4)

The reverse sweeps show a shoulder at about -0.6 V related with the reduction of Ni2+ that
increases with number of potential sweeping.

In the case of Ni/Cu/PPy/ABS the general shape of cyclic voltammetry curves are similar to those
recorded on Ni bare. Two kinds of Ni/Cu/PPy/ABS electrodes with different thicknesses have been
used. The first one corresponds to 10 um Ni and 38 um Cu thickness (Ni10um/Cu38um/PPy/ABS)
and the second one is 4 um Ni and 8 um Cu thickness (Ni4um/Cu8um/PPy/ABS).

The voltammetric curves of Ni10um/Cu38um/PPy/ABS in NiSO4 solution (Fig. 7 b) show an

oxidation peak at ca. 0 V attributed to nickel oxidation and a cathodic shoulder at -0.6 V related
with nickel ions reduction in full agreement with Ni bare i-E curves recorded in the same
electrolytic conditions. During the last sweeping potential, the anodic peak is shifted towards
more negative potential and a second complex cathodic peak appeared as a shoulder at ca.-0.33 V.
The anodic charge is attributed to PPy oxidation with anion insertion and cations expulsion and
the cathodic charge is assigned to PPy reduction with anions repulsion and cations insertion. This
redox process of PPy was not observed in the beginning of sweeping since the nickel and copper
layers are thick, and their dissolution require more cyclic sweeping. This phenomenon was already
explained in the case of Cu/PPy/ABS with thin copper thickness.

The Ni4um/Cu8um/PPy/ABS thin coating electrode, behaves in the same way as nickel bare during
the first potential scanning (Fig. 7 c). The oxidation peak of nickel is shifted towards negative
potentials and the current density decreases with number of potential sweeping. On the other
hand, the cathodic peak is progressively broader and is shifted towards negative potentials and its
curent density increases with the number of i-E cycles. This behaviour is similar to the thick nickel
coated on PPy and becomes progressively like thin copper coating during the last potential
scanning.

Indeed, the displacement of oxidation and reduction peaks towards negative potential is related
with the oxidation of PPy and the insertion of anions and expulsion of cations and reduction of PPy
with expulsion of anions and adsorption of cations.

We concluded from these results that metal plating on ABS has the same behaviour as metal bare.
Therefore, the metallization of ABS with this economic and environmentally friendly plating
process has the same feature than conventional plating techniques.

4. Conclusion

A process for direct plastic electroplating has been described.

The PPy pretreatment of ABS allows electrical conductivity to the samples. A deposition of copper
is directly achieved on PPy/ABS and no previous acidic etching or electroless steps are required.
Then, nickel is electrodeposited as a top coating of the sample.

This process is advantageous in comparison with a conventional electroplating method since

several steps are reduced among them chromium etching, and palladium autocatalysis. SEM, X-ray
mapping and EDS analysis shows that the coating is homogeneous, thick and strongly adherent.
Cyclic voltammetry shows that electroplating ABS samples have the same behaviour as simple
metal bare. This original electroplating method of plastics constitutes an economical and
ecological electroplating process.