Applied Surface Science 282 (2013) 741–745

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Applied Surface Science

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

Preparation of PMMA-Ni core-shell composite particles by electroless

plating on polyelectrolyte-modified PMMA beads
Kuan-Ju Lin a , Hong-Mao Wu a , Yi-Hsiuan Yu b , Chan-Yuan Ho b , Ming-Hsiung Wei b ,
Fu-Hsing Lu a , Wenjea J. Tseng a,∗
a
Department of Materials Science and Engineering, National Chung Hsing University, Taichung 402, Taiwan
b
Chemical System Research Division, Chung-Shan Institute of Science and Technology, Long-Tan, Tao-Yuan 325, Taiwan

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

Article history: Surface of poly(methyl methacrylate) (PMMA) beads was modified deliberately by poly(allylamine
Received 24 February 2013 hydrochloride) (PAH) molecules and poly(acrylic acid) (PAA) molecules through electrostatic adsorp-
Received in revised form 4 April 2013 tion in water. The adsorbed polyelectrolytes facilitated preferential deposition and growth of uniform
Accepted 4 April 2013
nickel (Ni) shell on the PMMA surface when electroless (autocatalytic) plating was carried out using
Available online 20 June 2013
nickel chloride as the metal source and dimethylamine borane (DMAB) as the reducing agent. A dense
Ni layer with an adhesive interface resulted. Crystallinity, film structure, and the electrical resistivity of
Keywords:
the PMMA-Ni core-shell composites were examined as the DMAB concentration varies.
Nickel
PMMA © 2013 Elsevier B.V. All rights reserved.
Polyelectrolyte
Electroless plating
Coating

1. Introduction In view of the literature, Guo et al. [18] first employed the elec-
troless Ni plating on poly(methyl methacrylate) (PMMA) beads
Organic–inorganic composite particles featuring specifically to form core-shell composite particles with magnetic response
metallic shell around polymeric core have received immense under an external magnetic field. The PMMA surface was first sen-
interests over the last decade because of their potential use sitized by adsorption of tin ions (Sn2+ ) before being replaced by
in electronics, catalysis, biochemistry, sensor, and optics [1–4]. palladium (Pd) through redox reactions occurring on the surface.
An astounding array of different synthetic strategies has been Similarly, Tierno and Goedel [19] prepared PMMA beads covered
used to prepare the colloidal core-shell structure with desired with nickel–phosphorus (Ni-P) alloys by electroless plating. Chen
chemical composition and tailored functionality. This includes et al. [20] recently employed a microwave irradiation on the Sn2+ -
preferential surface precipitation, seeded growth, Pickering poly- sensitized PMMA beads. The presence of microwave power induced
merization, electroless (autocatalytic) plating, sonochemistry, and localized heating around the adsorbed Sn2+ to promote the redox
electrostatic layer-by-layer (LbL) nanoparticle assembly [1,2,5–11]. reaction in the electroless bath. This led to a creation of abundant,
Among them, the electroless plating involves use of chemical non-aggregating Pd catalytic sites on the PMMA surface so that
reducing agent to facilitate reduction of metallic ions in solution the deposition of uniform Ni-P coating on the PMMA beads was
to their metallic state depositing preferentially on the core surface. rendered. More importantly, a microwave-assisted polyol process
The process is simple with good throwing power, versatile, cost- has been demonstrated recently that allowed a direct deposition
effective with deposition taking place only on the catalytic surface, of active Pd nanoparticles on the PMMA surface with ethanol as
and scale-up ready [12]. Considerable efforts have been devoted to a reducing agent in the subsequent electroless Ni plating [21].
the deposition of a variety of metals such as gold (Au) [13,14], silver This further simplifies the pre-treatment process prior the elec-
(Ag) [15,16], copper (Cu) [17], and nickel (Ni) [18–25] on various troless deposition and is environmentally benign since the need
organic beads with an aim that a uniformly smooth, complete, and for Sn2+ sensitization became not necessary. The microwave pre-
adhesive metal shell can be formed on the colloidal polymer beads. treatment is yet difficult to implement in mass production. Instead,
Song et al. [22] adsorbed palladium hydroxide on the surface of
polystyrene (PS) beads which was subsequently converted to cat-
alytic Pd active sites by using hydrazine as the reducing agent. This
∗ Corresponding author. Tel.: +886 4 2287 0720; fax: +886 4 2285 7017. operation avoids the use of toxic Sn in the Sn2+ sensitization while
E-mail address: [email protected] (W.J. Tseng). uniform Ni shell on the PS surface resulted after the electroless

0169-4332/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
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742 K.-J. Lin et al. / Applied Surface Science 282 (2013) 741–745

Fig. 1. Schematic illustration of the fabrication of PMMA-Ni core-shell compos-

ite microspheres by electrostatic polyelectrolyte adsorption and the subsequent
electroless plating.

plating. However, the toxic and flammable nature of the hydrazine

solvent prevents it from being used in massive productions.
In this study, the electrostatic LbL method which involves alter-
nate adsorption of oppositely charged polyelectrolyte polymers
on colloidal beads of various chemistries has been used in the
pre-treatment of PMMA beads prior the electroless Ni deposition.
The aim is to eliminate the need for the Sn2+ sensitization and
Pd activation for the electroless plating. As shown in Fig. 1, the
combination of LbL method with the electroless plating presents
advantages of at least two folds. First, the polyelectrolytes layer is
able to cover the polymeric beads uniformly and attract Ni2+ ions in
solution through electrostatic interactions. Second, the “soft” poly-
electrolytes layer on surface of the PMMA beads is able to provide
a “harbor” space, allowing the Ni2+ seeds be anchored within the
porous layer structure for further reduction to take place so that
a uniform Ni layer can be formed with a suitable reducing agent.
We have hence modified the surface of colloidal PMMA beads by
electrostatic adsorption of cationic poly(allylamine hydrochloride)
(PAH) and anionic poly(acrylic acid) (PAA) molecules sequentially.
Fig. 2. Surface morphology of (a) the as-received PMMA beads and (b) the PAH-PAA
The surface-modified beads were electroless-plated by Ni with the polyelectrolytes-modified PMMA beads.
presence of dimethylamine borane (DMAB) as the reducing agent in
aqueous electroless Ni bath. Crystallinity, interface structure, and
2.2. Electroless deposition of Ni
electrical property of the PMMA-Ni core-shell particles were then
examined.
The polyelectrolytes-mediated PMMA beads of 0.2 g were added
into nickel (II) chloride solution (NiCl2 , 98%, Sigma Aldrich, U.S.A.)
2. Experimental procedures of 50 ml containing DMAB (C2 H10 BN, Sigma Aldrich, U.S.A.) of var-
ious concentrations (0.005–0.170 M) as the reducing agent. The
2.1. Polyelectrolytes adsorption on surface of the PMMA beads

Commercially available PMMA beads (PPT-400, SAU Inc.,

Taiwan) with a mean particle size of 4 ␮m were used as the starting
material. The PMMA beads of 0.2 g were first mixed with de-ionized
water (D.I. water, electrical resistivity of 18.2 M·cm, Millipore
Super-Q Plus, U.S.A.) of 49.8 ml with the solution pH being kept
at 8 by addition of ammonia solution (NH4 OH, 28%, Sigma Aldrich,
U.S.A.). Cationic PAH polyelectrolyte ((C3 H7 N·HCl)n , reagent grade,
molecular weight ca. 60,000, Alfa Aesar, U.S.A.) was then added
into the PMMA solution. The solution was stirred vigorously at
room temperature for 30 min. before being vacuum-filtered and
washed by D.I. water. The washed beads were mixed with D.I.
water again to form uniform colloids of 50 ml. The solution pH was
then adjusted to 3 by adding hydrochloric acid (HCl, 37%, Sigma
Aldrich, U.S.A.) before anionic PAA polyelectrolyte ((C3 H4 O2 )n ,
reagent grade, molecular weight ca. 1800, Sigma Aldrich, U.S.A.)
was added into the PMMA solution. The solution was agitated vigor-
ously for 30 min. followed by the same filtration and water-rinsing
process. Note that both the PAH and PAA concentrations were held Fig. 3. Zeta potential of the as-received and the PAH-PAA polyelectrolyte-modified
at 1% relative to the PMMA weight. PMMA beads in water over a broad pH range.
 K.-J. Lin et al. / Applied Surface Science 282 (2013) 741–745 743

Fig. 4. Surface morphology of the PMMA-Ni core-shell composite particles prepared by electroless plating at DMAB concentrations of (a) 0.005 M, (b) 0.010 M, (c) 0.017 M,
(d) 0.032 M, and (e) 0.170 M.

NiCl2 concentration in the electroless bath was 0.255 M. The col- at a working temperature of 105 ◦ C. Their bulk electrical resistivity
loids were stirred uniformly at 85 ◦ C for 1 h with the solution pH was determined by a four-point probe (Everbeing SR-4, Taiwan)
being kept at 7. The beads were then filtered and washed to obtain under a constant current source of 20 mA at room temperature.
the PMMA-Ni core-shell composite particles. The voltage across the inner two probes with a spacing of 1 mm was
measured by a voltmeter (Keithley 2400, U.S.A.) with a precision of
1 ␮A.
2.3. Characterizations

At each process stage, some PMMA beads were siphoned out 3. Results and discussion
from the solution and diluted in water for determining zeta ()
potential by dynamic light-scattering analyzer (Zetasizer Nano ZS, Surface morphology of the as-received PMMA beads and the
Malvern Instrument, U.K.) and microstructural examination by polyelectrolytes-modified beads is shown in Fig. 2. The as-received
scanning electron microscopy (FE-SEM, JSM-6700F, JEOL, Japan). beads show smooth and featureless surface morphology while
The solution pH was adjusted with HCl and NH4 OH for the - the surface becomes wrinkled apparently after the polyelec-
potential measurement. Crystalline structure of the electroless trolytes adsorption, revealing that a “soft” polyelectrolytes layer
prepared Ni layer was determined by X-ray diffractometry (XRD, was formed on the PMMA surface. The polyelectrolytes adsorption
MAC MXP III, Japan) using Cu K␣ radiation ( = 1.5406 Å) with accel- is verified by the -potential measurement. As shown in Fig. 3,
erating voltage and current of 40 kV and 30 mA, respectively. The the as-received PMMA beads show a negative surface potential
measured 2 range was from 10◦ to 90◦ with a scan rate of 2◦ /min. in water over a broad pH range. The surface becomes positively
The crystallite size of the Ni coating was estimated by the Scherrer charged with the adsorption of PAH polyelectrolytes. The surface
equation from the diffracted Ni(1 1 1) peak at 2 = 44.5◦ . A focused then changes to a net negative charge with an increased magni-
ion beam (FIB, JEOL JIB-4601F, Japan) which uses a focused beam of tude in the -potential (than that of the as-received one) when
gallium (Ga) ions to scan across a sample was employed to image the PAA polyelectrolytes were subsequently adsorbed; to which,
the PMMA-Ni interface. The FIB is capable of sputter removal of the side chains of PAA molecules appear to have lost their protons
atoms in the sample from the surface at the micro- and nanoscale, and acquired a negative potential so long as the solution pH was
allowing for a direct observation at the composite interface. above 2. The electrostatic effect facilitates the adsorption of nega-
Some of the composite particles were uniaxially pressed at tively charged PAA molecules onto the positively charged surface
110 MPa into discs of 12.5 mm in diameter and 0.4 mm in thickness of the PAH-covered PMMA beads. The negative surface potential
744 K.-J. Lin et al. / Applied Surface Science 282 (2013) 741–745

Fig. 5. X-ray diffraction patterns of the PMMA-Ni composite particles prepared

by electroless Ni plating on the polyelectrolytes-modified PMMA beads at various
DMAB concentrations.

of the polyelectrolytes-modified beads were considered capable

to anchor Ni2+ ions on the surface in the aqueous Ni bath, facili-
tating nucleation and growth of Ni metals when catalyzed in the
subsequent electroless deposition.
When subjected to the electroless Ni plating, the DMAB was
used in the study as a reducing agent to supply electrons so that Ni
ions in the solution were converted to their metal state at locations
near the catalytic sites of the modified PMMA surface. In Fig. 4, the
deposition of Ni crystallites happens on the PMMA surface prefer-
entially but a continuous buildup of the Ni coating does not occur
at low DMAB concentrations (i.e., ≤0.010 M in Fig. 4(a) and (b))
because of the lack of continuous supply of electrons from the
reducing agent. Therefore, the deposited Ni crystallites are not of
catalytic for the deposition to continue, resulted in mostly isolated
Ni “islands” on the PMMA surface despite some beads do show
a greater deposition density of Ni on the bead surface (inset of
Fig. 4(b)). When the DMAB concentration was increased to 0.017 M Fig. 6. (a) Surface morphology of the PMMA-Ni composite particles prepared by
electroless Ni plating on the PMMA beads at DMAB concentration of 0.170 M for an
in Fig. 4(c), the Ni islands that form and grow around the nuclea-
isothermal soaking of 1 h. (b) An enlarged interface microstructure after the focused
tion sites appear to merge one another so that a continuous Ni film Ga ion bombardment (30 kV, 10 pA).
results on most of the bead surface. This becomes particularly true
when the DMAB concentration was further increased, as shown
in Fig. 4(d) and (e). From the inset of Fig. 4(d), thickness of the defect at the interface. In addition, the Ni film is dense in structure
deposited Ni coating is about 100 nm. In addition, film continu- with a uniform thickness about 100 nm.
ity with densely packed Ni grains on the modified PMMA beads is The Ni coating on the PMMA beads renders the composite par-
reached as the DMAB concentration approached toward 0.170 M ticles electrically conductive. In Fig. 7, the electrical resistivity
(inset of Fig. 4(e)). reduces by almost four orders of magnitude as the DMAB concen-
In Fig. 5, the Ni deposit shows an increasing diffraction intensity tration increased from 0.017 to 0.170 M. An additional preparation
as the DMAB concentration was increased from 0.005 to 0.017 M, of the PMMA-Ni composite particles by using DMAB of 0.850 M
revealing an increased Ni concentration in the composite particles. shows an essentially identical resistivity as that prepared from
This is in good agreement with that of Fig. 4(a)–(c), in which an
increased deposition density of Ni islands (i.e., the Ni concentra-
tion) is found. It may be interesting to note that the Ni diffraction
peaks then become apparently broadened as the DMAB concentra-
tion was further increased, revealing that a reduced crystallite size
results. An estimate of the crystallite size of the Ni coating by the
Scherrer equation shows that the crystallite size of Ni decreased
from 24.9 to 2.09 nm when the DMAB concentration was increased
from 0.017 to 0.17 M. This hence indicates that the abundant elec-
trons provided by the presence of reducing DMAB in the electroless
bath gave rise to the formation of densely populated Ni nuclei from
the Ni ions in the solution so that preferential deposition of the
Ni layer consisting of grains of a substantially reduced crystallite
size was formed. This increased density of Ni nucleation is found
beneficial to the film adhesion. As shown in Fig. 6, a typical PMMA-
Fig. 7. Bulk electrical resistivity of the PMMA-Ni composite particles prepared by
Ni composite particle that was selectively etched by the Ga-ion electroless Ni plating on the polyelectrolytes-modified PMMA beads at various
bombardment shows a hermetic interface without any apparent DMAB concentrations.
 K.-J. Lin et al. / Applied Surface Science 282 (2013) 741–745 745

the one with DMAB of 0.170 M, indicating that the Ni coating CSIST-0497-V201(101) and National Science Council under con-
was uniform on the non-conductive PMMA beads so that the bulk tract no. NSC 98-2221-E-005-031-MY3.
resistivity becomes rather insensitive to further Ni deposition.
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