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An Alternative Process For The Preparation of Cu-Coated Mica Composite Powder PDF
An Alternative Process For The Preparation of Cu-Coated Mica Composite Powder PDF
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Abstract
Metallization technique based electroless coating is used to prepare Cu-coated mica composite powder. The [Ag(NH3)2]+ activator is directly
employed to render the surface of mica substrate catalytically active towards copper deposition in the electroless coating solution. The mica
powder was characterized by scanning electron microscopy (SEM)/energy-dispersive X-ray (EDX), Auger electron spectroscopy (AES)/X-ray
photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Fourier transform infra-red spectroscope (FTIR) and transmission electron
microscopy (TEM) during and after the coating process. A possible mechanism of electroless copper coating of mica powder utilizing the [Ag
(NH3)2]+ activator is proposed. The results show that mica powder adsorbs the [Ag(NH3)2]+ ions mainly by surface adsorption, and relatively
uniform and continuous copper coating, which has fcc crystalline structure, is obtained under the giving coating conditions.
2006 Elsevier B.V. All rights reserved.
Keywords: Electroless coating; Copper; Mica powder; [Ag(NH3)2]+ activator; Surface adsorption
1. Introduction
The need for metal-coated fine powders in the area of composite materials has recently been recognized. They are new
types of composite materials, which can be used to fabricate
electromagnetic interference (EMI) polymer matrices and
metallic matrices composite materials [18].Various metalcoated fine powders can be prepared by adding the sensitized
and activated powders into electroless coating bath solutions.
Among various powder materials, mica was selected for this
project due to its low cost, light density and desirable structure.
Mica is widely used as a filler of paint and plastic [912] because
it consists of flakes with a high aspect ratio (ratio of diameter to
thickness), which tends to be favorable for contacting between
the fillers. Compared to metallic fillers, metal-coated mica has
lower density, lower cost, and easily disperses to avoid the
formation of sediment in the processing of polymer matrices
composites. Metal-coated mica can be produced with conductive
and magnetic properties, and retains its original high aspect ratio.
Corresponding author. Tel./fax: +86 24 23915906.
E-mail address: hbdai@imr.ac.cn (H. Dai).
0257-8972/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2006.05.043
Therefore, metal-coated mica can be used to fabricate electromagnetic interference (EMI) polymer matrices and metallic
matrices composite materials [1315].
Current techniques for metallization mica are usually employed by electroless coating method. The electroless deposition
on non-metallic species requites catalysis of the surface to be
coated. Typically the catalytic palladium treatment of particles is
carried out in two-step method [16]. First the core particles are
sensitized by immersion in an aqueous solution of stannous
chloride containing hydrochloric acid. The particles are then
isolated and activated by dispersing in an aqueous solution of
palladium chloride and hydrochloric acid. The particles are
again recovered from the activation bath and contacted with
electroless coating. The procedure needs SnCl2 to reduce Pd2+ to
Pd0. The Pd0 clusters were all surrounded by SnCl2 shells, but
the SnCl2 shells are not an active catalyst for electroless coating.
The growth of a metallic film may be inhibited by the presence of
the SnCl2 shells during electroless coating [17]. An acceleration
step or a pre-reduction step is used to eliminate the remaining tin
compounds after activation [18]. In addition, the procedure
needs several steps: etching, sensitization and activation, requiring the transfer of the particles between several baths, and
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2. Experimental
2.1. Materials
2.4. Characterization
2.2. Procedure
2.2.1. Preparation of the activation solution
6 g/l of AgNO3 was dissolved in distilled water, and then
dropped gradually about 10 ml 25 wt.% ammonia solutions
until dissolution of the brown silver oxide precipitate under
stirring condition. The obtained activation solution was stored
in dark bottle prior to use. The activator of the obtained solution
with the method is a complex of [Ag(NH3)2]+. The chemical
reaction equation for AgNO3 to form [Ag(NH3)2]+ is as follows:
Ag NH3 H2 OAgOH NH
4
2AgOHAg2 O H2 O
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Fig. 1. SEM micrographs of (a, b) mica powder, (c, d and e) Cu-coated mica powder at different magnifications [(e) corresponding to the white rectangular region in
(d)]; (f) EDX analyses of mica powder and (g) Cu-coated mica powder.
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FWHM (ev)
Area (%)
932.2 (Cu)
932.9 (Cu2O)
933.8 (CuO)
1.3 (Cu)
1.3 (Cu2O)
2.3 (CuO)
46.4
38.2
15.4
(BE and FWHM stand for binding energy and full width at half maximum,
respectively).
Fig. 5. Powder XRD patterns of (a) mica powder, (b) the activated mica powder,
(c) the organomica powder, (d) the Cu-coated mica powder. (The preparation of
the organomica was as follows: 5 g of K-TSM was added to 500 ml distilled
water, stirred magnetically for 20 min, then a 20 ml of 10% hexadecyltrimetuylammonium bromide (HLAB) solution was added, which is a long alkyl
chain kind of cationic surfactant, and usually used to interlay to prepare the
organoclays [23,24]), and reacted for 24 h at 80 C. The resulting product was
separated by vacuum filtration, washed thoroughly with distilled water, and then
dried for 2 h at 100 C).
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Fig. 8. TEM image and particle size distribution of the metallic Ag0 on the
reduced mica surface.
(NH3)2]+ ions on the mica surface. After the mica was reduced
with HCHO, which acted as a reducing agent in the electroless
copper coating, the band for the NH3 groups in Fig. 7 (c) disappeared, and those for the OH groups of the mica reappeared at
3454 cm 1 and 1643 cm 1, suggesting the [Ag(NH3)2]+ ions
adsorbed on the mica surface was reduced to the metallic Ag0.
Compared with the Fig. 7 (a), Fig. 7 (b) can be observed
obviously that the AlO peak shifted from 509 cm 1 to 465 cm 1,
while the SiO peak at 1018 cm 1 remained in the same position.
The negative shift implies the decrease of the AlO bonds intensity,
indicating the AlO groups adsorb the [Ag (NH3)2]+ ions. After the
reduction, the AlO peak shifted from 465 cm 1 to 471 cm 1, and
the SiO peak at 1022 cm 1 almost did not shift. The positive shift
implies the intensity of the AlO bonds increased, indicating the
decrease of silver chemical valence, which suggests that the [Ag
(NH3)2]+ ions adsorbed on the mica surface was reduced to the
metallic Ag0 by the reducing agent (HCHO). Nevertheless, Fig. 7
(c) can be observed obviously by comparison with the Fig. 7 (a) that
the AlO peak shifted from 509 cm 1 to 471 cm 1, the negative
shift indicates that the intensity of the AlO bonds decreased, and
the AlO groups still adsorbed the metallic Ag0 after the reduction
of the activated mica and washing step.
The FTIR spectra analyses show that the way of K-TSM
adsorbing the [Ag(NH3)2]+ activator mainly comes from the
AlO groups of the outside tetrahedral sheets of the
aluminosilicate layers.
A TEM image was taken to confirm further the metallic Ag0
on the mica surface after the reduction of the activated mica and
washing step, which is a catalyst for initiating copper deposition
on non-metallic materials during the electroless coating process.
As shown in Fig. 8, the metallic Ag clusters with an average size
of ca.13 nm could be observed on the mica surface.
3.5. The mechanism of electroless copper coating of mica
powder
Based on the above XRD, FTIR and TEM analyses, we
knew that K-TSM in this work can adsorb [Ag(NH3)2]+ ions
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adsorption
micaAgNH3 2
2a
2b
We are grateful to the National High-Tech Research and Development Program of China (863 Program) (no. 2002AA327110)
for the financial support, and take this opportunity to sincerely
acknowledge Professor Lees from the University of Manchester,
U.K. for helping us revise the manuscript.
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