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Surface & Coatings Technology 201 (2006) 2859 2866

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An alternative process for the preparation of Cu-coated


mica composite powder
Hongbin Dai , Hongxi Li, Fuhui Wang
State Key Laboratory for Corrosion and Protection, Institute of Metal Research, Chinese Academy of Sciences,
Wencui Road 62, Shenyang, 110016, China
Received 21 October 2005; accepted in revised form 31 May 2006
Available online 10 July 2006

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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palladium is a relatively expensive catalyst. As a result, the


overall cost of the electroless process for coating metal on mica
powder is still a major problem in commercialization.
As a result of its particular crystal structure, mica can adsorb
[Ag(NH3)2]+ ions directly by surface adsorption under the action
of static force [19], and silver can act as a catalyst for electroless
Cu coating [6,20]. Therefore, cheaper [Ag(NH3)2]+ activator can
be employed without etching and sensitization pretreatment
process for the preparation of Cu-coated mica composite powder. The activation process in this paper is a key concept with the
aim of simplifying the electroless copper coating of mica powder
because it eliminates the use of etching, sensitization and acceleration steps.

The copper coating was dissolved in 30% HNO3. Copper


was determined by inductively-coupled plasma-atomic emission spectroscopy (ICP-AES). The amount of copper was used
to calculate the weight percent of the deposits.
2.3. Specific volume resistivity of the powders

2. Experimental

In order to measure the specific volume resistivity of the


powders with the four probe method, pellets of a known mass of
mica or Cu-coated-mica were produced by applying a pressure
25 MPa for 5 min to samples of each of the powders. The
following equation was used to calculate the specific volume
resistivity: = RS / L, where is the volume resistivity ( cm),
R the measured resistance, L the distance between electrodes
(cm), and S is the pellet cross sectional area (cm2).

2.1. Materials

2.4. Characterization

The mica powder in this paper was potassium-type synthetic


fluorotetrasilisic mica (fluorophlogopite, K-TSM), KMg3Si3
AlO10F2, supplied by Sino Surplus International Co. Ltd., Beijing, China. It had an average particle size of 43 m and a density
of 2.80 g/cm3.The chemical reagents used for electroless Cu
coating of mica powder were all of analytical grade and used as
received.

SEM studies were performed using an XL 30 Phillips FEG


microscope equipped with EDX (to determine the chemical
composition). AES and XPS spectra were recorded on a LAS3000 multi-technique spectrometer using an Mg K source.
Near-surface elemental depth profiles of the Cu-coated mica
were obtained using a LAS-3000 Auger electron spectrometer,
at a base pressure of 2.0 10 7 Pa, beam voltage of 2.5 keV, ev/
step 1 ev, and time/step 0.3 s. Calibration was conducted on the
C1s peak of the CC and CH bonds at 284.6 ev. The curve
fitting was performed using XPS PEAK 4.1 software. The
structure analyses were carried out (within 2 range of 5100)
using a Rigaku X-ray Diffractometer (XRD) utilizing Cu K
X-radiation of wavelength 0.15405 nm. FTIR measurements
were carried out using a Magna-IR 560 spectrometer. A TEM
image was taken using a Philips EM420 transmission electron
microscope with an operating voltage of 100 kV.

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

3.1. SEM/EDX analyses of mica and Cu-coated mica powder

2AgOHAg2 O H2 O

3. Results and discussion

Ag2 O 4NH3 H2 O2AgNH3 2  2OH 3H2 O


2.2.2. Electroless Cu coating
3 g of as received mica powder was placed in the above
activation solution and stirred magnetically for 2 h at room
temperature, and then separated by vacuum filtration, washed
thoroughly with distilled water. The activated mica powder was
transferred in the electroless copper coating solution with a pH of
12 at room temperature, and stirred for coating 2 h. The pH was
adjusted with 5 wt.% NaOH solution. The Cu-coated mica powder
was separated by vacuum filtration, washed thoroughly with
distilled water and ethanol respectively, and dried at 80 C for 1 h.
The composition of the coating bath was as follows: 15 g/l of
CuSO45H2O, 12 ml of HCHO (37 wt.%), 55 g/l of KNaC4H4
O44H2O, 12 g/l of NaOH, 12 mg/l of K4Fe (CN)3, 12.5 mg/l of
2, 2-dipyridyl, C10H8N.

SEM micrographs of mica and Cu-coated mica powder are


presented in Fig. 1.The morphology seen in Fig. 1 (a) is typical
of mica powder with irregular-sized flakes and a particle size
range of 1060 m, where a small amount of debris is also seen
at high magnification (Fig. 1 (b)). In Fig. 1(c), all the mica
particles are observed to be uniformly coated by the present
electroless method. It is also to be noted that the Cu-coated mica
particles also exhibit the irregular-sized flakes morphology,
indicating that the Cu-coated mica retains its original high aspect
ratio by this technique. Fig. 1 (d) and (e) show SEM micrographs
for the Cu-coated mica at different high magnifications, it is
evident that there was a relatively continuous, dense and uniform
layer of Cu on the surface of all the mica particles, so was there
on the small amount of debris.
EDX of mica and Cu-coated mica powder are presented in
Fig. 1 (f) and (g). K-TSM is composed of O, F, Mg, Al, Si and K
as indicated by the EDX analysis in Fig. 1 (f); while the Cucoated mica as indicated by Fig. 1 (g) mainly consisted of

H. Dai et al. / Surface & Coatings Technology 201 (2006) 28592866

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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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H. Dai et al. / Surface & Coatings Technology 201 (2006) 28592866


Table 1
Cu 2p3/2 BE, FWHM (0.1 ev) values and relative area (%) of coated-Cu mica
BE (ev)

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. 2. XPS survey spectrum for the coated-Cu mica powder.

76.05 wt.% Cu with the other underlying small amount substrate


elements such as Mg, Al, Si and K. It should be noted that the
peaks corresponding to Cu were not present in the as-received
mica, and it appeared only after the electroless coating process,
indicating successful Cu deposition on the mica surface by the
present electroless technique. The ICP-AES analysis showed
that the weight percent of Cu deposited on mica powder at 12 of
pH, at room temperature and 2 h of coating was 65.40 wt.%.
The density of the Cu-coated mica composite powder calculated by measuring the mass and volume was about 4.93 g/cm3.
The average specific volume resistivity, obtained by the four
probe method, was 4.12 1013 cm for mica and 5.67 10 2
cm for the Cu-coated mica. This great reduction in the specific
resistivity confirms that the mica was covered by the copper.
3.2. Cu 2p XPS and AES depth profile analyses of Cu-coated
mica powder
XPS survey spectrum for the coated-Cu mica powder was
presented in Fig. 2. In the spectrum, only Cu element with a

Fig. 3. Cu 2p narrow XPS spectrum for Cu-coated mica powder.

small amount of O and C elements was detected on the mica


surface, which indicates thick coating developed on the mica
surface. The carbon signal from the surface came from the
contaminants, and the oxygen mainly from oxygen in the air.
The Cu-coated mica powder was extremely reactive towards
atmospheric oxygen. This affinity of the Cu coating towards
oxygen is attributed to the large specific surface area of fine
powder coating. Narrow XPS scan of Cu 2p within the binding
energy (BE) interval of 925965 ev is showed in Fig. 3. Table 1
gives the values of BE, FWHM and relative area of the Cu 2p3/2.
The Cu 2p spectrum presents a doublet corresponding to Cu
2p1/2 and Cu 2p3/2 with a BE difference of 19.9 ev [21]. The
spectrum can be fitted with three two spin-orbit-spilt doubles.
The main doubled with the Cu 2p3/2 peaks lying at 932.2, 932.9
and 933.8 ev with a FWHM of 1.3, 1.3 and 2.3 ev are attributed
to Cu (0), Cu2O and CuO, respectively. The relative area from
XPS spectrum allows for the determination of the relative
quantity of total Cu, their concentration was 46.4, 38.2 and
15.4 at.%, respectively. The oxidized copper (CuO and Cu2O,
54 at.%, at a depth of around 10 nm) is non-conducting,
therefore, the application of Cu-coated mica powder for using as
a conductive filler will be affected if this problem is not well
solved.
The results of AES profiles performed on Cu-coated mica
powder are shown in Fig. 4. Only C, O and Cu signals were
detected from the surface, and there was no signal from the
elements of the mica substrate. It has to be noticed that all carbon
peaks, located around 284.5 and 288.2 ev and characteristic of
CC and CO bonding, disappear after the first run of sputtering. For this reason, the contribution of carbon contamination

Fig. 4. AES depth profiles for Cu-coated mica powder.

H. Dai et al. / Surface & Coatings Technology 201 (2006) 28592866

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).

will be neglected. At a depth of around 28 nm, the oxygen


concentration was close to zero and the copper concentration
was 99.6 at.%. From the trends of the signals, we can assume that
there is a metallic Cu layer of at least 240 nm thickness with an
oxidized copper layer of about 28 nm on the mica surface.
The analyses of the Cu 2p XPS and AES depth profiles of
Cu-coated mica show that there is a relatively uniform metallic
Cu layer on the mica surface, which is extremely reactive
towards atmospheric oxygen.

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(no.04-0836); the peaks of the (111), (200), (220), (311) and


(222) planes of Cu were identified, indicating that the Cu-coating
has the fcc crystalline structure. Moreover, a trace of Cu2O and
CuO can also be seen in Fig. 5 (d), which is in an agreement with
the analysis of the Cu 2p3/2 XPS of Cu-coated mica.
Because of the strong preferred-orientation of K-TSM during
the powder XRD data collection, the (00l) diffraction lines are the
prominent lines, as shown in Fig. 5(a). For the three strongest lines
with d values of 0.9995, 0.3314 and 0.1998 nm of K-TSM, their
d values are in line with the relationship d (003) = 3 d (009) = 5 d(0015).
The spacing distance of (003) plane corresponding to the basal
space was 0.9995 nm. The K-TSM (florophlogopite) in this work
is a 2:1 type synthetic layer lattice silicate material, its crystal
structure consists of layers made up of two tetrahedral coordinated
silicon atoms joined to one edge-shared octahedral sheet of either
aluminum or magnesium hydroxide, and there usually exists isomorphic substitution within the layers (for example, Si4+ replaced
by Al3+, Al3+ replaced by Mg2+) [22]. The schematic drawing of
structure of K-TSM in this work is shown in Fig. 6.
It is well known that the ion-exchange properties of naturally
occurring aluminosilicates as the clays and layered silicates (e.g.
montmorillonite, hectorite, saponite, zeolites, sodium fluorotetrasilisic mica (Na-TSM), etc.) [23,24]. Isomorphic substitution of the
layers within these silicates will generate negative charges in the
silicate lamellae surface. To keep the charge balance, they need to
adsorb cations. The ways of adsorbing cations include: (1) cationic
exchange the silicate layers are negatively charged, which is
compensated by the cations being incorporated in the interlamellar
spaces; (2) surface adsorption the negatively charges from
isomorphic substitution within the layers can adsorb cations by
static force. The hydrated Na+ ions located in the sheets of the clays
and layered silicates can undergo a cationic exchange reaction with
other cations [2225]. Since the structure of K-TSM is similar to
that of the above clays, the cationic exchange in the interlayer
might be expected with K-TSM, too. If this kind of reaction could
occur in K-TSM, a change of its basal space would be anticipated
by the exchange of internal K+ ions with other cations such as the
[Ag(NH3)2]+ ions and more the bulky alkylammonium compounds. XRD analyses of K-TSM in different conditions was
carried out to identify the way in which it adsorbs cations, whether
by interlamellar cationic exchange or by surface adsorption.

3.3. Powder XRD analyses


The powder XRD patterns are presented in Fig. 5. Compared
with PDF card (no.16-0352), Fig. 5 (a) shows the three strongest
major peaks of mica powder (K-TSM) are (009), (003) and
(0015) plane respectively, indicating that the mica structure in
this work belongs to the hexagonal crystal system. The pattern of
Cu-coated mica in Fig. 5 (d) was compared with PDF card

Fig. 6. Structure of potassium-type synthetic fluorotetrasilisic mica (fluorophlogopite, K-TSM).

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H. Dai et al. / Surface & Coatings Technology 201 (2006) 28592866

The samples of the activated mica and the organomica were


prepared, the XRD patterns for the activated mica and the
organomica were plotted in Fig. 5 (b) and (c). The d (003)
diffraction peaks of the activated mica and the organomica were
at 2 = 8.83 and at 2 = 8.82, respectively, and their basal
spacing was 1.001 nm and 1.002 nm. Compared with K-TSM
[d (003) = 0.9995 nm], the spacing of d (003) plane for the activated mica and the organomica keeps almost no change,
indicating that the [Ag(NH3)2]+ ions and the HLA+ did not
intercalate the aluminosilicate layers. Hence, it is inferred that KTSM in this work differs from the above clays, it does not
expand and its interlayer K+ ions are not exchangeable under
ambient conditions, and it adsorbs cations mainly by surface
adsorption [2628]. One of the reasons for this may be that the
size of K+ ions in the interlayer is large [29], and there exists
much strong electrostatic force in the layers of K-TSM, resulting
in holding aluminosilcate layers and the interlayer K+ ions
together under ambient conditions [30].
3.4. FTIR spectra analyses
Fig. 7 shows the FTIR spectra of electroless copper coating of
mica powder at different stages. Fig. 7 (a) shows the IR bands at
3456 cm 1 and 1639 cm 1 respectively, resulted from the
stretching and bending vibrations of the OH groups of mica
surface, and the bands at 1018 cm 1 and 509 cm 1 respectively,
resulted from the stretching vibrations of the mica surface SiO
and AlO groups. After the mica was activated with the [Ag
(NH3)2]+ activator, a band which resulted from the stretching
vibration of NH3 groups appeared at 3448 cm 1, which overlaps
the mica surface OH groups, indicating the presence of the [Ag

Fig. 7. FTIR spectra of electroless copper coating of mica powder at different


stages [(a) mica powder, (b) the activated mica powder, and (c) the reduced mica
powder]. (The preparation of the reduced mica was as follows: 3 g of the
activated mica was transferred to 500 ml distilled water, and then 5 ml of
reducing agent HCHO (37 wt.%) was added under stirring, reacted for 10 min at
room temperature. The resulting product was separated by vacuum filtration,
washed thoroughly with distilled water, and then dried for 2 hours at 80 C).

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

H. Dai et al. / Surface & Coatings Technology 201 (2006) 28592866

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The overall reaction can be written as:


2HCHO Cu2 4OH YCuA 2HCOO H2 z
2H2 O

Fig. 9. Schematic representation of electroless Cu coating of mica powder.

directly mainly by surface adsorption, and silver can act as a


catalyst for the reducing agent HCHO [20]. As a result of the
properties of the mica and silver, we suggest that the possible
mechanism of electroless copper coating of mica powder is as
follows (Fig. 9):
(1) The activation of mica powder
When mica powder was transferred to the activation bath, the
activator [Ag(NH3)2]+ ions was adsorbed on the mica surface
by the static force between the AlO anions and [Ag(NH3)2]+
ions [in step (1) of Fig. 9].
mica AgNH3 2 

adsorption

micaAgNH3 2 

(2) Electroless Cu coating of mica powder


After the activated mica powder was transferred to the electroless Cu coating bath, the reducing agent (HCHO) in the bath
solution immediately reduced the [Ag(NH3)2]+ions adsorbed
on the mica surface to the metallic Ag0 clusters [in step (2a) of
Fig. 9], according to the following reaction:
2AgNH3 2  HCHO 2OH Y2AgA 3NH3
HCOO NH
4 H2 O

2a

2b

In the reaction initiation, the metallic Ag0 clusters act as


nucleation sites for the copper deposition. In aqueous alkaline
solutions (usually pH > 11), formaldehyde (HCHO) adsorbed on
the catalytic Ag0 surfaces is easily oxidized to yield HCOO,
the activated hydrogen atom (H) and release electrons (Anodic
reaction), whereas Cu ions in the coating bath are reduced to
metallic Cu0 by the electrons generated through the oxidation of
HCHO (cathodic reaction). The combination of two activated
hydrogen atoms will be responsible for part of the observed gas
evolution. Once the Cu deposition was initiated, the deposited
Cu atoms themselves acted as self-catalysts for further Cu
deposition and well-developed copper coating on the mica
powder surface was then obtained via this electroless coating
process.
4. Conclusions
Cu-coated mica composite powder has been prepared
successfully by electroless Cu coating using cheaper activator
[Ag(NH3)2]+, without etching, sensitization or acceleration
pretreatment process. Analyses of the XRD and FTIR indicated
that K-TSM adsorbs the activator [Ag(NH3)2]+ ions mainly by
surface adsorption, and the Cu-coating has the fcc crystalline
structure. The SEM/EDX, XPS, and AES analyses showed that
there was a relatively densely, uniformly distributed metallic
Cu layer on the mica surface. The composite powder obtained
under the giving coating conditions contains 65.40 wt.% copper, with a density of about 4.93 g/cm3 and an average specific
volume resistivity of 5.67 10 2 cm. The activation process
in this work has the advantages of simplicity and lower cost, and
it could be extended other substrates with same crystal structure,
especially the swelling layer lattice materials. AgNO3 could be a
potential alternative to the relatively expensive PdCl2 catalyst
for electroless Cu coating.
Acknowledgements

It is the metallic Ag clusters that function as the actual


catalyst for electroless copper coating. It is known that the
electroless copper coating process is electrochemical in nature
[16,3133].The beginning of the copper deposition is controlled by the anodic processes. Under the catalytic action of
metallic Ag0 clusters adsorbed on the mica surface [in step (2b)
of Fig. 9], Cu2+ ions get deposited on to the catalytic silver
surface by capturing electrons furnished by reducing agent
(HCHO) via the following chemical reactions:Anodic reaction:
Ag

HCHO 2OH Y HCOO H H2 O e2 HYH2 z


Cathodic reaction:
Cu2 2eYCuA

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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