Surface & Coatings Technology 201 (2006) 371 383

www.elsevier.com/locate/surfcoat

Electrodeposition of composite coatings containing

nanoparticles in a metal deposit
C.T.J. Low, R.G.A. Wills, F.C. Walsh
Electrochemical Engineering Group, School of Engineering Sciences, University of Southampton, Highfield, Southampton, SO17 1BJ, United Kingdom
Received 19 September 2005; accepted in revised form 24 November 2005
Available online 24 January 2006

Abstract

Recent literature on the electrodeposition of metallic coatings containing nanosized particles is surveyed. The nanosized particles, suspended in
the electrolyte by agitation and/or use of surfactants, can be codeposited with the metal. The inclusion of nanosized particles can give (i) an increased
microhardness and corrosion resistance, (ii) modified growth to form a nanocrystalline metal deposit and (iii) a shift in the reduction potential of a
metal ion. Many operating parameters influence the quantity of incorporated particles, including current density, bath agitation (or movement of work
piece) and electrolyte composition. High incorporation rates of the dispersed particles have been achieved using (i) a high nanoparticle concentration
in the electrolyte solution, (ii) smaller sized nanoparticles; (iii) a low concentration of electroactive species, (iv) ultrasonication during deposition and
(v) pulsed current techniques. Compositional gradient coatings are possible having a controlled distribution of particles in the metal deposit and the
theoretical models used to describe the phenomenon of particle codeposition within a metal deposit are critically considered.
2005 Elsevier B.V. All rights reserved.

Keywords: Electrodeposition techniques (direct current, pulsed direct current, pulsed reverse current); Nanosized particles; Compositional gradient coatings;
Codeposition of particles; Composite coatings; Modelling codeposition; Rotating cylinder electrode

1. Introduction sistance in memory storage systems and increased microhard-

The electrodeposition of metallic coatings containing inert
particles can be traced back to studies which produced a
graphitecopper composite coating for self-lubricating surfaces
in car engines [1]. In the early 1950s and late 1960s, the
development of electrodeposited composite coatings developed
progressively [2]. During the 1970s and 1980s, investigations
were focused on the need to produce coatings with enhanced
mechanical, corrosion and tribological properties.
The advanced physical properties of composite coatings
quickly became clear and during the 1990s, new areas such as
electrocatalysts and photoelectrocatalysts were considered [3].
With the emergence of nanostructured materials over the last
decade, electrodeposition techniques have provided a route to a
variety of new nanomaterials. These include nanocrystalline
deposits, nanowires, nanotubes, nanomultilayers and nanocom-
posites. Strengthened composite coatings, enhanced electrical
resistance in printed circuit boards, improved giant magnetore-
Corresponding author.
E-mail address: F.C.Walsh@soton.ac.uk (F.C. Walsh).
0257-8972/$ - see front matter 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2005.11.123
ness for microdevices in micro-electro-mechanical systems
have been the focus of numerous studies.
This paper surveys recent techniques used to produce nano-
composite coatings where nanosized particles are suspended in
the electrolyte and codeposited with the metal. The effect of ope-
rating parameters that influence the quantity of nanosized particles
incorporated into the metallic deposit is discussed and theoretical
models used to describe the codeposition phenomenon are high-
lighted. Table 1 shows the categories of nanostructured materials
along with various electrodeposition manufacturing techniques.
Readers are directed to a number of earlier reviews [220] for a
detailed background to composite electrodeposition of larger
particles which typically have sizes in the range 180 m.
2. The mechanism of codeposition of particles into a metal
deposit
Two common processes involved in the incorporation of
particles into metallic coatings can be recognised, namely
physical dispersion of particles in the electrolyte and electro-
phoretic migration of particles [15].
372 C.T.J. Low et al. / Surface & Coatings Technology 201 (2006) 371383

Table 1
Various types
typesofof
nanostructured
nanostructured
materials
materials
whichwhich
may bemay
produced
be produced
by electrodeposition
by techniques
electrodeposition techniques
Methods of electrodeposition Types of nanostructure materials
Nanoparticles in a metal deposit Nanomultilayers Nanotubes/nanowires Nanocrystalline materials

Single metal deposit Metal type 1 Nanotubes Single metal

Direct current (DC) e.g. Ni layer

Pulsed direct current (PDC)

Nanoparticles
Pulsed reverse current (PRC) Alloy deposit Nanowires Alloy

Potentiostatic (P) Metal type 2

Multilayer deposit e.g. Cu layer
Tree-like
Pulsed potentiostatic (PP)
nanowires Fe Co

Table 2
Examples of theoretical models used to describe the behaviour of metal electrodeposition containing particles
Model Characteristics and assumptions Deposit and process conditions
Reaction Particles Current density j, Rotation Ref.
sizes, m mA cm2 speed , rpm
Guglielmi, 1972 Describes both adsorption and electrophoresis. Ni/TiO2 Ni/SiC 12 20100 NG [21]
The particles are covered by adsorbed metal ions.
Particle characteristics and electrolyte conditions
are accounted semi-empirically. The effect of flow
is not considered.
Celis et al., 1987 Uses probability concept to describe the amount Cu/Al2O3 Au/Al2O3 0.05 090 400600 [23]
of particles that can be incorporated at a given
current density. Mass transport of particles is
proportional to the mass transport of ions to the
working electrode. Volume ratio of particles in
the metal deposit will: (1) increase under charge
transfer control; (2) decrease under mass
transport control.
Fransaer et al., 1992 Uses trajectory to describe the codeposition of Cu/PS 11 080 0700 [24]
non-Brownian particles. Involves two steps: Ni/SiC 0.0110 0200 02000 [25]
(1) reduction of metal ions (described by
Butler-Volmer expression); (2) codeposition of
particle (described by trajectory expression).
Hwang et al., 1993 An improvement of Guglielmi's model. Uses three Co/SiC 3 160 400 [26]
modes of current density (low, intermediate, high)
to distinguish the reduction of adsorbed ion on
particles. Involves three steps: (1) forced
convective of particles to surface; (2) loose
adsorption on the surface; (3) irreversible
incorporation of particles by reduction
of adsorbed ions.
Vereecken et al., 2000 The transport of particles to the surface is controlled Ni/Al2O3 0.3 540 5002000 [27]
by convective-diffusion. The influence of particle
gravitational force and hydrodynamics is
accounted for at various current densities. Valid
only when the particle size is smaller than the
diffusion layer thickness.
Bercot et al., 2002 An improvement of Guglielmi's model, which Ni/PTFE 0.5 1070 4001000 [28]
incorporates a corrective factor (a 3rd order
polynomial equation) to account for the effects
of adsorption and hydrodynamic conditions.
More details on the accuracy of each model are available elsewhere [11,18,37].
NG: not given.
 C.T.J. Low et al. / Surface & Coatings Technology 201 (2006) 371383
Codeposition mechanisms for the dispersion of inert
particles into metallic coatings have been developed from
investigations of micron sized particles. Many theories have
been suggested including the transport of particles due to (1)
electrophoresis, (2) mechanical entrapment, (3) adsorption and
(4) convective-diffusion. Table 2 [2128] provides an overview
of the existing models and their main assumptions. The
mechanism proposed by Guglielmi [21] has been adopted by
various authors. This model enables a quantitative treatment of
the influence of particle concentration and current density on the
incorporation rate of particles into a metal deposit but excludes
hydrodynamic effects and particle characteristics. A corrective
factor (3rd order polynomial equation) has been included into
Guglielmi's model to account for the effects of adsorption and
hydrodynamics on the incorporation of 500 nm PTFE
nanoparticles into a nickel deposit [28]. However, the validity
of this function may only lie within a narrow range of
experimental parameters and its ability to accurately predict
other systems requires study.
Fig. 1 shows the common processes involved in the
codeposition of particles into growing metallic layers. Five
Cathode
Deposit Bulk
electrolyte
Electrical Diffusion Convection
double layer layer
layer
Particles (conductive or non conductive)
Surfactant (ionic, non-ionic or organic)
Clouding of particles by surfactants
Clouding of particles by cations
Deposited metal
Fig. 1. Mechanisms of particle codeposition into a metal deposit [7]. The regions
include: formation of ionic clouds around the particles (bulk electrolyte, typical
length in cm); convective movement toward the cathode (convection layer,
typical length b1 mm); diffusion through a concentration boundary layer
(diffusion layer, typical dimensions of hundreds of m); electrical double layer
(typical dimensions of nm) followed by adsorption and entrapment of particles.
373
consecutive steps during the codeposition process can be
identified [7]: (1) formation of ionic clouds on the particles,
(2) convection towards the cathode, (3) diffusion through a
hydrodynamic boundary layer, (4) diffusion through a
concentration boundary layer and finally, (5) adsorption at
the cathode where particles are entrapped within the metal
deposit. Other models include a statistical approach [710,24]
which predicts the probability of a particle being incorporated
into a deposit and particle trajectory models [24,25] which
describe non-Brownian particles. The relationships between
the quantity of particles in the metal deposit and current
density or hydrodynamics have been the focus of many
experimental studies.
Although many theoretical models have been proposed, the
flexibility and reliability of each to describe the behaviour of
a wide range of metallic coatings and particle types still
requires validation. Often, the existing models involve
mathematical relationships that are interrelated to an extensive
set of parameters and, in all the models available so far, the
effects of particle inclusion on deposit electrocrystallisation
have not been considered. This aspect is important since the
inclusion of particles into a metal deposit may cause (1)
reduction of the cathode surface area if the particles are non-
conductive, (2) enlargement of the cathode surface area if the
particles are conductive or (3) modification of the deposit
morphology.
Presently, the models used to describe the inclusion of
micron sized particles are restricted to specific conditions and
empirical laboratory trials remain important. Future models
describing the codeposition process will require adequate
attention to interactive variables such as the particle character-
istics (type, dimensions and concentration), the operating
parameters (temperature, current density, pH and hydrody-
namics) and the electrolyte composition (concentrations,
presence of surfactants and additives).
3. Experimental parameters
A variety of nanosized particles (typically with spherical
dimensions), ranging from 4 nm to 800 nm diameters, have
been successfully incorporated into metal electrodeposits.
These include aluminium dioxide (Al2O3), chromium (Cr),
diamond (C), silicon carbide (SiC), gold (Au), silicon dioxide
(SiO2), zirconium dioxide (ZrO2), titanium dioxide (TiO2),
polystyrene (PS) and silicon nitride (Si3N4). Amongst many
metals used, copper and nickel have featured strongly.
Alumina particles have been the subject of many investigations
compared to other nanoparticles. Table 3 [23,2942] shows the
recent examinations of the codeposition of alumina particles
while Table 4 [22,25,4357] considers other particulate
inclusions.
The inclusion of nanosized particles into metal deposits is
dependent on many process parameters, including particle
characteristics (particle concentration, surface charge, type,
shape, size), electrolyte composition (electrolyte concentra-
tion, additives, temperature, pH, surfactant type and
concentration), current density (direct current, pulsed current,
374 C.T.J. Low et al. / Surface & Coatings Technology 201 (2006) 371383

Table 3
Investigations of the inclusion of Al2O3 particles into metal deposits by electrodeposition techniques
Nanoparticles Metal Nanoparticle concentration Experimental characteristics
deposit
In solution, In deposit Method Current density j, Rotation Temp. T, pH Substrate Ref.
g dm3 mA cm2 speed , rpm K
10 nm -Al2O3 Ni 220 030 wt.% DC 250 2001600 NG 3 Cr, Au [29]
25 nm -Al2O3 Ni 10, 150 NG DC, PC 0.15, 0.77, 1 NG 298 3.5, 4 Cu [30]
32 nm -Al2O3 Cu 060 135 wt.% DC 0 to100 9003600 NG 0.22 Au [31]
32 nm -Al2O3 Ni 10, 25 07.5 wt.% DC, PRC 92.8 to 26.5 225, 1600 NG 3, 4, 4.5 Au [32]
32 nm Al2O3 Cu 12.5, 25 2.912.7 wt.% PRC 5, 10 800, 1600 NG 4 Au [33]
32 nm Al2O3 Ni, Cu 3.125, 12.5 16 wt.% PC 10, 15 1000 299 8 Au [34]
37 nm Al2O3 Cu 12.550 317 wt.% DC, PRC 0.6 to 0.15 C/cm2 800 NG 4 Au [35]
37 nm Al2O3 Cu 12.5 317 wt.% DC, PRC 5, 10 800 298 4 Au [36]
50 nm -Al2O3 Cu 3.9158 NG NG NG 5001500 NG 0.3 Cu [37]
50 nm -Al2O3 Cu, Au 090 023.5 wt.% DC 20 400 293 0.3 NG [23]
50 nm Al2O3 Ni 0.1, 2 vol.% 020 vol.% DC 5, 20, 40 5001000 NG 3 Cu [38]
80 nm Al2O3 Ni 50 NG PC 15 600 313 4.2 SS [39]
80 nm Al2O3 Ni 5 1.426.8 vol.% NG 30, 60 200 318 4 CS [40]
300 nm Al2O3 Ni 2 vol.% 925 vol.% DC 540 500, 2000 297 3 Cu [41]
50, 300 nm Al2O3 Ni 2 vol.% 1025 vol.% DC 540 500, 2000 297 3 Cu [42]
DC, direct current; PC, pulsed current; PRC, Pulsed reverse current; NG, not given.

pulse time, duty cycle, potentiostatic control) and hydro-
dynamics (laminar, mixed, turbulent regimes) of together
with electrode geometry (rotating disk electrode, rotating
cylinder electrode, plate-in-tanks, parallel plate electrodes
and many variations).
Electrolyte composition is known to be a significant
factor affecting the codeposition process. However, a clear
picture of the exact effect of the experimental parameters
is often difficult to obtain. The majority of recent
investigations have suggested that three global factors can
be identified as influencing the codeposition processes,
namely (1) the applied current density, (2) the particle type
and concentration and (3) bath agitation or electrode
movement.
3.1. Current density
A variety of galvanostatic techniques can be utilised,
including direct current, pulsed direct current and pulsed
reverse current techniques. Galvanostatic control, as shown

Table 4
Inclusion of other types of particles into metal deposits by electrodeposition techniques
Nanoparticles Metal Nanoparticle concentration Experimental characteristics
deposit
In solution, In deposit Method Current density j, Rotation Temp. T, pH Substrate Ref.
g dm 3 mA cm 2 speed , rpm K
20 nm SiC Ni 1050 025 vol.% NG 580 100, 200 318 4 Ni [43]
20 nm SiC Ni 20 NG PC 50 200 323 4.4 Brass [44]
20 nm SiC Ni 20, 50 925 vol.% DC 40 0250 5.7 CS [44]
100 nm SiC Ni 0100 06 wt.% DC 10200 02000 323 4.5 Ti, Ni [25]
400 nm SiC Ni 20, 100 03 wt.% PC 900 750 313 4.5 Ti [45]
400 nm SiC Ni 20, 100 0.310.5 vol.% PC 900 750 313 4.5 Ti [46]
310 nm Au Ni 10 N.G NG 1050 100, 500 318 3, 5 SS [47]
Au Ni 20 N.G NG NG NG NG NG NG [48]
50 nm SiO2 Zn 0.3 N.G DC 100 798 323 2 CS [49]
4, 10 nm ZrO2 Ni 10, 50 04 wt.% DC 10, 100 NG 333 2.5 Ti [50]
10 nm diamond Ni 10 N.G NG NG NG? 318 34.5 S [51]
25 nm diamond Ni 340 N.G DC 2550 45450 303 NG Cu [52]
30 nm Si3N4 Ni, Fe 50300 23 vol.% NG 9 NG 298 4.8 Cu [53]
39 nm Cr Ni NG 9.6 DC 30 NG 308 5.5, 6 Ni [54]
12 nm TiO2 Ni 0200 011 wt.% DC 66.7 NG NG NG Cu [55]
20 nm TiO2 Ni 10 to120 020 wt.% DC 20 NG NG 3 Cu [56]
4 nm diamond Au 0.110 NG DC 5, 10 NG 335 5.8, 6 Cu [57]
32 nm Al2O3
30 nm Al2O3 60 nm Ni 1.5 vol.% NG NG 1.580 0 298323 2, 6 Cu [22]
ZrO2 62 nm SiC
DC, Direct current; PC, pulsed current; PRC, pulsed reverse current; NG, not given.
 C.T.J. Low et al. / Surface & Coatings Technology 201 (2006) 371383 375

in Fig. 2, can also be employed however direct current has most
commonly been used to obtain nanoparticle composites. This
technique is based on the concept that the incorporation of
nanoparticles occurs simultaneously with the reduction reaction
of an ionic species to form the metal surface.
The application of a pulsed current has enabled the
incorporation of higher concentrations of nanoparticles as
well as producing a wider range of deposit compositions and
properties. The pulsed direct current technique is based on
alternating two or more direct cathodic currents for various
deposition times. While the pulsed reverse current technique has
similar characteristics but imposes a cathodic current during the
on time and an anodic current during the off time. This method
has been the most successful for embedding higher concentra-
tions of nanoparticles because it helps to eliminate a fraction of
the electrodeposited metal during the off time.
Various authors have compared direct current and pulsed
current deposition. For example, during the electrodeposited
nanocrystalline nickel it is reported that under direct current, the
nanoparticles (25 nm alumina) are the main inhibiting factor for
the growth of nickel nuclei (average grain diameter of 30 nm).
Under pulsed direct current, however, the pulse length is the
(a) Current
whiskers in the nickel deposit was observed with significant
0 Time
+ deposit at high frequency.
(b) Current
0 Time
+
(c) Current
reduction in the current efficiency as well as hindering the
0 Time
+ Using a sulfamate bath containing 600800 nm -Al2O3
(d) Current
incorporated in the metal deposit (Fig. 3) [58]. Another study of
0 Time
+ nanoparticle content in the deposit was established at low
Fig. 2. Various modes of current density vs. time control during electrodeposi-
tion; (a) pulsed direct current with zero current during off-time, (b)
superimposed pulsed direct current with cathodic current during off-time, (c)
pulsed reverse current with anodic current during off-time, and (d) pulsed
reverse current with combination of zero and anodic current during off-time.
limiting factor (average grain diameter of 20 nm) [30]. This is
because selective entrapment of nanoparticles occurs with the
larger particles being preferentially removed during the reverse
pulse period, producing a finer deposit with less agglomeration
of nanoparticles.
The pulsed reverse current technique has been used to
produce a copper deposit containing high concentrations of 30
nm alumina nanoparticles [3336]. By using a steady state
pulsed reverse current and long pulse times, three main
advantageous can be achieved compared to the direct current
method: (1) the amount of nanoparticles in a metal deposit can
be enhanced, (2) a lower concentration of nanoparticles in the
electrolyte solution can be used and (3) selective entrapment of
similar sizes of nanoparticles can be achieved. All three
advantages can be associated with the partial dissolution of
the metal deposit during the anodic period where larger sizes of
nanoparticles tend to be lost from the deposit while smaller
nanoparticles continue to be entrapped.
Uniform and well-dispersed nanoparticle (80 nm alumina)
dispersions in a nickel deposit were achieved by the combina-
tion of pulsed current and ultrasound [39]. The introduction of
ultrasound reduced the quantity of alumina whiskers in the
nickel deposit and only large pyramidal grains were observed at
high frequency (50 Hz) with no alumina whiskers. At low
frequency (5.6 Hz) an increase in the amount of alumina
agglomeration of nanoparticles. The employment of ultrasound
during electrodeposition can reduce nanoparticle agglomeration
as well as removing the absorbed nanoparticles from the metal
Direct current combined with ultrasound has also been
studied as a function of concentration of the electroactive
species and it has been shown that agglomeration of alumina
nanoparticles can be reduced by using a lower concentration of
metal ions. For example, in a 1.27 M Ni2+ electrolyte, the
average nanoparticle size is approximately 280 nm; in a 0.20 M
Ni2+ electrolyte, the average nanoparticle size is 178 nm [40].
Although a lower concentration of electroactive species tends to
favour well-dispersed and less agglomerated nanoparticles, the
occurrence of hydrogen evolution must considered to avoid a
adsorption of nanoparticles to the metal surface.
The current density is also found to influence the amount of
alumina nanoparticles incorporated into electrodeposited nickel.
nanoparticles, an increase in current density resulted in a rough
surface microstructure and lead to less nanoparticles being
32 nm alumina nanoparticle, however, has demonstrated that
the degree of nanoparticle incorporation was dependent on the
electrolyte type [32]. In a chloride electrolyte, a higher
current density but in a citrate electrolyte, higher nanoparticle
contents were found at elevated current density. It was also
found that the current efficiency increased at higher current
densities in both electrolytes but the amount of nanoparticles in
the nickel deposit was higher in the presence of citrate ions. This
376 C.T.J. Low et al. / Surface & Coatings Technology 201 (2006) 371383

40 nanoparticles (50 nm and 300 nm) into a nickel deposit has

been studied. Using similar operating parameters (1000 rpm,
Percentage volume of particles in deposit

20 mA cm 2 and 73 C cm 2), it was found that the

30 percentage volume fraction of the 300 nm Al2O3 in the nickel

(a)
20 10

Percentage volume of C in Cu/Sn alloy deposit

8
10

0
0 5 10 15 20 25 30 4
Current density / A dm-2

Fig. 3. Influence of current density on the percentage volume of 600 to 800 nm 2

-Al2O3 particles in a nickel deposit [58]. 75 g dm 3, 150 g dm3 and
225 g dm 3. Electrolyte composition: 400 g dm 3 Ni(NH2SO3)24H2O, 30 g
dm 3, H3BO3, 5 g dm 3 NiCl26H2O, 0.5 g dm 3 CH3(CH2)10CH2OSO3Na, 0.1
g dm 3 C6H4OCOCHCH, 50 C and pH 4. 0
10 20 30 40 50 60
Amount of graphite in solution / g dm-3
suggests that the influence of current density can vary with (b)
12
electrolyte compositions.
Percentage volume of particles in deposit

3.2. Effects of nanosized particles on deposit characteristics 10

The effect of nanoparticle concentration in the electrolyte on 8

their concentration in the metal deposit has been predicted to
follow a Langmuir isotherm adsorption phenomenon 6
[22,42,5962]. Fig. 4 shows the relationship found by various
investigators. The amount of nanoparticles in the solution has
4
significant effect on the percentage volume fraction of the
nanoparticles incorporated into the metal deposits. Two general
observations can be made: (1) the volume fraction of 2
nanoparticles in the metal deposit increases substantially
when the amount of nanoparticles concentration in the solution 0
increases and (2) a saturation state of particles in the deposit is 0 30 60 90 120 150
reached at high nanoparticle concentration in the solution. Concentration of particles in solution / g dm-3
The size of particles will affect the rate of incorporation (c)
into the metal deposit. Findings have suggested that as the 0.25

size of nanoparticles becomes smaller, more can be incorpo-

Ratio of particle volume to deposit volume

rated into a metal deposit per unit volume. For example, the
0.20
rate of incorporation of two different sizes of Al2O3

0.15
Fig. 4. Langmuir isotherm showing the relationship between the quantity of
particles in the metal deposit and their concentration in the electrolyte. (a) CuSn
alloy deposit with 10 m graphite [62], showing the effect of rotation rate. Speed of
0.10
magnetic stirrer: 50 rpm, 100 rpm and 200 rpm. Electrolyte compositions:
29 g l1 CuCN, 35 g l1 K2SnO3, 64 g l1 KCN, 10 g l1 KOH, 45 g l1 Rochelle
salt, pH 12 and 40 C. (b) NiCo alloy deposit with 500 nm -Al2O3 [61], showing
the effect of temperature. Bath temperature: 50 C and 60 C. Electrolyte 0.05
compositions: 300 g l1 Co(NH2SO3)24H2O, 300 g l1 Ni(NH2SO3)24H2O, 20
ml l1 CH3NO and pH 4.5. (c) Ni deposit with Al2O3 [38,42], showing the effect of
particle sizes. 300 nm and 50 nm -Al2O3. Electrolyte compositions: 1.24 0.00
mol l1 Ni(NH2SO3)2, 0.5 mol l1 H3BO3, 0.02 mol l1 NiCl2, 0.5 g l1 CH3 0.0 0.5 1.0 1.5 2.0
(CH2)11OSO3Na, 0.1 g l1 C9H6O2, pH 3 and 25 C. Percentage volume of particle in solution
 C.T.J. Low et al. / Surface & Coatings Technology 201 (2006) 371383
deposit was much higher compared to the 50 nm Al2O3.
However, the quantity of 50 nm Al2O3 particles in the nickel
deposit was much larger than the quantity of 300 nm Al2O3
particles [38,42].
In the case of electrodeposition of nickel containing titanium
dioxide particles, the weight percentage of 12 nm anatase in the
nickel deposit was higher than for 1 m rutile particles in the
nickel deposit. The deposit incorporating 12 nm anatase displayed
superior corrosion resistance in acidic solution (pH 3.13.3
glacial acetic acid, 5.0% NaCl, 1.0 g dm 3 CuCl22H2O, 50 C
and 1 week) but showed only a slight increase in Vickers
microhardness compared to the 1-m rutile containing deposit.
Nanoparticle concentration in the deposit has been found to
affect both surface roughness and deposit microstructure. For
example, the surface microstructure of a nickel deposit
containing 32 nm -Al2O3 nanoparticles changed from rough
to smooth as the concentration of particles in the solution
increased from 0 g dm 3 to 60 g dm 3 [31].
The presence of nanosized particles in a metal deposit may
induce changes in the crystalline structure of the metallic
coating. It has been shown that 20 nm SiC nanoparticles
influence the competitive formation of nickel nuclei and
crystal growth [63]. The presence of 20 nm SiC nanoparticles
shifted the reduction potential of nickel ions to more positive
potentials and increased the current density. This can be
associated with an increase in surface area of the cathode due
to the adsorbed nanoparticles. By increasing the surface area,
more nucleation sites are available for the nickel ions and
crystalline growth is suppressed during electrodeposition.
Consequently, a smaller crystal grain size can be obtained
giving an enhanced microhardness.
Other investigations have demonstrated that 20 nm SiC
nanoparticles can lead to a more uniform dispersion in a nickel
deposit than 1 m SiC microparticles [40]. Besides the
incorporation of nanoparticles at the borders and edges of the
nickel crystals, the authors showed that the nanoparticles could
also be embedded in the nickel crystal itself [44]. These
observations are echoed in other investigations [45,54,55,63]
and lead to the conclusion that the presence of nanoparticles will
perturb the crystalline growth of a metal deposit, resulting in an
increased number of defects in the crystal structure, facilitating
a nanocrystalline structure with increased microhardness.
During the incorporation of 39 nm Cr particles into a nickel
deposit, the average nickel grain size was reduced from 42 nm
to 31 nm in the presence of Cr nanoparticles [54]. The authors
used X-ray diffraction to show that the codeposited nanopar-
ticles suppressed the preferred growth direction of the nickel,
producing a more homogeneous surface. Enhanced surface
properties depend not only on the quantity of nanoparticles in
the metal deposit but also on the crystal structure and
distribution of nanoparticles in the coating.
There appear to be no investigations on structurally different
nanosized particles in a single metal deposit. The type of particles
(conducting or non-conducting) and their shape (e.g. nanotubes,
nanorods or nanopellets) may have different effects during the
incorporation process. Other factors that may affect deposition
processes include the ageing of nanosized particles suspended in
377
the electrolyte, the suspension stability of particles at long times
and the use of electrolyte additives, particularly surfactants.
3.3. Influence of bath agitation and cathode movement
Bath agitation serves two purposes, namely to keep the
particles suspended in the electrolyte and to transport the
particles to the cathode surface. Many investigations have found
that increased agitation generally enhances the amount of
particles in the metal deposit. However, excessive agitation may
lead to a lower quantity of particles in the metal deposit. This
may be explained by vigorous hydrodynamic forces in the
electrolyte removing the particles from the cathode surface
before they can be entrapped in the metal deposit.
Fig. 5 shows the relationship between electrode rotation rate
and particle inclusion for a nickel deposit containing 500 nm
PTFE particles [28]. An optimum incorporation rate is seen which
depends on both particle concentration and rotation speed. At a
fixed applied current density of 3 A dm 2, the maximum rotation
speed observed before any fall off in volume percentage of
particles varies with loading of particles in the electrolyte. This
effect is also seen during the codeposition of 32 nm -Al2O3
particles in a copper deposit [31]. In the latter case, the influence of
electrode rotation rate on the polarization curves did not show a
dependence on particle concentration. The authors showed that, at
a 12.5 g dm 3 alumina nanoparticle concentration in the bath, the
charge transfer region did not alter with rotation rate; at 39 g dm 3
of alumina nanoparticles, the reduction of copper ions is inhibited
at all rotation rates and at 60 g dm 3 of alumina nanoparticles,
both the inhibition and enhancement of the copper ion reduction
occurred at different rotation rates. This complex, non-linear
relationship as observed on the polarization curves, suggests that a
10
Percentage volume of particles in the deposit
8
6
4
2
0
400 600 800 1000
Magnetic follower rotation rate / rev min-1
Fig. 5. Influence of rotation speed (of a magnetic stirrer) on the amount of 500 nm
PTFE particles incorporated into a nickel deposit [28]. 10 g dm 3, 20 g
dm 3; and 30 g dm 3 of PTFE particles in the solution. An optimum
incorporation rate can be observed as a function of both the particle concentration
and rotation speed. Electrolyte composition: 300 g l 1 Ni(NH2SO3)2, 10 g l 1
NiCl2, 30 g 1 H3BO3, pH 4 and 55 C.
378 C.T.J. Low et al. / Surface & Coatings Technology 201 (2006) 371383
simple mechanism based on the adsorption and electrophoretic
effects cannot sufficiently be explained by a simple model.
Two common techniques have been used to keep particles
suspended in the electrolyte, namely (1) physical dispersion of
particles by bath agitation and (2) chemical dispersion of
particles by surfactants. A combination of cationic, anionic and
non-ionic surfactants can be used to achieve control of surface
charge on the particles and the degree of suspension in the
electrolyte [15]. The strategies for bath agitation can be
controlled in many ways depending on the dimensions of the
electroplating bath, as shown in Fig. 6. For industrial
applications, the popular methods used in open tanks include
the overhead blade stirrer, the reciprocating plate plunger or a
pumped recycle loop of the electrolyte [15]. For laboratory
investigations, magnetic stirrers, rotating disk or cylinder
electrodes and parallel plate channel flow can be employed.
In contrast, the commonly used plate-in-tank geometry provides
poorly defined fluid flow conditions.
(a) (b) (c)
Object to be plated Particles in solution
(d) (e) (f)
Magnetic bar Surface to be plated
(g) (h) (i)
Particles
Surface to be plated
Fig. 6. Strategies for bath agitation. For industrial applications, the popular
methods used in open tanks include: (a) overhead blade stirrer, (b) reciprocating
plate plunger, and (c) pumped electrolyte [15]. For laboratory investigations,
methods include: (d) magnetic stirrer, (e) rotating disk, (f) rotating cylinder
electrodes, and (g) flow between parallel plates. The black area is the cathode
surface where electrodeposition occurs and the white areas are insulating
surfaces. The particles can also be suspended in the solution by (h) use of a
cationic surfactant and (i) a combination of ionic and non-ionic surfactants.
The rotating disk electrode, rotating cylinder electrode and
parallel plates channel flow provide controllable hydrody-
namics for quantitative characterisation of electrolytes con-
taining particle suspensions. Three different flow regimes can
be distinguished: laminar, transition (laminar to turbulent) and
turbulent. For micron-sized particles, there is generally no
significant influence of electrolyte flow on particle content in
the laminar region; in the transition regime, the particle
content increased at higher flow rates; and in the turbulent
regime, the particle content tended to decrease at higher rates
[11].
The presence of micron-sized particles can provide an
enhancement of mass transport to the cathode. As an
example, the expression for mass transport dimensionless
correlation for a solution containing 1030 vol.% of 2546
m microparticles [64]:
Sh aRe0:43 Sc0:33 1
a 0:14U0:64 2
where a is a constant and is the volume fraction of
microparticles in the solution, Sh is the Sherwood number
describing the mass transport due to forced convection, Re is the
Reynolds number describing the fluid flow and Sc is the Schmidt
number describing the electrolyte transport properties. The
influence of nanosized particles on mass transport enhancement
has yet to be studied systematically. It was suggested that the
amount of 32 nm alumina nanoparticles in a nickel deposit is
strongly influenced by hydrodynamics but an increased
nanoparticle concentration at low rotation rates did not follow
a 0.7 power relation for a mass transport controlled rotating
cylinder electrode [32]. This can be attributed to the shearing and
adsorption forces being the rate controlling steps at high rotation
speeds, resulting in a lower particle concentration in the nickel
deposit.
Rotating cylinder electrodes (RCEs) have been used in
many investigations to obtain controlled mass transport during
the deposition of single metal, alloy, composite and multilayer
deposits (Table 5). Further details concerning hydrodynamics,
mass transport and fundamental characteristics of RCEs are
available elsewhere [20,6567]. Pulsed reverse current regimes
have been used at RCE cathodes for the incorporation of 32
37 nm -Al2O3 nanoparticles into a copper deposit [32,34,36].
The authors have shown that the pulsed reverse current
technique was most beneficial at low nanoparticle concentra-
tions in the electrolyte, minimizing agglomeration and assisting
high nanoparticles level in the metal deposit.
Linear sweep voltammetry has been used to study the
influence of various bath concentrations on the codeposition of
50 nm -Al2O3 nanoparticles and copper at a rotating cylinder
electrode [37]. The nanoparticle concentrations were 3.9, 19.5,
39, 120 and 158 g dm 3 with electrode rotation speeds of 500,
1000 and 1500 rpm. It was found that increasing the alumina
content from 3.9 g dm 3 to 158 g dm 3 decreased the effective
concentration of copper ions, increased the viscosity and
lowered the electrolyte conductivity. The presence of alumina
 C.T.J. Low et al. / Surface & Coatings Technology 201 (2006) 371383 379

Table 5
Examples of studies using rotating cylinder electrode cathodes
Materials deposited Rotation Peripheral Current RCE characteristics
speed , velocity density j,
Diameter d, cm Length l, cm Area A, cm2 Substrate Ref.
rpm U, cm s 1 mA cm 2
800 nm polystyrene, Zn NG NG 01000 NG NG 6.7 Al [11]
32 nm -Al2O3, Ni 2251600 11.883.8 140 to 140 1.0 1.2 3.77 Au [32]
32 nm -Al2O3, Cu 800 41.9 100 to 100 1.0 1.2 3.77 Au [33]
32 nm Al2O3, Ni/Cu 1000 52.4 050 1.0 1.2 3.77 Au [34]
37 nm -Al2O3, Cu 800 41.9 100 to 100 1.0 1.2 3.77 Au [36]
50 nm Al2O3, Cu 5001500 31.494.3 0100 1.2 0.8 3.02 Stainless steel [37]
NG, not given.

nanoparticles also resulted in a lower current density in the (a)

24
charge transfer controlled and mixed controlled regions but no
systematic relationships were obtained in the mass transport
controlled region.
Other investigations using rotating cylinder electrodes 22

Deposition rate / m h-1

include: (1) the study of non-ionic, anionic and cationic
surfactants (cetylpyridinium chloride, cetytrimetylammonium
bromide, cetyltrimetylammonium chloride, nonylphenol 20
(ethoxylate)28(propoxylate)13(NPE1800) and sodium dodecyl-
sulphate) on the electrodeposition of zinc containing 800 nm
polystyrene nanoparticles [11], (2) the electrodeposition of an
AuCu alloy with B4C particles using a galvanodynamic 18
technique where the current density was stepped at 1 mA min 1
from 4 to 12 mA cm 2 [68] and (3) the codeposition of 32 nm
alumina nanoparticles into a NiCu and NiCo alloy deposit. In 16
the last case, the addition of alumina particles caused no 0.0 0.1 0.2 0.3 0.4 0.5 0.6
significant change in the percentage of copper concentration in FC-4 surfactant concentration / g dm -3

the CuNi deposit over the current density range 0 to 45 mA (b)

12
cm 2 although the copper level decreased over the range of 0
Percentage volume of particles in the deposit

20 mA cm 2 [34].
10

35 8

30
6
Deposition rate / m h-1

25
4
20
2
15

0
10 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5

Ratio of surfactant to particles / 10-3 mol surfactant per g SiC

5
Fig. 8. (a) Influence of a cationic fluorocarbon surfactant, FC-4
0 (C20H20F23N2O4I) on the deposition rate of NiCuP containing 50500 nm
7.0 7.5 8.0 8.5 9.0 9.5 10.0 PTFE particles [82]. The concentration of FC-4 in the solution: 4 ml dm 3,
pH 8 ml dm 3, 10 ml dm 3, 14 ml dm 3 and 18 ml dm 3. Electrolyte
compositions: 50 g l 1 NiSO4.6H2O, 1 g l 1 CuSO4.5H2O, 60 g l 1
Fig. 7. Effect of bath temperature and pH on the electroless deposition of Ni Na3C6H5O7.2H2O, 25 g l 1 NaH2PO2.H2O, 40 g l 1 NH4CH3COO, pH 7 and
CuP containing 50500 nm PTFE particles. The rate of deposition increases 85 C. (b) Influence of cetyltrimethylammonium bromide, CTAB surfactant on
with an increase in the solution pH (this can be associated with an enhancement the percentage volume of 100400 nm SiC particles incorporated in the nickel
in the reducing ability of sodium hypophosphite) and increasing temperature deposit [40]. The concentration of CTAB in the solution is 1 g dm 3, 10 g
leads to a faster rate of reaction [82]. 70 C, 76 C, 80 C, 85 C and dm 3 and 20 g dm 3. Electrolyte compositions: 70 g l 1 Ni(NH3SO3)2, 10 g
88 C. l 1 NiCl2, 40 g l 1 H3BO3, pH 4 and 50 C.
380 C.T.J. Low et al. / Surface & Coatings Technology 201 (2006) 371383

3.4. Other operating parameters increased with small increases in pH (possibly due to
enhanced reducing ability of sodium hypophosphite) and
Important operational parameters include pH, bath tempera- increasing temperature resulting in a faster deposition rate
ture, additives type and concentration. Some investigations [69].
have shown that further enhancement of surface properties can The influence of cationic fluorocarbon surfactants on the rate
be obtained by appropriate selection of deposition conditions. of deposition is shown in Fig. 8(a) [69]. Fig. 8(b) shows the
Examples include the addition of cobalt to a nickel deposit volume fraction of 100400 nm SiC particles in a nickel deposit
containing 310 nm diamond nanoparticles, which were increased with higher concentrations of cetyltrimethylammo-
claimed to give (1) an enhancement in the microhardness of nium bromide (CTAB) surfactant. This is attributable to more
the deposited coating, (2) an increased quantity of diamond surfactant molecules being available for adsorption onto the
nanoparticles in the nickel deposit, (3) uniform and well- particles surface, increasing the strength of the surface charge
dispersed diamond nanoparticles in the nickel deposit and (4) on the particles leading to stronger attraction to the cathode
improved wear resistance [46]. The addition of sodium surface [40].
dodecylsulfate additive was claimed to improve the dispersion,
uniformity and quantity of 20 nm SiC nanoparticles in a nickel 4. Gradient distribution of particles in the metal deposit
deposit [43].
Bath temperature and pH of an electrolyte can also affect Careful modulation of the deposition conditions can lead to
the rate of deposition at the cathode surface. Fig. 7 shows the metal layers with a non-uniform, gradient or a layered distribution
pH vs. deposition rate for electroless deposition of NiCuP of incorporated particles. Examples include a Ni deposit with 15
containing 50500 nm PTFE particles. The rate of deposition m SiC microparticles [70], 110 m SiC microparticles [71],

(a)
% Volume in solution % Volume in deposit
Al Al2O3 Al Al2O3 Outside surface of deposits

2.5 6.8 9 24

2.6 3.5 9 16

7.7 0 12 0

Substrate 20 m
(b)
Growth of deposits

Region 3 Region 2 Region 1 Ni substrate

800

700
Knoop hardness / 100 g indenter

600

500

400

300

200 30 % vol. 15 % vol. Ni

-Al2 O3 -Al2O3
100
0 50 100 150 200
Distance from surface of deposit / m

Fig. 9. (a) Gradient distribution of 14 m Al conductive particles and 6080 nm -Al2O3 non-conductive nanoparticles in a nickel deposit. Darker spots: -Al2O3.
Lighter regions: Al [66]. Three distinct layers with different compositions of particles have been achieved using a current density of 5 A dm 2 and various
concentrations of particle in the solution. (b) Knoop hardness profile for a gradient distribution of -Al2O3 nanoparticles in a nickel deposit. Three regions of
microhardness are achievable in a single coating. Region 1 is a pure Ni deposit, Region 2 has 15 vol.% of -Al2O3 in the deposit and Region 3 has 30 vol.% of -Al2O3
in the deposit [60].
 C.T.J. Low et al. / Surface & Coatings Technology 201 (2006) 371383 381

1000
particles in the solution. Fig. 9(b) shows the Knoop hardness
Coating using profile for a gradient distribution of -Al2O3 nanoparticles in
PDC
Ni/Co/Au a nickel deposit. Three different regions of microhardness can
be seen for 30%, 15% and 0% of -Al2O3 nanoparticles in
Nanocrystalline
800 Ni/TiO2
Vickers microhardness / HV

Coating using Nanocrystalline

Nanocrystalline PDC High ZrO2 Ni/C
the deposit. In all these investigations, many analytical
Ni
content in methods have been used to quantify the physical properties
Ni matrix
600 Nanocrystalline
of the deposited metals including gravimetric analysis, X-ray
coating
fluorescence, atomic absorption spectrophotometry, optical
Microcrystalline
Ni/C
microscopy, scanning electron microscopy, X-ray diffraction,
transmission electron microscopy and wavelength dispersive
400 Microcrystalline X-ray spectroscopy.
Ni/TiO2
Coating made
Microcrystalline from DC
Ni/Au 5. Physical properties of nanocomposite deposits
Low ZrO2
200 content in
Microcrystalline Ni matrix
Ni Common targets for metallic nanocomposite deposits are
After annealing at After annealing at
high temperature high temperature
increased corrosion resistance and greater microhardness. A
0
comparison of Vickers microhardness for a wide range of
Pure Ni

nanoparticles in nickel deposits is shown in Fig. 10

Ni/TiO2

Ni/Al 2O3

Ni/Si3N4
Ni/SiC

Ni/C
Ni/ZrO2
Ni/Au

[38,39,41,42,4448,5157]. Several trends were identified:

(1) nanocrystalline structure gave a higher microhardness than
Type of deposit a microcrystalline structure, (2) coatings produced by pulse
current technique could be superior in microhardness com-
Fig. 10. Vickers microhardness values for different ranges of particle size in a
nickel deposit. The values are displayed from minimum to maximum (bottom to pared to a direct current technique and (3) annealing at high
top) found in the literature [38,39,41,42,4448,5157]. DC: direct current; temperature could have a non-uniform affect on the
PDC: pulsed direct current. microhardness.
The corrosion rate of nickel coatings containing TiO2
particles was investigated in acidic solution (5.0% NaCl, 1 g
1.220 m SiC microparticles [72], 3050 nm ZrO2 nanoparti- dm 3 CuCl22H2O, 50 C, 1 week immersion) [55]. Fig. 11
cles [73], 50 nm -Al2O3 nanoparticles [74], 79 m SiC shows that the rate of corrosion was dependent on both the
microparticles [69], 600800 nm -Al2O3 nanoparticles [58] and size and quantity of TiO2 particles in the nickel deposit. The
14 m Al microparticles and 6080 nm -Al2O3 nanoparticles presence of nanosized particles in the nickel deposit gave
[75]. More information related to the development of gradient better corrosion resistance than a pure nickel layer. Anatase
distributions of materials is available elsewhere [7679]. The particles (average diameter 12 nm) gave lower corrosion
gradient distribution of particles in the metal deposit can be rates than the rutile (average diameter 1 m) containing
achieved in a single electrolyte bath by simple alterations of the composites. However, these findings cannot be generalised
applied current density or potential and/or by modulation of the
hydrodynamics and concentration of particles in the solution. 18
For example, by varying the degree of compressed air
agitation in the bath, multilayers of nickel containing different 16
quantities and sizes of SiC particles were achieved [70,71]. The
resulting nickel deposit was shown to contain three different
Corrosion rate / gm-2 h-1

14
layers: (1) under static bath conditions, 0.71.1 vol.% of SiC; (2)
under intermediate hydrodynamic conditions, 9.211.8 vol.% 12
finely dispersed SiC; and (3) under intensive hydrodynamic
conditions, 12.6 vol.% coarse SiC. A more recent investigation 10
controlled the influence of particle concentration (0150 g
dm 3), current density (2550 mA dm 2), electrode rotation (0 8
1200 rpm) and deposition period (40150 min) to produce a
continuous gradient distribution of SiC (79 m) in a nickel 6
deposit [69].
Single and mixed particles (14 m Al conductive 4
particles and 6080 nm -Al2O3 non-conductive nanoparti- 0 2 4 6 8 10 12
cles) in a nickel deposit were produced by varying the current Weight percentage of particles in the nickel deposit
density and concentration of particles in the solution [58,75].
Fig. 11. Dependence of corrosion rate on the amount of TiO2 particles in the
Fig. 9(a) shows an example of a gradient distribution of Al nickel deposit [55]. anatase (average diameter = 12 nm) and rutile (average
and -Al2O3 particles in a nickel deposit, achieved by diameter = 1 m). Electrolyte conditions: 250 g l 1 NiSO46H2O, 25 g l 1
constant current deposition with varied concentration of H3BO3, 5 g l 1 saccharin, pH 3, 30 C. Applied current density: 66.7 mA cm 2.
382 C.T.J. Low et al. / Surface & Coatings Technology 201 (2006) 371383

for other systems for example, in nickel coatings containing tance of experimental trials on the current density, mass
150 nm Al2O3 and 300 nm TiO2 particles, the corrosion rates transport and hydrodynamics to the incorporation rate of
were higher compared to the nickel coatings without particles nanoparticles are crucial to produce good theoretical
[80]. models.
The performance of wear resistant nickel coatings 6. A gradient distribution of particles in metal deposits (single
(produced by direct current, pulsed current and pulsed reverse metal, alloy or multilayers) may lead to the production of
current techniques) containing 1030 nm ZrO2 has been enhanced coatings that have the ability to self-control
compared [81]. The tests were conducted using a ball-on-disc chemical or physical properties as a function of coating
tribometer (dry sliding at 160 rpm with 11.3 N loading and thickness.
1200 cycles). It was found that the hardness of the three 7. It is important to control fluid flow during the co-deposition
coatings increased in the order direct current b pulsed of nanosized particles in a metal deposit and geometries such
current b pulsed reverse current deposition. All the coatings as the rotating cylinder electrode provide established
showed better wear resistance than a pure nickel coating. research tools.
The magnetic properties of a nickel coating containing
300 nm Al2O3 particles were found to be similar to a pure References
nickel coating. The coercivity of the nanocomposite coatings
increased with increasing particle content in the deposit (50 [1] C.G. Fink, J.D. Prince, Trans. Am. Electrochem. Soc. 54 (1928) 315.
nm Al2O3 has higher coercivity than the 300 nm Al2O3) and [2] R.V. Williams, Electroplat. Met. Finish. 19 (3) (1966) 92.
[3] M. Musiani, Electrochim. Acta 45 (2000) 3397.
saturation magnetization of the nanocomposite coatings
[4] E.C. Kedwood, Metallurgia 79 (476) (1969) 225.
remains similar for a wide range of particle content in the [5] V.P. Greco, Plating Surf. Finish. 76 (7) (1989) 62.
deposit [42]. In the majority of the investigations, the [6] V.P. Greco, Plating Surf. Finish. 76 (10) (1989) 68.
physical properties of coatings are fundamentally dependent [7] J.R. Roos, J.P. Celis, J. Fransaer, C. Buelens, J. Met. 42 (11) (1990) 60.
not only on the quantity of nanosized particles in the metal [8] J.P. Celis, J.R. Roos, C. Buelens, J. Fransaer, Trans. Inst. Met. Finish. 69
(4) (1991) 133.
deposit but also on the quality of the particle dispersion in
[9] C. Buelens, J. Fransaer, J.P. Celis, J.R. Roos, Bull. Electrochem. 8 (8)
the coating and the electrodeposition technique. (1992) 371.
[10] J. Fransaer, J.P. Celis, J.R. Roos, Met. Finish. 91 (6) (1993) 97.
6. Conclusions [11] A. Hovestad, L.J.J. Janssen, J. Appl. Electrochem. 25 (1995) 519.
[12] B. Doudin, J.P. Anserment, Nanostruct. Mater. 6 (1995) 521.
[13] U. Erb, Nanostruct. Mater. 6 (1995) 533.
1. Various electrodeposition techniques (direct current, pulsed
[14] D. Clark, D. Wood, U. Erb, Nanostruct. Mater. 9 (1997) 755.
direct current, pulsed reverse current, potentiostatic, pulsed [15] K. Helle, F.C. Walsh, Trans. Inst. Met. Finish. 75 (2) (1997) 53.
potentiostatic) have been employed to incorporate nanosized [16] A. Robertson, U. Erb, G. Palumbo, Nanostruct. Mater. 12 (58) (1999)
particles into metal deposits. These techniques have enabled 1035.
the fabrication of composite coatings possessing a wide [17] C. Kerr, D. Barker, F.C. Walsh, J. Archer, Trans. Inst. Met. Finish. 78 (5)
(2000) 171.
range of properties not available with pure metal or alloy
[18] J.L. Stojak, J. Fransaer, J.B. Talbot, Adv. Electrochem. Sci. Eng. 7 (2001)
coatings. 193.
2. Pulsing the current has, in some cases, shown superiority [19] W. Gao, Z. Li, Mater. Res. 7 (1) (2004) 175.
compared to direct current deposition for the production of [20] C.T.J. Low, C. Ponce-de-leon, F.C. Walsh, Aust. J. Chem. 58 (2005) 246.
nanocomposites. Benefits include refined surface micro- [21] N. Guglielmi, J. Electrochem. Soc. 119 (8) (1972) 1009.
[22] S. Wang, W.J. Wei, Mater. Chem. Phys. 78 (2003) 574.
structure, increased incorporation rate into the metal deposit
[23] J.P. Celis, J.R. Ross, C. Buelens, J. Electrochem. Soc. 134 (6) (1987)
and size selective entrapment of particles. 1402.
3. Applied current density, hydrodynamics and characteristics [24] J. Fransaer, J.P. Celis, J.R. Ross, J. Electrochem. Soc. 139 (2) (1992) 413.
of the particles in solution strongly influences their [25] G. Maurin, A. Lavanant, J. Appl. Electrochem. 25 (1995) 1113.
incorporation rate into metal deposits. High incorporation [26] B.J. Hwang, C.S. Hwang, J. Electrochem. Soc. 140 (1993) 979.
[27] P.M. Vereecken, I. Shao, P.C. Searson, J. Electrochem. Soc. 147 (7) (2002)
rates have been achieved by using: (i) high nanoparticle
2572.
concentration in the electrolyte solution, (ii) smaller sized [28] P. Bercot, E. Pena-Munoz, J. Pagetti, Surf. Coat. Technol. 157 (2002) 282.
nanoparticles, (iii) a low concentration of electroactive [29] P.R. Webb, N.L. Robertson, J. Electrochem. Soc. 141 (3) (1994) 669.
species, (iv) ultrasonication during deposition and (v) pulsed [30] J. Steinbach, H. Ferkel, Scr. Mater. 44 (2001) 1813.
reverse current techniques. [31] A. Lozano-Morales, E.J. Podlaha, J. Electrochem. Soc. 151 (7) (2004)
C478.
4. The inclusion of nanosized particles can give: (i) an
[32] A.B. Vidrine, E.J. Podlaha, J. Appl. Electrochem. 31 (4) (2001) 461.
increased microhardness and corrosion resistance which [33] E.J. Podlaha, Nano Lett. 1 (8) (2001) 413.
can be further enhanced with a nanocrystalline metal deposit, [34] A. Panda, E.J. Podlaha, Electrochem. Solid-State Lett. 6 (11) (2003) C149.
(ii) modified crystal growth to form a nanocrystalline metal [35] E.J. Podlaha, D. Landolt, AESF SUR/FIN Annual Intern. Technical
deposit and (iii) a shift in the reduction potential of a metal Conference, 1998.
[36] E.J. Podlaha, D. Landolt, J. Electrochem. Soc. 144 (7) (1997) L200.
ion.
[37] J.L. Stojak, J.B. Talbot, J. Appl. Electrochem. 31 (5) (2001) 559.
5. Flexibility and validity of various theoretical models to [38] I. Shao, P.M. Vereecken, R.C. Cammarata, P.C. Searson, J. Electrochem.
describe the behaviour of a wide range of metal deposits Soc. 149 (11) (2002) C610.
containing particles still requires attention. The impor- [39] N.S. Qu, K.C. Chan, D. Zhu, Scr. Mater. 50 (2004) 1131.
 C.T.J. Low et al. / Surface & Coatings Technology 201 (2006) 371383
[40] S. Kuo, Y. Chen, M. Ger, W. Hwu, Mater. Chem. Phys. 86 (2004) 5.
[41] P.M. Vereecken, I. Shao, P.C. Searson, J. Electrochem. Soc. 147 (7) (2000)
2572.
[42] I. Shao, P.M. Vereecken, C.L. Chien, P.C. Searson, R.C. Cammarata,
J. Mater. Res. 17 (6) (2002) 1412.
[43] L. Benea, P.L. Bonora, A. Borello, S. Martelli, F. Wenger, P. Ponthiaux,
J. Galland, J. Electrochem. Soc. 148 (7) (2001) C461.
[44] P. Gyftou, M. Stoumbouli, E.A. Pavlatou, N. Spyrellis, Trans. Inst. Met.
Finish. 80 (3) (2002) 88.
[45] A.F. Zimmerman, D.G. Clark, K.T. Aust, U. Erb, Mater. Lett. 52 (2002)
85.
[46] A.F. Zimmerman, G. Palumbo, K.T. Aust, U. Erb, Mater. Sci. Eng., A 328
(2002) 137.
[47] L. Wang, Y. Gao, H. Liu, Q. Xue, T. Xu, Surf. Coat. Technol. 191 (2005) 1.
[48] V.I. Kurmachev, Y.V. Timoshkov, T.I. Orehovskaja, V.Y. Tomoshkov, Fiz.
Tverd. Tela 46 (4) (2004) 679.
[49] K. Kondo, A. Ohgishi, Z. Tanaka, J. Electrochem. Soc. 147 (7) (2000)
2611.
[50] A. Moller, H. Hahn, Nanostruct. Mater. 12 (1999) 259.
[51] L. Wang, Y. Gao, Q. Xue, H. Liu, T. Xu, Mater. Sci. Eng., A 390 (2005)
313.
[52] W.-H. Lee, S.-C. Tang, K.-C. Chung, Surf. Coat. Technol. 120121 (1999)
607.
[53] X. Li, Z. Li, Mater. Sci. Eng., A 358 (2003) 107.
[54] Y. Zhang, X. Peng, F. Wang, Mater. Lett. 58 (2004) 1134.
[55] J. Li, Y. Sun, X. Sun, J. Qiao, Surf. Coat. Technol. 192 (2005) 331.
[56] J. Li, J. Liang, H. He, Y. Sun, J. Mater. Sci. Lett. 21 (2002) 939.
[57] F. Wunsche, A. Bund, W. Plieth, J. Solid State Electrochem. 8 (2004) 209.
[58] S.W. Banovic, K. Barmak, A.R. Marder, J. Mater. Sci. 34 (13) (1999)
3203.
[59] J. Fransaer, E. Leunis, T. Hirato, J.P. Celis, J. Appl. Electrochem. 32 (2002)
123.
[60] C.F. Malfatti, J. Zoppas-Ferreira, C.B. Santos, B.V. Souza, E.P. Fallavena,
S. Vaillant, J.P. Bonino, Corros. Sci. 47 (3) (2005) 567.
[61] G. Wu, N. Li, D. Zhou, K. Mitsuo, Surf. Coat. Technol. 176 (2004) 157.
383
[62] A. Afshar, M. Ghorbani, M. Mazaheri, Surf. Coat. Technol. 187 (23)
(2004) 293.
[63] L. Benea, P.-L. Bonora, A. Borello, S. Martelli, Wear 249 (1011) (2002)
995.
[64] D.W. Gibbons, R.H. Muller, C.W. Tobias, J. Electrochem. Soc. 138 (1991)
3255.
[65] D.R. Gabe, J. Appl. Electrochem. 4 (1974) 91.
[66] D.R. Gabe, F.C. Walsh, J. Appl. Electrochem. 13 (1983) 3.
[67] D.R. Gabe, G.D. Wilcox, J. Gonzalez-Garcia, F.C. Walsh, J. Appl.
Electrochem. 28 (1998) 759.
[68] B. Bozzini, G. Giovannelli, P.L. Cavallotti, J. Appl. Electrochem. 29 (6)
(1999) 685.
[69] H. Wang, S. Yao, S. Matsumura, J. Mater. Process. Technol. 145 (2004)
299.
[70] L. Orlovskaja, N. Periene, M. Kurtinaitiene, G. Bikulcius, Surf. Coat.
Technol. 105 (12) (1998) 8.
[71] L. Orlovskaja, N. Periene, M. Kurtinaitiene, S. Surviliene, Surf. Coat.
Technol. 111 (23) (1999) 234.
[72] S.K. Kim, H.J. Yoo, Surf. Coat. Technol. 108109 (1998) 564.
[73] L. Jun, D. Changsong, W. Dianlong, H. Xinguo, Surf. Coat. Technol. 91
(1997) 131.
[74] Y.S. Dong, P.H. Lin, H.X. Wang, Surf. Coat. Technol. (2005) (Available
online 15 January 2005).
[75] . K. Barmak, S.W. Banovic, C.M. Petronis, D.F. Susan, A.R. Marder,
J. Microsc. 185 (2) (1997) 265.
[76] Z.Q. Zheng, S.Q. Liang, Mater. Sci. Eng. 10 (1) (1992) 1.
[77] N. Periene, A. Cesuiniene, L. Taicas, Plating Surf. Finish. 80 (10) (1993)
73.
[78] B.Y. Chen, Mater. Sci. Eng. 7 (1993) 45.
[79] X.S. Lei, N. Ling, H.J. Wang, Mater. Prot. 28 (7) (1995) 12.
[80] F. Erler, C. Jakob, H. Romanus, L. Spiess, B. Wielage, T. Lampke, S.
Steinhauser, Electrochim. Acta 48 (2003) 3063.
[81] W. Wang, F. Hou, H. Wang, T. Guo, Scr. Mater. 53 (2005) 613.
[82] Q. Zhao, Y. Liu, Surf. Coat. Technol. (2004) (Available online 29 July
2004).