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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
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
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 373
Codeposition mechanisms for the dispersion of inert consecutive steps during the codeposition process can be
particles into metallic coatings have been developed from identified [7]: (1) formation of ionic clouds on the particles,
investigations of micron sized particles. Many theories have (2) convection towards the cathode, (3) diffusion through a
been suggested including the transport of particles due to (1) hydrodynamic boundary layer, (4) diffusion through a
electrophoresis, (2) mechanical entrapment, (3) adsorption and concentration boundary layer and finally, (5) adsorption at
(4) convective-diffusion. Table 2 [2128] provides an overview the cathode where particles are entrapped within the metal
of the existing models and their main assumptions. The deposit. Other models include a statistical approach [710,24]
mechanism proposed by Guglielmi [21] has been adopted by which predicts the probability of a particle being incorporated
various authors. This model enables a quantitative treatment of into a deposit and particle trajectory models [24,25] which
the influence of particle concentration and current density on the describe non-Brownian particles. The relationships between
incorporation rate of particles into a metal deposit but excludes the quantity of particles in the metal deposit and current
hydrodynamic effects and particle characteristics. A corrective density or hydrodynamics have been the focus of many
factor (3rd order polynomial equation) has been included into experimental studies.
Guglielmi's model to account for the effects of adsorption and Although many theoretical models have been proposed, the
hydrodynamics on the incorporation of 500 nm PTFE flexibility and reliability of each to describe the behaviour of
nanoparticles into a nickel deposit [28]. However, the validity a wide range of metallic coatings and particle types still
of this function may only lie within a narrow range of requires validation. Often, the existing models involve
experimental parameters and its ability to accurately predict mathematical relationships that are interrelated to an extensive
other systems requires study. set of parameters and, in all the models available so far, the
Fig. 1 shows the common processes involved in the effects of particle inclusion on deposit electrocrystallisation
codeposition of particles into growing metallic layers. Five 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-
Cathode 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
Deposit Bulk
electrolyte
A variety of nanosized particles (typically with spherical
dimensions), ranging from 4 nm to 800 nm diameters, have
Electrical Diffusion Convection been successfully incorporated into metal electrodeposits.
double layer layer These include aluminium dioxide (Al2O3), chromium (Cr),
layer diamond (C), silicon carbide (SiC), gold (Au), silicon dioxide
(SiO2), zirconium dioxide (ZrO2), titanium dioxide (TiO2),
Particles (conductive or non conductive) polystyrene (PS) and silicon nitride (Si3N4). Amongst many
Surfactant (ionic, non-ionic or organic)
metals used, copper and nickel have featured strongly.
Alumina particles have been the subject of many investigations
Clouding of particles by surfactants compared to other nanoparticles. Table 3 [23,2942] shows the
recent examinations of the codeposition of alumina particles
Clouding of particles by cations
while Table 4 [22,25,4357] considers other particulate
Deposited metal inclusions.
The inclusion of nanosized particles into metal deposits is
Fig. 1. Mechanisms of particle codeposition into a metal deposit [7]. The regions dependent on many process parameters, including particle
include: formation of ionic clouds around the particles (bulk electrolyte, typical characteristics (particle concentration, surface charge, type,
length in cm); convective movement toward the cathode (convection layer,
typical length b1 mm); diffusion through a concentration boundary layer shape, size), electrolyte composition (electrolyte concentra-
(diffusion layer, typical dimensions of hundreds of m); electrical double layer tion, additives, temperature, pH, surfactant type and
(typical dimensions of nm) followed by adsorption and entrapment of particles. 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- be identified as influencing the codeposition processes,
dynamics (laminar, mixed, turbulent regimes) of together namely (1) the applied current density, (2) the particle type
with electrode geometry (rotating disk electrode, rotating and concentration and (3) bath agitation or electrode
cylinder electrode, plate-in-tanks, parallel plate electrodes movement.
and many variations).
Electrolyte composition is known to be a significant 3.1. Current density
factor affecting the codeposition process. However, a clear
picture of the exact effect of the experimental parameters A variety of galvanostatic techniques can be utilised,
is often difficult to obtain. The majority of recent including direct current, pulsed direct current and pulsed
investigations have suggested that three global factors can 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 limiting factor (average grain diameter of 20 nm) [30]. This is
commonly been used to obtain nanoparticle composites. This because selective entrapment of nanoparticles occurs with the
technique is based on the concept that the incorporation of larger particles being preferentially removed during the reverse
nanoparticles occurs simultaneously with the reduction reaction pulse period, producing a finer deposit with less agglomeration
of an ionic species to form the metal surface. of nanoparticles.
The application of a pulsed current has enabled the The pulsed reverse current technique has been used to
incorporation of higher concentrations of nanoparticles as produce a copper deposit containing high concentrations of 30
well as producing a wider range of deposit compositions and nm alumina nanoparticles [3336]. By using a steady state
properties. The pulsed direct current technique is based on pulsed reverse current and long pulse times, three main
alternating two or more direct cathodic currents for various advantageous can be achieved compared to the direct current
deposition times. While the pulsed reverse current technique has method: (1) the amount of nanoparticles in a metal deposit can
similar characteristics but imposes a cathodic current during the be enhanced, (2) a lower concentration of nanoparticles in the
on time and an anodic current during the off time. This method electrolyte solution can be used and (3) selective entrapment of
has been the most successful for embedding higher concentra- similar sizes of nanoparticles can be achieved. All three
tions of nanoparticles because it helps to eliminate a fraction of advantages can be associated with the partial dissolution of
the electrodeposited metal during the off time. the metal deposit during the anodic period where larger sizes of
Various authors have compared direct current and pulsed nanoparticles tend to be lost from the deposit while smaller
current deposition. For example, during the electrodeposited nanoparticles continue to be entrapped.
nanocrystalline nickel it is reported that under direct current, the Uniform and well-dispersed nanoparticle (80 nm alumina)
nanoparticles (25 nm alumina) are the main inhibiting factor for dispersions in a nickel deposit were achieved by the combina-
the growth of nickel nuclei (average grain diameter of 30 nm). tion of pulsed current and ultrasound [39]. The introduction of
Under pulsed direct current, however, the pulse length is the 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
(a) Current frequency (5.6 Hz) an increase in the amount of alumina
whiskers in the nickel deposit was observed with significant
agglomeration of nanoparticles. The employment of ultrasound
during electrodeposition can reduce nanoparticle agglomeration
0 Time as well as removing the absorbed nanoparticles from the metal
+ deposit at high frequency.
Direct current combined with ultrasound has also been
(b) Current 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
0 Time
+
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
(c) Current
occurrence of hydrogen evolution must considered to avoid a
reduction in the current efficiency as well as hindering the
adsorption of nanoparticles to the metal surface.
The current density is also found to influence the amount of
0 Time alumina nanoparticles incorporated into electrodeposited nickel.
+ Using a sulfamate bath containing 600800 nm -Al2O3
nanoparticles, an increase in current density resulted in a rough
(d) Current
surface microstructure and lead to less nanoparticles being
incorporated in the metal deposit (Fig. 3) [58]. Another study of
32 nm alumina nanoparticle, however, has demonstrated that
the degree of nanoparticle incorporation was dependent on the
0 Time electrolyte type [32]. In a chloride electrolyte, a higher
+ nanoparticle content in the deposit was established at low
current density but in a citrate electrolyte, higher nanoparticle
Fig. 2. Various modes of current density vs. time control during electrodeposi- contents were found at elevated current density. It was also
tion; (a) pulsed direct current with zero current during off-time, (b)
superimposed pulsed direct current with cathodic current during off-time, (c) found that the current efficiency increased at higher current
pulsed reverse current with anodic current during off-time, and (d) pulsed densities in both electrolytes but the amount of nanoparticles in
reverse current with combination of zero and anodic current during off-time. 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
(a)
20 10
0
0 5 10 15 20 25 30 4
Current density / A dm-2
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 377
deposit was much higher compared to the 50 nm Al2O3. the electrolyte, the suspension stability of particles at long times
However, the quantity of 50 nm Al2O3 particles in the nickel and the use of electrolyte additives, particularly surfactants.
deposit was much larger than the quantity of 300 nm Al2O3
particles [38,42]. 3.3. Influence of bath agitation and cathode movement
In the case of electrodeposition of nickel containing titanium
dioxide particles, the weight percentage of 12 nm anatase in the Bath agitation serves two purposes, namely to keep the
nickel deposit was higher than for 1 m rutile particles in the particles suspended in the electrolyte and to transport the
nickel deposit. The deposit incorporating 12 nm anatase displayed particles to the cathode surface. Many investigations have found
superior corrosion resistance in acidic solution (pH 3.13.3 that increased agitation generally enhances the amount of
glacial acetic acid, 5.0% NaCl, 1.0 g dm 3 CuCl22H2O, 50 C particles in the metal deposit. However, excessive agitation may
and 1 week) but showed only a slight increase in Vickers lead to a lower quantity of particles in the metal deposit. This
microhardness compared to the 1-m rutile containing deposit. may be explained by vigorous hydrodynamic forces in the
Nanoparticle concentration in the deposit has been found to electrolyte removing the particles from the cathode surface
affect both surface roughness and deposit microstructure. For before they can be entrapped in the metal deposit.
example, the surface microstructure of a nickel deposit Fig. 5 shows the relationship between electrode rotation rate
containing 32 nm -Al2O3 nanoparticles changed from rough and particle inclusion for a nickel deposit containing 500 nm
to smooth as the concentration of particles in the solution PTFE particles [28]. An optimum incorporation rate is seen which
increased from 0 g dm 3 to 60 g dm 3 [31]. depends on both particle concentration and rotation speed. At a
The presence of nanosized particles in a metal deposit may fixed applied current density of 3 A dm 2, the maximum rotation
induce changes in the crystalline structure of the metallic speed observed before any fall off in volume percentage of
coating. It has been shown that 20 nm SiC nanoparticles particles varies with loading of particles in the electrolyte. This
influence the competitive formation of nickel nuclei and effect is also seen during the codeposition of 32 nm -Al2O3
crystal growth [63]. The presence of 20 nm SiC nanoparticles particles in a copper deposit [31]. In the latter case, the influence of
shifted the reduction potential of nickel ions to more positive electrode rotation rate on the polarization curves did not show a
potentials and increased the current density. This can be dependence on particle concentration. The authors showed that, at
associated with an increase in surface area of the cathode due a 12.5 g dm 3 alumina nanoparticle concentration in the bath, the
to the adsorbed nanoparticles. By increasing the surface area, charge transfer region did not alter with rotation rate; at 39 g dm 3
more nucleation sites are available for the nickel ions and of alumina nanoparticles, the reduction of copper ions is inhibited
crystalline growth is suppressed during electrodeposition. at all rotation rates and at 60 g dm 3 of alumina nanoparticles,
Consequently, a smaller crystal grain size can be obtained both the inhibition and enhancement of the copper ion reduction
giving an enhanced microhardness. occurred at different rotation rates. This complex, non-linear
Other investigations have demonstrated that 20 nm SiC relationship as observed on the polarization curves, suggests that a
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
10
nickel crystals, the authors showed that the nanoparticles could
Percentage volume of particles in the deposit
simple mechanism based on the adsorption and electrophoretic The rotating disk electrode, rotating cylinder electrode and
effects cannot sufficiently be explained by a simple model. parallel plates channel flow provide controllable hydrody-
Two common techniques have been used to keep particles namics for quantitative characterisation of electrolytes con-
suspended in the electrolyte, namely (1) physical dispersion of taining particle suspensions. Three different flow regimes can
particles by bath agitation and (2) chemical dispersion of be distinguished: laminar, transition (laminar to turbulent) and
particles by surfactants. A combination of cationic, anionic and turbulent. For micron-sized particles, there is generally no
non-ionic surfactants can be used to achieve control of surface significant influence of electrolyte flow on particle content in
charge on the particles and the degree of suspension in the the laminar region; in the transition regime, the particle
electrolyte [15]. The strategies for bath agitation can be content increased at higher flow rates; and in the turbulent
controlled in many ways depending on the dimensions of the regime, the particle content tended to decrease at higher rates
electroplating bath, as shown in Fig. 6. For industrial [11].
applications, the popular methods used in open tanks include The presence of micron-sized particles can provide an
the overhead blade stirrer, the reciprocating plate plunger or a enhancement of mass transport to the cathode. As an
pumped recycle loop of the electrolyte [15]. For laboratory example, the expression for mass transport dimensionless
investigations, magnetic stirrers, rotating disk or cylinder correlation for a solution containing 1030 vol.% of 2546
electrodes and parallel plate channel flow can be employed. m microparticles [64]:
In contrast, the commonly used plate-in-tank geometry provides
poorly defined fluid flow conditions. Sh aRe0:43 Sc0:33 1
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.
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
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
700
Knoop hardness / 100 g indenter
600
500
400
300
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
Ni/Al 2O3
Ni/Si3N4
Ni/SiC
Ni/C
Ni/ZrO2
Ni/Au
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 383
[40] S. Kuo, Y. Chen, M. Ger, W. Hwu, Mater. Chem. Phys. 86 (2004) 5. [62] A. Afshar, M. Ghorbani, M. Mazaheri, Surf. Coat. Technol. 187 (23)
[41] P.M. Vereecken, I. Shao, P.C. Searson, J. Electrochem. Soc. 147 (7) (2000) (2004) 293.
2572. [63] L. Benea, P.-L. Bonora, A. Borello, S. Martelli, Wear 249 (1011) (2002)
[42] I. Shao, P.M. Vereecken, C.L. Chien, P.C. Searson, R.C. Cammarata, 995.
J. Mater. Res. 17 (6) (2002) 1412. [64] D.W. Gibbons, R.H. Muller, C.W. Tobias, J. Electrochem. Soc. 138 (1991)
[43] L. Benea, P.L. Bonora, A. Borello, S. Martelli, F. Wenger, P. Ponthiaux, 3255.
J. Galland, J. Electrochem. Soc. 148 (7) (2001) C461. [65] D.R. Gabe, J. Appl. Electrochem. 4 (1974) 91.
[44] P. Gyftou, M. Stoumbouli, E.A. Pavlatou, N. Spyrellis, Trans. Inst. Met. [66] D.R. Gabe, F.C. Walsh, J. Appl. Electrochem. 13 (1983) 3.
Finish. 80 (3) (2002) 88. [67] D.R. Gabe, G.D. Wilcox, J. Gonzalez-Garcia, F.C. Walsh, J. Appl.
[45] A.F. Zimmerman, D.G. Clark, K.T. Aust, U. Erb, Mater. Lett. 52 (2002) Electrochem. 28 (1998) 759.
85. [68] B. Bozzini, G. Giovannelli, P.L. Cavallotti, J. Appl. Electrochem. 29 (6)
[46] A.F. Zimmerman, G. Palumbo, K.T. Aust, U. Erb, Mater. Sci. Eng., A 328 (1999) 685.
(2002) 137. [69] H. Wang, S. Yao, S. Matsumura, J. Mater. Process. Technol. 145 (2004)
[47] L. Wang, Y. Gao, H. Liu, Q. Xue, T. Xu, Surf. Coat. Technol. 191 (2005) 1. 299.
[48] V.I. Kurmachev, Y.V. Timoshkov, T.I. Orehovskaja, V.Y. Tomoshkov, Fiz. [70] L. Orlovskaja, N. Periene, M. Kurtinaitiene, G. Bikulcius, Surf. Coat.
Tverd. Tela 46 (4) (2004) 679. Technol. 105 (12) (1998) 8.
[49] K. Kondo, A. Ohgishi, Z. Tanaka, J. Electrochem. Soc. 147 (7) (2000) [71] L. Orlovskaja, N. Periene, M. Kurtinaitiene, S. Surviliene, Surf. Coat.
2611. Technol. 111 (23) (1999) 234.
[50] A. Moller, H. Hahn, Nanostruct. Mater. 12 (1999) 259. [72] S.K. Kim, H.J. Yoo, Surf. Coat. Technol. 108109 (1998) 564.
[51] L. Wang, Y. Gao, Q. Xue, H. Liu, T. Xu, Mater. Sci. Eng., A 390 (2005) [73] L. Jun, D. Changsong, W. Dianlong, H. Xinguo, Surf. Coat. Technol. 91
313. (1997) 131.
[52] W.-H. Lee, S.-C. Tang, K.-C. Chung, Surf. Coat. Technol. 120121 (1999) [74] Y.S. Dong, P.H. Lin, H.X. Wang, Surf. Coat. Technol. (2005) (Available
607. online 15 January 2005).
[53] X. Li, Z. Li, Mater. Sci. Eng., A 358 (2003) 107. [75] . K. Barmak, S.W. Banovic, C.M. Petronis, D.F. Susan, A.R. Marder,
[54] Y. Zhang, X. Peng, F. Wang, Mater. Lett. 58 (2004) 1134. J. Microsc. 185 (2) (1997) 265.
[55] J. Li, Y. Sun, X. Sun, J. Qiao, Surf. Coat. Technol. 192 (2005) 331. [76] Z.Q. Zheng, S.Q. Liang, Mater. Sci. Eng. 10 (1) (1992) 1.
[56] J. Li, J. Liang, H. He, Y. Sun, J. Mater. Sci. Lett. 21 (2002) 939. [77] N. Periene, A. Cesuiniene, L. Taicas, Plating Surf. Finish. 80 (10) (1993)
[57] F. Wunsche, A. Bund, W. Plieth, J. Solid State Electrochem. 8 (2004) 209. 73.
[58] S.W. Banovic, K. Barmak, A.R. Marder, J. Mater. Sci. 34 (13) (1999) [78] B.Y. Chen, Mater. Sci. Eng. 7 (1993) 45.
3203. [79] X.S. Lei, N. Ling, H.J. Wang, Mater. Prot. 28 (7) (1995) 12.
[59] J. Fransaer, E. Leunis, T. Hirato, J.P. Celis, J. Appl. Electrochem. 32 (2002) [80] F. Erler, C. Jakob, H. Romanus, L. Spiess, B. Wielage, T. Lampke, S.
123. Steinhauser, Electrochim. Acta 48 (2003) 3063.
[60] C.F. Malfatti, J. Zoppas-Ferreira, C.B. Santos, B.V. Souza, E.P. Fallavena, [81] W. Wang, F. Hou, H. Wang, T. Guo, Scr. Mater. 53 (2005) 613.
S. Vaillant, J.P. Bonino, Corros. Sci. 47 (3) (2005) 567. [82] Q. Zhao, Y. Liu, Surf. Coat. Technol. (2004) (Available online 29 July
[61] G. Wu, N. Li, D. Zhou, K. Mitsuo, Surf. Coat. Technol. 176 (2004) 157. 2004).