Ceramics International 45 (2019) 21835–21842

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Deposition of ceramic nanocomposite coatings by electroplating process: A T

review of layer-deposition mechanisms and effective parameters on the
formation of the coating
Saeid Mersagh Dezfulia, Masoud Sabzib,*
a
Department of Materials Engineering, Science and Research Branch, Islamic Azad University, Tehran, Iran
b
Young Researchers and Elite Club, Dezful Branch, Islamic Azad University, Dezful, Iran

A R T I C LE I N FO A B S T R A C T

Keywords: Nowadays, the demand for the metal matrix composites for various applications such as aerospace and defense
Electroplating process industries, chemical industries and fluid transfer facilities and so on has increased in order to cope with severe
Deposition environmental conditions and service stresses. Electroplating technique is one of the suitable methods that has
Effective parameters on co-precipitation been considered by researchers in the past decade due to its simplicity, low cost and low temperature of the
Ceramic nanocomposite coatings
process, easy access to the nanoscale structure as well as the production of high-density and porosity-free
Layer-deposition mechanisms
coatings. Electroplating is a low temperature process that is used as an economical method to develop nano-
composite coatings in one step without secondary operation. In the process of electroplating, various factors
including bath parameters such as pH, concentration of different additives, concentration of different lubricants,
temperature as well as process parameters such as current density, frequency of applied current and stirring
speed of the bath on morphology, roughness, co-precipitation of nanoparticles and microhardness of coatings, as
well as wear and corrosion behavior of nanocomposite coatings in direct and pulsed current conditions are of
great importance. Therefore, in this research, the mechanisms and factors affecting the formation of the film and
coating by electroplating process have been studied.

1. Introduction surface diffusion rate, the nucleation of crystals is dominant [6–9].

1.1. Electroplating
Electroplating is a metal coating process that deduces the cation by
electric current and precipitates it as a layer on another material such as
metal. This process is used to enhance features such as wear and cor-
rosion resistance as well as decorative purposes [1–3]. Electroplating is
a process by which a nanoscale structure can be made, provided that
the plating conditions such as bath composition, pH, temperature, po-
tential difference and other factors contribute to high nucleation and
reduced grains growth [4,5]. The crystallization during electroplating is
competing through two processes, that is, the growth of available
crystals and nucleation of new crystals which are affected by many
parameters. In addition, the controlling process of the formation rate of
crystals is influenced by two fundamental steps, i.e. the exchange of
charge at the electrode surface and diffusion of ions on the crystal
surface. Grain growth is predominant at low potential difference and
high surface diffusion rate, while at high potential difference and low
Electroplating through the pulsed current provides the two required
conditions for the predominance of nucleation, since in pulsed mode, it
is possible to apply higher current densities than the limited direct
currents in the direct mode [9–11]. In addition to making metal coat-
ings such as Cu, Co, Ni and Pd by electroplating process, it can be made
binary and ternary alloys and nanocomposite coatings using external
nanoparticles [10,12]. The presence of alloying elements and external
nanoparticles leads to a reduction of friction coefficient and increased
wear resistance in the coating, which is caused by reduced contact
surface due to the high hardness of the coating and consequently re-
duced adhesion surface [11–13]. In Fig. 1, a variety of materials pro-
vided by the electroplating process are shown. In this figure, it has been
shown that the type of current used for the electroplating process has a
great influence on the properties of the coatings. Also, a schematic of
the electroplating process for depositing reinforced coatings with
ceramic nanoparticles is presented in Fig. 2.
Due to the fact that composite coatings combine the properties of
the matrix phase and secondary particles, they can result in specific

*
Corresponding author.
E-mail address: mas.metallurg88@gmail.com (M. Sabzi).

https://doi.org/10.1016/j.ceramint.2019.07.190
Received 19 April 2019; Received in revised form 22 June 2019; Accepted 16 July 2019
Available online 17 July 2019
0272-8842/ © 2019 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
S. Mersagh Dezfuli and M. Sabzi
Fig. 1. Schematic of nanostructure materials that can be produced using electroplating method.
Fig. 2. A schematic of the electroplating process for depositing reinforced
coatings with ceramic nanoparticles.
properties such as high strength at high temperatures, good thermal
fatigue resistance, thermal shock resistance, high thermal conductivity
and low expansion coefficient. Secondary particles may cause cracks or
porosity, or the formation of internal stresses especially in the interface;
therefore they can lead to stress corrosion, local corrosion and brittle-
ness of the coating. In fact, the presence of ceramic reinforcement na-
noparticles directly affects the properties of corrosion, mechanical,
microstructural and thermal shock absorption of nanocomposites. Even
the shape and size of these nanoparticles can affect the fracture mode of
these nanocomposites. In general, the lower the size of the ceramic
particles and the higher the distribution of these nanoparticles in the
matrix phase, the properties of ceramic nanocomposite coatings will
improve [12–14]. Electroplating of hard particles as a secondary phase
in the metal matrix has advantages such as low operating temperature,
low cost and development of coatings with different properties by
changing the electrochemical conditions. Secondary phase hard parti-
cles play a major role in the properties of composite coatings. These
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Ceramics International 45 (2019) 21835–21842
properties depend on the nature of the particles and their distribution in
the coating [13,15]. The uniform distribution of secondary phase par-
ticles will enhance the mechanical, tribological, anti-corrosion and anti-
oxidation properties of the coating [8]. The development of metal-
based composites using nanoscale and micro particles has been tech-
nologically considered for the production of new coatings with con-
trolled and reinforced properties. As the possibilities of production such
nanoparticles are increasing dramatically, it is still unknown how they
are to be used and to what extent they will be effective [16–18]. When
two particles collide in the electrolyte, there are energies between the
two particles that determine the repulsion and attraction forces be-
tween them. When the latter is higher than the former, agglomeration
occurs. The pure force between the two particles depends on the con-
dition and nature of the system. Physical or chemical methods can be
used to change the interface of particles and reduce the agglomeration
of particles. The chemical method involves the use of additives and the
physical method includes ultrasonic approach. The distribution of
particles due to ultrasonic waves comes from the formation and re-
moval of cavitational bubbles. The use of ultrasonic stirring during
plating can reduce the agglomeration of particles and at low fre-
quencies leads to the removal of particles from the deposited metal
[19–21].
Electroplating coatings are one of the most widely used coatings in
various industries. On the other hand, the identification of the pro-
duction process of these coatings was felt with all the details. Therefore,
it was decided in this research to study the production conditions of
ceramic nanocomposite coatings by electroplating.
2. Layer deposition mechanisms in electroplating
2.1. The general mechanism of ceramic or metal deposition
The deposition process involves applying electrical potential by
means of a pulsed or direct current source between an anode with a
positive pole and a cathode (metal matrix) with a negative pole, which
results in an electric current between anode and cathode and the
transfer of the ions in electrolyte, completes the circuit. The general
mechanism consists of two stages of nucleation and growth, comprising
S. Mersagh Dezfuli and M. Sabzi Ceramics International 45 (2019) 21835–21842

three stages: (i) Transfer of ion from the solution to the surface of the
cathode. (ii) Transfer of the charge and conversion of the ion to the
metal atom. (iii) The diffusion of the metal atom into the crystalline
lattice of the metal and grain growth [22–24].
For example, during the process of copper deposition, first, the bi-
valent ions of the metal react with the electron according to reaction (1)
and they are adsorbed into the cathode as a univalent copper ion, and
then in the next step they convert into single-atomic metals according
to reaction (2), and subsequently these single-atoms are placed in sui-
table places and produce deposition layers.

Cu2++ e →Cu+(ads) (1)

Cu+(ads) + e → Cu (2)

The reaction (1) is the slower stage of the process and is the de-
termining stage of the process rate [25,26].

2.2. Co-precipitation mechanism of the ceramic or metal of the matrix and Fig. 3. Schematic representation of charge distribution during electrolyte
reinforcing particles coating of nanoparticles.

Over the past decades, a number of co-precipitation mechanisms
have been proposed. There are three general mechanisms in this regard
(i) Transfer of neutral particles to the cathode surface by electro-
phoretic operation (ii); Mechanical trapping by stirring or van der
Waals forces and (iii) Sedimentation of the particles in the cathode by
metal electro-deposition [27,28]. Two general processes can be iden-
tified in co-precipitation of the particles in metallic coatings: 1) physical
distribution of particles in electrolyte and 2) electrophoretic migration
of particles. Co-precipitation mechanisms related to the distribution of
particles in composite coatings have been derived from the researches
on micro particles. There are a lot of proposed theories that base their
ideas on the transfer of neutral particles due to 1) electrophoresis 2)
mechanical trapping 3) absorption and 4) convection diffusion.
Common processes in the co-precipitation of particles in the growing
metal layer can be described by Celis model. Based on the Celis model,
five successive stages can be identified for particles co-precipitation.
1) The formation of an electron cloud around particles (inside the
electrolyte, in the range of centimeter)
2) Convection movement towards the cathode (convective layer, in the
range less than 1 mm)
3) Diffusion through the hydrodynamic boundary layer
4) Diffusion from the concentration boundary layer (diffusion layer, in
the range of several hundred micrometers)
5) Diffusion from electric double layer (in the range of nm) and sub-
sequent absorption in the cathode, in which particles are trapped
inside a metal deposit.
high-quality and fine grain matrix is formed [32–34]. The effect of pH
on the distribution and particle size can also be checked by Zeta po-
tential. It is the electrical potential between the surface of the solid
particle and the aqueous medium which is calculated by the Zetasizer in
accordance with the Henry relation (Equation (3)).
3ηUE
Z=
2εf (Ka) (3)
In Equation (3), Z is the Zeta potential, η solution viscosity, UE
electrophoretic mobility (particle velocity in the unit electric field), ε
dielectric constant of solution and f (Ka) is the Henry function which is
often used from 1 or 1.5 numbers [35,36]. Fig. 4 shows a charged
colloidal particle with a zeta potential location. Therefore, the change
in the layer deposition parameters leads to a change in the micro-
structure and coating properties [37–44]. As far as Zeta potential is
concerned, the larger the particle in the negative PH, due to the ab-
sorption of more metal ions with a larger electron superconductor.
According to the Stokes model, assuming that the colloidal particle is
spherical, the electrophoretic velocity (VE) in the electric field (E) can
be explained as follows [45,46].
q
VE = μ E E = E
6πη (4)
Where μE is the electrophoretic mobility, q is the electric charge of

In alkali electrolytes, the surface of particles is adsorbed by anions

[29–31]. During the plating, the double layer is formed in front of the
cathode, which has an additional positive charge. Particles are absorbed
by the double layer and when they reach at the double layer, they lose
their negative charge and then, due to their positive charge, very
quickly absorbed to the surface with the negative charge (Fig. 3).

3. Effective parameters in the electroplating process (bath

parameters and external parameters affecting the composite
matrix and particles)

3.1. pH

One of the effective factors in the electroplating process is pH. The

increased pH leads to metal ion deposition, increased impurities and
residual stress. At lower pHs, the current efficiency is reduced and the
residual stress also increases, and due to hydrogen attack, the coating
becomes prone to pitting. Therefore, at an optimal pH a coating with Fig. 4. The charged colloidal particle and the location of zeta potential.

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S. Mersagh Dezfuli and M. Sabzi
the particle, r is the particle radius, and η is the viscosity of the sus-
pension. The Stoke equation implies that, under the same conditions, a
particle with a greater q has more electrophoretic velocity. Resulting in
a higher sediment and sediment rate [45,46].
The value of Zeta potential indicates the particles collisions which is
a criterion for the suspension stability. If the zeta potential of the par-
ticles is very negative or positive, the particles tend to repulse each
other and resist against agglomeration. If the zeta potential of the
particles is low and close to zero, there is no factor to prevent the
particles from attracting each other and agglomeration of particles
occurs. Most of the materials in contact with water have zeta potential
that is affected by the pH, concentration of the additive or ionic in-
tensity of the medium. pH is the most important parameter that affects
the zeta potential. When the pH is increased by the addition of alkali,
the particles surface will be more negative. If acid is added to the
medium, ionization leads to a reduction in the hydroxyl ions, which
leads to a more positive surface. Therefore, materials are more positive
at lower pHs and at higher pH values become more negative
[42,45,46]. By plotting the zeta potential curve in terms of pH, at a
certain pH value the zeta potential is zero, which is called the iso-
electric point. This point is very important which indicates the pH value
that the colloidal system is at least stability, and in this point the double
layer capacity is minimum. A large number of theories have been
proposed for the distribution of neutral particles in a metal matrix in-
volving particle transport:
1) Convection diffusion, 2) Electrophoresis, 3) Absorption, 4)
Mechanical trapping.
Electrophoresis is the induced motion of colloidal particles or sus-
pended molecules in an ionic solution due to the applied electric field.
The electrophoretic velocity is a function of the electrostatic forces on
the surface charge, the electrostatic forces on their electric double
layers, the viscous force of the colloidal particles motion and the motion
of ion cloud of the colloidal particles. Colloidal particles are charged in
aqueous solution. The charge can be due to ionization of surface groups,
chemical bonding or physical absorption of ions from the aqueous
medium. Therefore a suspended charged particle in an electrolyte so-
lution tends to be surrounded by the ion cloud [45–47].
3.2. Temperature
Another important parameter in the electroplating process is the
temperature. In the study of the effect of temperature on the metal
matrix, it is observed that at higher temperatures the diffusion of single-
atoms increases and leads to a much higher rate of grain growth.
Therefore, by reducing the temperature of the bath, we can obtain finer
grain structure, but we know that with decreasing temperature, the
diffusion coefficient of the metal ion (D) decreases and the mass
transfer in the diffusive layer becomes difficult. Therefore, there is also
an optimal amount for the bath temperature to minimize the grain size
of the metal matrix [48,49]. Study of the effect of temperature on the
distribution and the percentage of the deposited particle has shown that
with increasing temperature the particle's activity increases and it re-
sults in more co-precipitation of the particles. However, with higher
temperature than optimum value, the thermodynamic motion of the
ions is much increased and leads to an increase in the kinetic energy of
the particles. According to Langmuir's absorption theory, the increased
temperature leads to a decrease in the absorption ability of the particles
and subsequently a decrease in the cathodic potential difference as well
as electric field, which makes the absorption of the particles more dif-
ficult, reducing the particles co-precipitation [49–51]. In Fig. 5, the
effect of the electroplating bath temperature on the coating deposition
rate is shown schematically. It is seen in this figure that the rate of
deposition is usually increased with increasing temperature. But after
an optimal temperature, the deposition rate is reduced.
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Fig. 5. A schematic of the influence of the electroplating bath temperature on
the coating deposition rate.
3.3. Additives
Another important factor in the process of electroplating is the ad-
ditives. Different Types of wetting additives include: 1) anionic 2) ca-
tionic and 3) nonionic.
1-The anionic additives like Sodium dodecylsulfate (SDS): An an-
ionic SDS additive has two sections of a tail (non-polar and hydro-
phobic) and a head (polar and hydrophilic). 2- The cationic additives
like Cetyl Trimethyl Ammonium Bromide (CTAB). The additives reduce
the agglomeration by increasing the wettability. The cationic additive
leads to a positive surface charge on the particle surface, resulting in
repulsion between the particles, reduction of agglomeration, attraction
toward the cathode and increased co-precipitation of the particles.
Anionic additive, by generating a negative charge on the particles
surface and absorbing metal ions, leads to positive polarity on the
surface and leads to the repulsion of other particles.3- Non-ionic ad-
ditives cause repulsion of the particles by generating spatial inhibition
[49,51,52].
Various additives such as Cetiltreemetilamonium Bromide (CTAB),
Sodium Dodecil Solfamate (SDS), Hexadecylpyridinium Bromide (HPB)
and Polyelectrolyte Dispersant (PED) are used to achieve better coating
properties such as surface roughness, particles co-precipitation, and
uniform particles distribution in the coating and increased wear re-
sistance and hardness. According to Ming-Der Ger's studies [12,17,19],
the addition of CTAB results in better surface fineness and a higher
degree of co-precipitation and decreased agglomeration. When the
concentration of the cationic additive increases, the zeta potential of
the particles increases as the cationic additives are absorbed. Increasing
Zeta potential contribute to an increase in the attraction force between
the neutral particles and the cathode. In other words, it makes the
particles more effective and increases the effective size of the neutral
particles, and a larger number of particles with larger size will pre-
cipitate. As a result, it increases the particles co-precipitation. On the
other hand, by increasing the concentration of the additives, the re-
pulsive force generates between the absorbed additives on the cathode
and those the particles should be selected which are in optimal condi-
tion of additives [49–51].
The SDS additive also makes the particles surface's charge more
negative, which can reduce the agglomeration, but its effect on the
percentage of deposited particles is different. Since the cathode has a
negative pole and this anionic additive also generates a negative charge
on the surface, repulsion is made between the particles and the cathode.
But, on the other hand, when the particle surface is negatively charged,
a positive cloud of ions generates around the particles that can create
attraction with cathode [50–52].
Thus, its effect depends on the type of the bath. In addition to the
S. Mersagh Dezfuli and M. Sabzi
above additives, there are growth inhibitors of the nuclei in the elec-
trochemical precipitation, the most important of which is saccharin,
which blocks active sites for the growth and reduces the growth rate of
the crystals. Its concentration is between 0.05 and 4 gr/litr. Also, sac-
charin is the most effective factor in reducing stress and also helps to
reduce opacity. It is possible to produces nano-sized grains using sac-
charin under special conditions; however, the limitation is that its
chemical composition introduces the impurities of carbon and sulfur
into the structure. Due to the presence of sulfur, saccharin can reduce
grain size and increase mechanical properties, but it leads to a decrease
in toughness, especially at high temperatures [48–50].
3.4. Concentration of the particles
Particles concentration and current density are two fundamental
factors in the particles co-precipitation in the electroplating process, in
which the particles flux as a function of current density (i) and particles
volume fraction in the layer (xv) can be described by equation (5).
3Vm, M
xv
JP = i
4πr 3zFNA 1 − x v (5)
In equation (5), Vm, M is the molar volume of the metal, r is the
particles radius, z is the metal ion charge, F is Faraday constant and NA
is the Avogadro constant [53–55]. By increasing the concentration of
particles in the solution, the percentage of particles in the coating in-
creases to a certain extent. However, by increasing the excess con-
centration of particles due to the increase in surface free energy, the
tendency to agglomeration becomes higher and can lead to a decrease
or a fixed percentage of particles [49–51]. By increasing the content of
particles in the solution, the amount of particles that reach the surface
of the cathode will increase as well. Only those particles that stick to the
surface of the cathode for a sufficient amount of time are more likely to
co-precipitate. Therefore, the trapping of particles in the matrix of
growing metal depends on the particle rate that reaches to the cathode
surface and the metal deposition rate. By increasing the particle con-
tent, the magnitude of the co-precipiation reaches to its maximum value
or in fact, its equilibrium state. The equilibrium state occurs when the
number of particles that precipitates is equal to the particles numbers
that reach to the cathode surface. By increasing the amount of particles
more than optimal value, the possibility of particles agglomeration in-
creases. The agglomerated particles themselves resist against co-pre-
cipitation, and they prevent the flux of particles entering the cathode.
Therefore, the particles co-precipitation in the coating matrix can be
reduced. If the particles do not agglomerate, since the capacity for
trapping the growing metal remains constant, after a certain con-
centration, co-precipitation can hardly increase or becomes constant
[49–52].
3.5. Type of current
Different types of currents that are used in electroplating include:
(1) direct current (DC), (2) pulsed direct current (PDC), and (3) pulsed
reverse current (PRC). In the pulsed direct current, the cathodic direct
current changes at different deposition times. While in the pulsed re-
verse current, during the on-time cycle, the cathodic current is applied
and during the off-time cycle anodic current is applied [54–56].
The pulsed reverse current has been more successful than other
currents for particles co-precipitation, which refers to the dissolved
deposited metal during off-time cycle. The application of the pulsed
current leads to the co-precipitation of more concentrations of nano-
particles and also improves a wide range of properties. The pulsed re-
verse current has advantages over direct current. These properties in-
clude: 1) increasing the amount of nanoparticles in the metal
deposition; 2) lower concentration of nanoparticles in the solution and
3) selective trapping of particles of the same size. All of these benefits
are due to the dissolution of the deposited metal during the off-time
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cycle, which results in the detachment of the particles larger than
precipitates and smaller particles remain in the metal deposition
[54,55]. The use of pulsed current leads to the use of higher current
densities than the direct current, as a result a nano-crystalline structure
can be obtained. The pulsed current also leads to lower porosity, greater
uniformity, improved properties and increased corrosion resistance
[55,56]. If the pulsed current is used, there is a change in the process of
absorption and repulsion of particles and ions through the presence of
off-time cycle, which allows better control of the microstructure. The
off-time cycle results in the loss of concentration polarization and the
release of hydrogen molecules at the cathode surface, and this leads to
an increase in metal ions around the cathode as well as further nu-
cleation and as a result refinement of the grains in the structure. An-
other advantage of using the pulsed current is to reduce the limitation
of the use of higher currents, and if higher currents are used, a higher
potential difference can be applied and ultimately leads to fine grains in
the coating [54–56].
3.6. Current density
According to previous studies, several types of current density de-
pendencies have been identified [57,58]. Some researchers have not
reported any effect of current density on the deposited particles and
thus on the microhardness. In another report, at high current densities,
increased release of hydrogen and reduction of metal deposition as well
as local increase in the pH have been stated. Consequently, metal hy-
droxide is formed near the cathode and, by incorporation in the coating,
has led to high microhardness values [54–57]. By increasing the mean
current density, the grain size of the composites matrix is reduced, and
by decreasing the grain size, hardness increases, which is in good
agreement with the theory of nucleation and growth. This indicates that
as the current density increases, the nucleation rate increases too. While
the growth of nuclei at low current densities is more probable. The
changes of current density lead to the variations in the surface mor-
phology, which in low current densities the structure is pyramidal-like,
and with increasing current density, the structure becomes spherical. At
low current densities the probability of agglomeration of particles is
also increased. At high current densities, metal ions which have been
dissolved from an anode are transmitted faster and the repulsive force
between metal ions and adsorbed particles at the surface are stronger at
high current densities relative to low current densities and therefore the
particles are better distributed and their agglomeration occurs less
frequently. Sometimes due to the less mobility of particles in compared
to ions, the percentage of deposited particles increases by decreasing
the current density. According to the studies, the effect of current
density on the amount of co-precipitation also depends on the type of
the bath [55–58].
3.7. Frequency of the current
By increasing the frequency in the electroplating process and using
higher current densities to a certain extent, a finer and more uniform
structure can be attained. However, at very high frequencies, the
double layer does not have the enough time to fully charge during on-
time cycle and full discharge during off-time cycle, which causes a
flattening effect on the applied waveform and drives it to the DC cur-
rent. For the most applications, the maximum useful frequency is up to
500 Hz. Co-precipitation of particles also depends on the on-time and
off-time durations. By increasing the frequency at a constant percent of
the on-time, no change in the total duration of the off-time and on-time
in a second occur. But it changes the duration of the off-time and on-
time in a cycle. In some cases, with increasing frequency, there is no
significant change in the rate of co-precipitation, but sometimes with
increasing frequency the percentage of particles increases. The reason
for this is that, as the frequency of the off-time decreases, detachment of
the particles occurs due to the stirring of the bath and as a result
S. Mersagh Dezfuli and M. Sabzi
reduction of particles co-precipitation occurs. Sometimes, the opposite
state is taken into account, by claiming that at high frequencies, ag-
glomerated particles during low on-time cycle do not experience strong
absorption and will detach at off-time cycle, which results in the uni-
form distribution of particles and less percentage of particles precipitate
[59,60].
3.8. The percentage of duty cycle
The percentage of the duty cycle is defined as equation (6).
t on
d.c =
t on + t off (6)
In Equation (5), ton depicts the on-time and toff depicts the off-time
durations. For example, by increasing the percentage of on-time at a
constant frequency, the co-precipitation of the ceramic particles in the
Cu–Al2O3 coating and the graphite particles in the Cu–Sn-graphite
coating is reduced. The maximum particle concentration is obtained
when the thickness of the deposited layer in a cycle is close to the
diameter of the particles. Therefore, the smaller the size of the particle
is, the lower the on-time or in fact the percentage of the on-time would
be, so that the maximum co-precipitation of particles can be achieved.
For Cu–Al2O3 coatings with particle size of 50 nm, the optimal per-
centage of on-time was obtained equal to 5%. Reduction of the per-
centage of on-time to a certain extent leads to an increase in the pre-
sence of particles in the coating during the off-time cycle and as a result
there will be an increase in structural defects. Therefore, with a de-
crease in the percentage of on-time, the hardness of the coating in-
creases. Free ions have high mobility relative to the ceramic particles
which have Cu2+ ion cloud. Therefore, there is competition between
ions and particles during the on-time and off-time cycles for the de-
position on the cathode. During the on-time cycle, due to the high
mobility of Cu2+ ions relative to ceramic particles the co-precipitation
of particles is lower, while during the off-time cycle the ions and par-
ticles are in the same conditions in terms of competition. These con-
ditions increase the chance of the presence of particles on the cathode
surface. Thus, with increasing the off-time cycle, the co-precipitation of
particles is increased [55–58].
3.9. The effect of stirring speed
Stirring of the bath is done for two reasons: 1) suspending the
particles in the electrolyte; 2) transferring the particles to the cathode
surface [50–53]. The co-precipitation rate of nano-particles with in-
creasing stirring speed increases first and then decreases which it can be
attributed to the co-precipitation of particles and metal deposition rate.
Regarding the co-precipitation of micro-particles, it can be stated that
the increase in stirring speed leads to the movement of particles toward
the cathode more rapidly and the speed of particles collisions increases.
Increasing the collision rate does not provide sufficient time for parti-
cles to remain on the surface of the cathode and will result in particles
rejection. Therefore, with increasing stirring speed, the possibility of
particles co-precipitation in the metal matrix is reduced. Nanoparticles
tend to agglomerate and at low rates of stirring, stirring energy is too
low to reduce agglomerates. These particles also have a strong tendency
to deposit in the bottom of the bath at low speeds. As the stirring speed
increases, stirring strength increases for the floating of particles. If the
stirring speed is exceeded by a certain amount, the collision rate of the
particles increases and the residence time decreases so the co-pre-
cipitation rate decreases. At high stirring speeds, the hydrodynamic
forces applied to the particle also increased and the particles were se-
parated from the cathode surface before being remained in the deposit
[56–60]. Nanoparticles have a tendency to agglomeration due to their
high surface energy which stirring of the bath is used to reduce ag-
glomeration during electroplating. However, stirring can reduce ag-
glomeration up to a certain extent [51–55].
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4. Adhesion of electroplating coatings
Good adhesion, defined by construction, testing, and service con-
ditions, is one of the most basic needs of any substrate-coating system.
Good adhesion is defined by a large number of factors, many of which
are very difficult without a gradual process. In engineering applica-
tions, the adhesion of physical strength is a common interface between
areas of a material system. Such common surfaces are found in the
boundaries of the grain, the surfaces of wear and fracture, and also in
substrate-coating system [61–63]. The adhesion of electroplating
coatings to most metals is desirable. The primary substitution reaction
in a substrate allows for electroplating, in addition to creating a me-
chanical bond between the coating and the substrate, to form a metallic
bond (metal bond) with the substrate. The strength of this bond is
measured in a steel substrate of 200–300 MPa. In a non-catalytic sub-
strate, the initial substitution reaction does not occur and the adhesion
strength decreases. Upon initial preparation of the surface and its ac-
tivation, the bond strength increases. In some aluminum substrates,
after applying the coating, the parts are placed at 170–200 °C for about
60–120 min to increase the adhesion of the electroplating coating to the
substrate. It should be noted that the adhesion of the coating to the
substrate is heavily subjected to initial operations on the surface
[61,63]. Therefore, the production parameters, production process
conditions, and post-production operations will greatly affect the mi-
crostructure [64–67], phase equilibrium [67–69], mechanical proper-
ties [70–72], corrosion resistance [73,74], and all metallurgical prop-
erties [75,76] of the engineering components.
5. Conclusions
In this paper, the influence of the parameters of the electroplating
process on ceramic nanocomposite coatings was investigated. The re-
sults are as follows:
a) It was concluded that the general mechanism of ceramic or metal
deposition consists of two stages of nucleation and growth, which
these two stages are subdivided into three stages: 1) Transfer of ion
or nanoparticles from the solution to the surface of the cathode. 2)
Transfer of the charge and conversion of the ion to the metal atom.
3) The diffusion of the ceramic or metal atom into the matrix phase
of the coating and grain growth.
b) Increasing the pH of the electroplating bath leads to the metal ion
deposition, increased impurities and residual stresses in nano-
composite coatings. At lower pHs, the current efficiency is reduced
and the residual stresses in nanocomposite coatings are also in-
creased and due to hydrogen attack, the coating becomes suscep-
tible to pitting. Therefore, a coating with fine grains and high-
quality is obtained at an optimal pH value.
c) By decreasing the temperature of the electroplating bath, we can
obtain a fine-grained structure, but with decreasing temperature,
the diffusion coefficient of the metal ion (D) decreases and the mass
transfer to the diffusive layer becomes difficult. By increasing the
temperature of the electroplating bath, the diffusion of single-atoms
increases in the surface and leads to a much higher rate of grain
growth.
d) By increasing the concentration of nanoparticles in the electro-
plating bath, the amount of nanoparticles in the coating is partially
increased. But with the increasing concentration of nanoparticles in
the bath too, due to an increase in the surface free energy of na-
noparticles tend to agglomerate more.
e) Pulsed reverse current has been more successful than other currents
for particles co-precipitation in the electroplating process, which is
due to the dissolving of the deposited metal during off-time cycle.
The application of pulsed current during the electroplating process
results in the co-precipitation of higher concentrations of nano-
particles and also the improvement of a wide range of properties.
S. Mersagh Dezfuli and M. Sabzi
f) By increasing the frequency in the electroplating process, a finer and
more uniform structure in nanocomposite coatings can be achieved
using higher current densities. However, at very high frequencies,
the double layer doesn't have enough time fully charge during on-
time cycle and full discharge during off-time cycle which this causes
a flattening effect on the applied waveform and drives it to the DC
current.
g) Increasing the current density raises the nucleation rate in nano-
composite coatings. While at lower current densities the growth of
nuclei is more probable.
h) By increasing the percentage of on-time cycle at constant frequency
during the pulsed reversed current electroplating process, the co-
precipitation of ceramic nanoparticles in nanocomposite coatings
also decreases.
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