Surface & Coatings Technology 187 (2004) 293 – 299

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Electrodeposition of graphite-bronze composite coatings and study

of electroplating characteristics
A. Afshar, M. Ghorbani, M. Mazaheri *
Department of Materials Science and Engineering, Sharif University of Technology, P. O. Box 11356-8639, Tehran, 8639, Iran
Received 5 June 2003; accepted in revised form 30 April 2004
Available online 28 August 2004

Abstract

The aim of this research is to obtain composite coatings of bronze (90% Cu – 10% Sn) with graphite particles. The electrodeposition of
G – Cu (Sn) composites from an alkaline bath containing cyanide is described. Composite coatings consisting of graphite particles and
copper-tin were prepared by means of the conventional electrocodeposition (CECD) and sediment codeposition (SCD) techniques. The
graphite particles involved were less than 10 Am. The dependence of graphite amount in the composite coatings was investigated in relation
to the graphite concentration in bath, cathode current density, stir rate and technique type and it was shown that these parameters strongly
affected the volume percentage of graphite. The deposition efficiency with and without graphite particles in bath was studied. The
morphology and phases of the electrodeposited composite were studied. Composite coatings were obtained with roughness significantly
higher than the bronze alloy coatings. The graphite distribution in composite coatings at low concentrations of graphite in bath was uniform
across the coating, but at high concentrations, graphite particles on the surface were agglomerated. The graphite percentage in composite
coatings obtained was up to 8.5% (vol.) in the CECD and 11.8% (vol.) form the SCD technique.
D 2004 Elsevier B.V. All rights reserved.

Keywords: Electrodeposition; Graphite-bronze coating; Sediment codeposition

1. Introduction
Research into the production of composite coatings by
electrolytic codeposition of fine particles with metal from
plating baths has been investigated by numerous investi-
gators. Interest in electrodeposited composites has in-
creased substantially during the past two decades due
mainly to the fact that composite coatings can give various
properties, such as wear resistance, high temperature
corrosion protection, oxidation resistance and self-lubrica-
tion, to a plated surface. Research on electrodeposition of
composite coatings has been attention directed towards the
determination of optimum conditions for their production,
i.e., current density, temperature, particle concentration and
bath composition.
Occlusion plating of a second phase with a metal matrix
has been carried out by employing both CECD and SCD
techniques [1]. In the CECD technique, particles were kept
in suspension in the bath by continuous agitation throughout
* Corresponding author. Tel: +98-21-8066726; fax: +98-21-8066726.
E-mail address: mazaherii@yahoo.com (M. Mazaheri).
the duration of the experiment. On the other hand, for the
SCD technique, particles were suspended in the electrolyte
and allowed to settle onto the horizontal cathode as a
sediment. The layer of sedimented particles was periodically
disturbed by vigorous agitation, and then permitted to settle
again for codeposition [2,3].
Several copper-based composites have been successfully
produced by occlusion plating. Sediment codeposition
(SCD) has been developed such that it gives a higher
percentage incorporation of the second phase material and
better control of operational parameters [3].
Codeposition of particles in a metal matrix is the result of
adsorption of metal ions at the particle surface and thus
making them attracted to the cathode [4]. The influence of
the particles presence in the electrolyte on the mass transfer
enhancement [5] and effect of hydrodynamic conditions on
the particle content in codeposits has also been investigated
[6]. The kinetics of the deposition of inert particles from
electrolytic baths has been investigated by Guglielmi [7]
and Celis and Roos [8]. A mathematical model for electro-
lytic codeposition of particles with a metallic matrix was
discussed by Celis et al. [9].

0257-8972/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2004.04.096
294 A. Afshar et al. / Surface & Coatings Technology 187 (2004) 293–299

Table 1 types were examined by XRD method. The graphite, copper

Composition and deposition parameters of Cu – Sn bath used
and tin content of the composite coating were analyzed by
Deposition parameters Amount the weight method and EDX. Etching of the surface is
CuCN 29 g/l necessary to reveal the presence of graphite particles incor-
K2SnO3 35 g/l porated in the coating. A nitric acid solution (10 vol.%) was
KCN 64 g/l
used during 5 s for experiments.
KOH 10 g/l
Rochelle salt 45 g/l
T 30 – 70 F 2 jC
PH 12 3. Results and discussion
CD 2 – 5 A/dm2
3.1. Bronze coating

Composite coatings have been produced by electrolytic The purpose of this work was to find the dependence of
codeposition of fine inert, semi conductive and conductive the Cu – Sn alloy composition on the different bath param-
particles with metal from plating baths [10]. An overview of eters and also the optimum conditions for the electrodepo-
electrodeposited composite coatings of copper with inert, sition of a 90% Cu –10% Sn coatings. Fig. 1 shows the
semi conductive and conductive particles is done by Stan- chemical composition of matrix as a function of current
kovic and Gojo [10]. density at 40 and 70 jC. An increase in current density at 70
Numerous studies have been devoted to electrodeposited jC from 2 to 7 A/dm2 led to an increase in tin percent from
copper-based composites [11,12], but very few have exam- 10% to 18%, but at 40 jC, the effect of current density on
ined the influence alloying aspects on the codeposition chemical composition was less and the tin percent is
process and the properties of the resulting composite coat- approximately 10% for current densities between 2 and 7
ings. Some experiments have been carried out on electro- A/dm2. Thus, the dependence of chemical composition on
deposition of a-Al2O3, CaF2 and talc particles with Cu – 10 temperature is more significant than current density. Fig. 2
wt.% Sn alloy [13] and graphite with a brass alloy (Cu – 30 shows the XRD pattern of alloy coating. It shows that the
wt.% Zn) [14]. This paper presents results of research into deposit has a mono-phase matrix (a-bronze).
the electrodeposition of graphite-bronze composite coatings
with particular reference to the electroplating parameters of 3.2. Cathode efficiency
the bath used.
Fig. 3 indicates the variation in cathode efficiency of the
bronze bath with current density for two temperatures, 40
2. Experimental and 70 jC. It can be seen that the cathode efficiency
declines with the increase of current density. The efficiency
The electrolyte used in this study was a cyanide system, is higher at 40 jC than at 70 jC at a given current density.
containing graphite particles. The composition of the solu- This can be attributed to polarization at surface of cathode
tion and operating parameters for electrodeposition are with increasing current density and temperature. The cath-
shown in Table 1. The graphite powder used in the process ode efficiency at 40 jC varies from 78% to 47% (related to
has size less than 10 Am and was added to bath with 90% Cu – 10% Sn).
concentration of 20 – 100 g/l.
Cathodes, made of cold-rolled steel, were positioned in
horizontal plane with anode above them (in SCD) and vertical
(in CECD). The distance between anode and cathode was 4
cm. Steel specimens 50  50  0.5 mm were used for the
cathode efficiency determination and other experiments.
Before each experiment, cathode was consecutively
polished up to 600-grain emery paper, washed with deter-
gent, dipped in acid solution (HCl), rinsed with distilled
water and dried. Anode was prepared from bronze (90%
Cu – 10% Sn) and reference electrode was Ag/AgCl.
Occlusion plating of bronze-graphite was carried out by
employing both CECD and SCD techniques. Experiments
were performed in a cell with magnetic stirring in order to
keep particles in suspension. Stirring intensity was up to 200
rev/min.
Surface morphologies of composite coatings were exam- Fig. 1. Chemical composition of matrix as a function of current density at
ined by scanning electron microscope F S.E.M.) and phase 40 and 70 jC.
 A. Afshar et al. / Surface & Coatings Technology 187 (2004) 293–299
Fig. 2. The XRD pattern of alloy coating (a-bronze).
The introduction of graphite to bath gives a variation
cathode efficiency. Fig. 4 shows the change in cathode
efficiency with addition of graphite particles to bath. When
graphite particles collide at the cathode surface because of
good conductivity of graphite, the conditions for deposit
formation are established and so the cathode efficiency
increases.
3.3. Content of graphite embedded in coating
The volume fraction of particles in composite coatings
(denoted by Vp) was determined by gravimetric analysis.
Electroplating of the G –Cu (Sn) coating was carried out by
employing both the CECD and the SCD techniques. The
graphite percent in composite coating as a function of
graphite concentration and stir rating is shown in Fig. 5.
In constant stir rating, an increased concentration of
particles in the bath corresponded to an increased Vp for
composite coating. The results shown in Fig. 5 can be
explained by the Guglielmi two-step adsorption model
where a higher particle concentration in the electrolyte
increases the adsorption, thus resulting in a higher Vp
Fig. 3. The variation in cathode efficiency of the bronze bath with current
density.
295
Fig. 4. The change in cathode efficiency with addition of graphite particles
to bath at 40 jC.
[1,2]. Also, the graphite amount in coating decreases with
increasing of the stir rating. At a high stir rate, because of
turbulent flow in bath, graphite particles on the cathode
surface are washed away and thus the graphite percent in
composite coating decreases. In terms of the Foster model,
with increase of stir rate resulting in increasing the forces
acting on the particles resting on the cathode surface, this
decreases Vp. In Fig. 5, it can be seen that with increase of
graphite concentration above 50 g/l in bath, the graphite
percent in composite coating becomes almost constant,
which is similar to the observed for Al2O3 – Cu (Sn), talc –
Cu (Sn) [15] and G –Cu (Sn) composites [16]. This can be
attributed to the effective saturation particle concentration.
In high concentrations (50 g/l), because of the agglomera-
tion of particles in bath, the effective particle concentration
is constant, thus resulting in constant graphite percent in the
composite coating.
Fig. 6 shows the relationship between current density and
VP for the CECD and the SCD processes at 40 jC where %
Sn is constant (10 wt.%). An increase in current density
Fig. 5. The graphite percent in composite coating as a function of graphite
concentration and stir rating.
296 A. Afshar et al. / Surface & Coatings Technology 187 (2004) 293–299

Fig. 8. The relationship between VP and stir rate in CECD and SCD methods.
Fig. 6. The relationship between current density and VP for the CECD and
the SCD processes at 40 jC.
gravity force on particles and then growth of bronze matrix
around the particles.
The relationship between VP and stir rate in the CECD
from 3 to 6 A/dm2 led to a decrease in VP. This can be
and the SCD methods is shown in Fig. 8. The graphite
explained by the fact that an increase in current density
percent in composite coating decreases with increase of stir
results in a more rapid deposition of metal matrix and less
rate, as shown in Fig. 8. This can be explained in terms of
graphite is embedded in the composite coating, as reported
the Foster theory where the effect of stirring increases the
by Fawzy [15] and Wang et al. [13]. Hence, the metal
forces acting on the particles resting on the cathode surface
deposition dominates over particle deposition in the code-
(which decreases Vp) [16].
position process. To increase the graphite percent in the
coating, the SCD technique is the best process. In Fig. 6, it
3.4. Content of tin in matrix of composite coating
can be seen that at each current density, the graphite amount
in the SCD process is higher than the CECD process.
Fig. 9 shows the dependence of the matrix composi-
Fig. 7 compares the SCD and the CECD techniques. In
tion on temperature at a cathode current density of 3 A/
constant graphite concentration, the amount of graphite in
dm2. The alloy composition substantially affects the color
composite coating is higher in the SCD compared to the
of the deposit. Electrodeposits containing over 92%
CECD technique, which is similar to that observed by
copper demonstrate a rose tint. A golden yellow color
Ghouse for Cu –G and Cu – SiC composite coatings [4,8].
is provided at a copper content of 80% to 90%. The
This results from sedimentation of the graphite particles on
phases in composite coating are a-bronze and graphite.
the horizontal cathode in the SCD technique because of the

Fig. 9. The dependence of the matrix composition with temperature at the

Fig. 7. Comparison of the SCD and the CECD techniques. cathode current density of 3 A/dm2.
 A. Afshar et al. / Surface & Coatings Technology 187 (2004) 293–299
Fig. 10. The XRD pattern of composite coating containing of mono-phase matrix (a-bronze) with embedded graphite particles.
In Fig. 9, it was found that the presence of graphite in
bath increases the tin percent in matrix of composite
coatings.
3.5. Study of morphology
Traditional optical microscopy and electronic scanning
microscopy F S.E.M.) are used to realize the surface
morphology.
The XRD method of G –Cu (Sn) coatings is a suitable
method to determine the phase kind and presence of
graphite in the alloy matrix. Fig. 10 shows the XRD pattern
of composite coating. It shows that the deposit has mono-
phase matrix (a-bronze) with embedded graphite particles.
Fig. 10 shows the comparison of bronze alloy coating with a
graphite-bronze composite coating.
Micrographies presented allow comparison between a Cu
(10% Sn) coating (Figs. 11 and 12) and Cu (10% Sn)– G
Fig. 11. Micrograph of Cu – Sn alloy coating without graphite particles.
297
coatings containing of 8.5%G (Figs. 13 and 14) at different
magnification.
The morphology of the bronze (Cu– Sn) is uniform
and the deposit has a regular surface. The introduction of
graphite to coatings in both the CECD and the SCD
caused dendritic growth. The morphology of the G –Cu
(Sn) composite coatings is irregular and at a low graphite
percent, the graphite particles are clearly visible on the
surface with a homogeneous distribution but when graph-
ite content in bath increases, the agglomeration of par-
ticles in coating increases. One of the most reliable
methods to observe the distribution of the graphite par-
ticles in the bronze matrix consists of taking photographs
of cross-section.
The micrographies show the presence and distribution of
graphite particles in the metal matrix. Those that appear as
black points. The thickness of composite coatings was 20
Am. Figs. 15 and 16 show agglomeration of graphite
Fig. 12. Micrograph of Cu – Sn alloy coating without graphite particles.
298 A. Afshar et al. / Surface & Coatings Technology 187 (2004) 293–299
Fig. 13. Micrograph of G – Cu (Sn) composite coating containing of 5.4% G.
particles in composite coating in bath containing of 50 g/l G,
where the size of agglomerated graphite particles reach
above 20 Am.
4. Conclusions
The composition of matrix depends on current density
and temperature. Coatings with 90% Cu – 10% Sn can be
obtained from the cyanide bath at 40 jC. However, the
variation of current density has negligible effect on %Sn in
matrix at 40 jC. The composite coating has mono-phase
matrix (a-bronze) and graphite particles. The current
density and graphite content in solution influence the
cathode efficiency; with decrease of current density or
increase of the graphite content in bath, the cathode
efficiency increases. Graphite particles can be successfully
codeposited with bronze alloy by both the CECD and the
SCD techniques.
The graphite content of the composite coatings depends
on the particle concentration in bath, current density, stir
rating and method of deposition (CECD and SCD). The
Fig. 14. Micrograph of G – Cu (Sn) composite coating containing of 5.4% G.
Fig. 15. Micrograph of G – Cu (Sn) composite coating containing of
11.8% G.
amount of graphite obtained by the SCD technique is
greater than that obtained by the CECD technique under
all the conditions studied. While the percentage of the
second phase obtained is up to 8.5% (vol.) in the CECD
process, where it was 11.8% (vol.) for the SCD technique.
The graphite amount in composite coating decreases with
the current density employed for both techniques. The
extent of incorporation of graphite increases with the
concentration of graphite suspended in the bath. The effect
is much more marked at the lower concentrations and it is
less significant at the higher concentrations.
The distribution of graphite particles in composite coat-
ing at low concentrations is uniform, but at high concen-
trations of graphite in bath, agglomeration of graphite
particles takes place on the surface. The bronze alloy
coating has a regular surface. Metallographies of deposits
obtained for bronze alloy coating without graphite particles
show a smooth surface. The introduction of graphite par-
ticles into solution in both the CECD and the SCD causes
dendritic growth.
Fig. 16. Agglomeration of graphite particles in G – Cu (Sn) composite
coating at bath containing of 50 g/l G.
 A. Afshar et al. / Surface & Coatings Technology 187 (2004) 293–299
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