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Surface & Coatings Technology 204 (2010) 35923598

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Surface & Coatings Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / s u r f c o a t

Pulsed-reverse current electrodeposition of Zn and Zn-TiO2 nanocomposite lms

T. Frade, V. Bouzon, A. Gomes , M.I. da Silva Pereira
C.C.M.M., Departamento de Qumica e Bioqumica da Faculdade de Cincias da Universidade de Lisboa, Campo Grande, 1749-016 Lisboa, Portugal

a r t i c l e i n f o a b s t r a c t

Article history: Zn and Zn-TiO2 nanocomposite lms were prepared by pulsed-reverse current electrolysis, from acidic zinc
Received 19 November 2009 sulphate solutions, on a Ti support. The inuence of the anodic pulse current, on the electrodeposit structural
Accepted in revised form 12 April 2010 and morphological characteristics, has been investigated. The samples were characterized by X-ray
Available online 18 April 2010
diffraction (XRD) and scanning electron microscopy (SEM) coupled with energy dispersive X-ray
spectroscopy (EDS). The amount of TiO2 incorporated into the lm was determined by induced coupled
plasma spectroscopy (ICPS).
Metal matrix
It was found that the anodic pulse current density (ia) plays a remarkable inuence on the coatings
Nanocomposite materials morphology and zinc crystallite size. When no anodic pulse is applied, both the zinc average crystallite size
Pulsed-reverse current electrodeposition and TiO2 content present the minimum values. By contrast, the nanocomposites prepared with the highest ia
Preferred orientation value (19 mA cm 2), exhibit the highest values for the zinc average crystallite size and TiO2 content.
SEM results conrm that the pulse-plating parameters and the presence of boric acid have a strong inuence
on the deposit surface morphology. Moreover, an increase of the anodic current pulse leads to smoother
coating surfaces. XRD, SEM and ICPS data indicate that the increase on the anodic current pulse promotes the
incorporation of the nanoparticles into the nanocomposite deposits.
2010 Elsevier B.V. All rights reserved.

1. Introduction applications as photocatalysts, particularly in the treatment of

polluted water [11].
Electrolytic co-deposition is widely used to obtain metal matrix In previous works, we have used, successfully, pulsed direct
composites due to its ease of preparation, low cost and versatility [1]. current on the preparation of Zn-TiO2 nanocomposite lms on Fe and
Pulsed direct current (PDC) is an alternative technique, to direct Ti substrates [12,13]. It has been found that the zinc matrix crystal
current, for the preparation of metallic lms, which allows the orientation changes with Zn2+ ion concentration, presence of the TiO2
tailoring of the deposit properties [2]. Specically, for composite lms, nanoparticles and pH of the electroplating bath. Furthermore, the
the application of a pulsed current enables the incorporation of presence of a surfactant led to a decrease on the metallic grain size
particles in high concentration in addition to a wider range of deposit [12]. Additionally, for the solutions with higher concentration in
compositions. Moreover, it is also possible to control the deposited metallic ions, the grain size of the metallic matrix is practically
lm composition and thickness at the atomic level by regulating the independent of the TiO2 concentration. On the other hand, for the
pulse amplitude and width [3,4]. more diluted solutions, a dependence between the metallic matrix
In the pulsed-reverse current (PRC) technique [2,5] a stripping grain size and the TiO2 concentration in the bath is observed and the
time is introduced into the plating cycle, during which the metal grain size decreases with nanoparticle concentration.
surface protrusions selectively dissolves, that ensures a uniform The goal of the present work is to investigate the inuence of the
deposit. This feature makes this technique most adequate for the anodic pulse current value on the structural and morphological
preparation of composites, enabling an increase of the particle characteristics of the as-deposited Zn and nanocomposite coatings,
incorporation in the metal matrix [59]. prepared by PCR. It is expected that higher anodic current values
The deposition parameters, namely current prole, bath compo- favour the formation of nanocomposites with high quantity of
sition, pH, particle concentration and temperature have a marked incorporated nanoparticles [9]. With this aim only deposition baths
inuence in the nanocomposite characteristics [10]. with a low concentration of TiO2 nanoparticles were tested.
Composites containing occluded TiO2 particles are interesting
materials, due to the semiconducting properties of TiO2, with several 2. Experimental

The electroplating bath for the nanocomposite preparation was a

Corresponding author. Tel.: + 351 21 750 09 13; fax: +351 21 750 00 88. mixture of 0.10 mol dm 3 ZnSO47H2O, 0.20 mol dm 3 MgSO4,
E-mail address: (A. Gomes). 0.15 mol dm 3 H3BO3 and 1 g dm 3 TiO2 (Degussa P25). A similar

0257-8972/$ see front matter 2010 Elsevier B.V. All rights reserved.
T. Frade et al. / Surface & Coatings Technology 204 (2010) 35923598 3593

bath was used for the Zn electrodeposition. The bath pH was adjusted The average crystallite size of zinc, D, was estimated from the line
to 4 by adding a diluted H2SO4 solution. The solutions were made daily widths at half maximum of the zinc diffraction peaks (002), (100) and
with Millipore Milli-Q ultra pure water without further purication, (101), using the Scherrer equation [1820].
followed by deaeration with nitrogen before and during the The morphology and elemental composition of the lms were
electrodeposition. investigated by scanning electron microscopy (SEM) coupled with
A glass cell with two compartments was used, with a Zn plate as energy dispersive spectroscopy (EDS). SEM/EDS analysis was per-
counter electrode and a commercial Ag/AgCl as reference. The formed with a JEOL (JSM-6301F) microscope with an electron beam
working electrode was a Ti disc with a 10 mm diameter. The Ti disc voltage of 25 kV.
was etched with HF 40%, polished with 0.05-m silica powder The chemical analysis of the composite coatings was performed by
(Buehler) and ultrasonically cleaned for 10 min in pure water. induced coupled plasma spectroscopy, to determine the amount of
The Zn and Zn-TiO2 nanocomposite lms were prepared by the TiO2, following the methodology used by Deguchi et al. [21]. A
pulsed-reverse current technique. The values of the pulse-plating Perkin-Elmer Optima 2000 DV has been used.
parameters and average current densities are showed in Table 1,
where ic and ia represent the cathodic and anodic pulse current 3. Results and discussion
densities, tc and ta the cathodic and anodic pulse durations and im the
average current density. The electrodeposition frequency (f) and duty 3.1. Electrodeposition studies
cycle () were xed at 42 Hz and 67%, respectively. These values were
calculated following expressions (1) and (2) [2]: The nanocomposite mass (mdeposit = mZn + mTiO2), electrodepos-
ited by applying the different galvanostatic proles is presented in
Table 2 as well as the Zn electrodeposits. As can be seen, the values are
f = 1 = ta + tc 1
slightly sensitive to the anodic pulse current, decreasing when an
anodic pulse is applied. The same trend is observed for the zinc
and deposits prepared in the absence of TiO2 nanoparticles. These results
were unexpected since the deposition charge has been kept constant
= tc = ta + tc : 2 for all the prepared samples. A possible explanation may be related to
processes that could occur during the anodic pulse, that enhances the
reaction of hydrogen evolution.
The deposition duration was adjusted in order to obtain an average The amount of TiO2 in the composites, obtained by ICPS, is also
charge value of 30 C, corresponding to electrodeposits with similar presented in Table 2. Considering these data, it can be assumed that
theoretical thickness (18 m). The deposition was performed under the mass of the deposit is mostly due to the metallic matrix. Based on
magnetic stirring at room temperature. When nished the electrode that, the current efciency was calculated and presented (Table 2). As
was removed from the cell, rinsed with Millipore Milli-Q ultra pure can be seen for the nanocomposite samples, the current efciency
water and dried under nitrogen atmosphere for 510 min at room values are slightly higher than the values for zinc electrodeposits. This
temperature. could be due to the benecial effect of the particles presence in the
The mass of the electrodeposits was evaluated by weighing the electrolytic bath, giving rise to a minimization of the hydrogen
samples before and after the electrodeposition. The obtained values reaction which is in competition with the zinc electrodeposition. The
were compared to the theoretic mass value, calculated using Faraday's solution pH variation observed during the deposition process
law, 13 mg cm 2. conrms this assumption, since the variation was lower for the
The electrochemical measurements were carried out using an solution containing TiO2 particles.
EG&G Princeton Applied Research potentiostat/galvanostat, Model
PAR 263. 3.2. Morphological studies
X-ray diffraction (XRD) analysis of the electrodeposits was carried
out using a Philips X-ray diffractometer (model PW 1710) with Cu K Figs. 1 and 2 show, respectively, the morphology of Zn and Zn-TiO2
radiation. The diffractograms were obtained in the 2 range of 20 to electrodeposited surfaces, obtained from the different PCR waves
80, using a 0.02 step and acquisition time of 2 s/step. Measurements tested. The SEM images reveal that the surface morphology changes
with acquisition time of 10 s/step were made in the 2 range of 22 to with the value of the anodic pulse current density for both
30. electrodeposit types. The smoothest surface is observed for the lms
The preferred orientation of the zinc electrodeposits was estimat- prepared with ia = 19 mA cm 2 (Fig. 1c and Fig. 2c). These observa-
ed from the X-ray data according to the methodology developed by tions support the argument that partial metal dissolution occurs
Brub et al. [14,15], using the relative texture coefcient (RTC) of a during the anodic pulse leading to an increase of the surface atness.
given (hkl) reection among the (six) rst order reections that were Reinforcing this assumption, other published studies on the electro-
monitored by XRD, namely the (00.2), (10.0), (10.1), (10.2), (10.3), deposition of composites, by pulsed electrolysis, report that smoothed
and (11.0), for the prepared samples. The RTC, expressed in surface morphologies are promoted by the use of pulse-reverse
percentage, is a weighed measure of the relative intensity of a given methods [5,22]. In addition, dissolution/precipitation processes, such
orientation, normalized against a randomly oriented zinc powder as dissolution of Zn and precipitation of ZnO or Zn(OH)2 could occur.
sample (JCPDS 4-0831) [16]. An orientation having a RTC value
greater than 16.7% (100%/6) can be considered as preferred when
Table 2
compared with zinc powder [17]. Average mass, ICPS data and current efciency for the deposits prepared with the
different galvanostatic proles.

Table 1 Galvanostatic Average mass of Ti/% Current

Pulsed-reverse electrodeposition parameters. prole deposit/mg cm 2 efciency/%

Galvanostatic prole ic/mA cm 2 ia/mA cm 2 tc/ms ta/ms im/mA cm 2 Zn Zn-TiO2 Zn-TiO2 Zn Zn-TiO2

1 19.0 0.0 16 8 12.0 1 11.94 0.34 12.59 0.78 0.16 91.8 96.8
2 19.0 6.0 16 8 10.7 2 11.74 0.16 12.241.04 90.3 94.2
3 19.0 19.0 16 8 6.3 3 10.89 0.04 11.210.46 0.25 83.8 86.2
3594 T. Frade et al. / Surface & Coatings Technology 204 (2010) 35923598

Fig. 1. SEM micrographies of the Zn lm surfaces prepared, by pulsed electrolysis, under Fig. 2. SEM micrographies of the Zn-TiO2 lm surfaces prepared, by pulsed electrolysis,
different anodic pulse current densities: a) 0, b) 6 and c) 19 mA cm 2. under different anodic pulse current densities: a) 0, b) 6 and c) 19 mA cm 2.

A closer examination of the SEM images presented in Fig. 1 shows adsorption on both the electrode and growing deposit surface,
that the metallic grains present a different shape/size depending on originates an increase of the deposition overpotential.
the applied anodic pulse current values. Furthermore the Zn lms According to Yim et al. [25], under high overpotential, the deposit
prepared with ia = 0 and 6 mA cm 2 present hexagonal grains grows in an outgrowth mode, resulting on the formation of tips, what
perpendicularly oriented to the surface, resulting in very rough can be attributed to the redistribution of Zn2+ ions in the vicinity of
surfaces. This kind of morphology was encountered by us for the rst the cathode surface. An ion decient area would then form locally, due
time. Assuming that boric acid may act as surface agent [23,24], its to differences in the Zn2+ ion consumption rate, at the electrode, in
T. Frade et al. / Surface & Coatings Technology 204 (2010) 35923598 3595

addition to the diffusion rate of Zn2+ ions from the bulk solution. on the zinc grains a ne ake microstructure is seen that, according to
Consequently, the growing tips of the deposit would encounter higher the EDS analysis, is composed of Zn and O.
Zn2+ ionic concentration than the lateral surfaces and would grow at A SEM image of the cross-section of the coating is presented in
a higher rate in the normal direction to the substrate surface [25]. A Fig. 3-b, that clearly shows the particles inside the coating.
similar microstructure was observed by Xia et al. [26], for zinc
electrodeposits prepared in the presence of gelatine.
When the anodic current density is 19 mA cm 2, there is sufcient 3.3. Structural studies
energy to dissolve the hexagonal perpendicular grains, that are more
susceptible to suffer dissolution than the other constituents of the The XRD patterns for the Zn and Zn-TiO2 composite lms are
base deposit, where the contact between the grains is larger. shown in Figs. 4 and 5.
From Fig. 2 it can be seen that the amount of TiO2 particles increase The analysis of the XRD patterns, prepared with the galvanostatic
with the increase of the anodic reverse current, and consequently the proles tested, shows that the majority of the diffraction lines can be
lms became smoother. Moreover, it isn't possible to detect clearly ascribed to Zn [16]. For the composite samples small peaks are
the vertical grains of zinc as it is possible in Fig. 1. From this it could be observed, between 24 and 28 2, that were attributed to the TiO2
assumed that the incorporation of the nanoparticles into the coatings particles [27].
favours the change in the zinc deposit morphology. In our previous Considering that the lms thickness does not differ signicantly a
published work [13], similar results were obtained, demonstrating the comparison between the different diffractograms has been per-
effect of the particles' presence on the zinc morphology. formed. The calculated relative texture coefcients, for the represen-
Fig. 3-a shows a SEM image for the nanocomposite prepared with tative planes of the Zn and Zn-TiO2 samples, are presented in Table 3.
ia = 19 mA cm 2. As can be observed the TiO2 nanoparticles are The RTC values of the (101) plane are always the most elevated for all
present in the form of agglomerates that are randomly dispersed on the samples studied. For the Zn electrodeposits, the second predom-
the matrix, especially on the sidewalls of the zinc grains. Additionally, inant texture components were the prismatic (100) and (110). The
RTC of the (002) basal plane is always smaller than 16.7% which is
considered as the limit to the preferred orientation according to
methodology used. Comparing the values of the three lines to the Zn,
it seems that no relationship exists between the RTC and the anodic
pulse current density values. For the Zn-TiO2 samples this behavior is
also observed except for the lms prepared with ia = 19 mA cm 2,

Fig. 3. a) SEM micrography of a Zn-TiO2 lm prepared, by pulsed electrolysis, with an

anodic pulse current density of 19 mA cm 2. b) SEM cross-section image of Zn-TiO2 lm Fig. 4. XRD patterns of the Zn lms prepared, by pulsed electrolysis, under different
prepared, by pulsed electrolysis, with an anodic pulse current density of 19 mA cm 2. anodic pulse current densities: a) 0, b) 6 and c) 19 mA cm 2.
3596 T. Frade et al. / Surface & Coatings Technology 204 (2010) 35923598

Table 4
Intensity of the ZnO diffraction peak for the different samples.

Sample type ia/mA cm 2 Intensity of the ZnO

diffraction peak/cts

Zn electrodeposits 0 16
6 21
19 36
Zn-TiO2 nanocomposites 0 12
6 18
19 28

hand high overpotentials create prismatic planes as preferential that

exhibit low atomic packing [28,29]. The hypothesis of zinc hydroxide
or zinc oxide formation is conrmed from the SEM/EDS results which
indicate that the ne ake microstructure observed is composed of Zn
and O. Moreover the diffraction analysis indicates the formation of
small amounts of ZnO in accordance with the observed diffraction
peak at 33 2 (Table 4). It is interesting to verify that this peak is more
intense for the Zn samples prepared with ia = 19 mA cm 2. This could
be promoted by the higher concentration of Zn2+ at the interface, due
to the dissolution of the Zn electrodeposit, followed by the slight
change of pH near the electrode surface occurring during the cathodic
pulse. However, this zinc deposit presents a similar orientation to
those prepared with other proles. This result suggests that the
presence of the surface agent is more critical for the preferential
orientation of zinc than the formation of ZnO [30]. Additionally, in
Table 4 it is also shown that for the nanocomposite coatings this
diffraction peak also exists and reects the same effect of the anodic
pulse current density.
For the Zn-TiO2 nanocomposite, a slight transition in crystal
orientation was observed indicated by the RTC value for the (103)
plane, the second most intense. This result is not completely
understood. This could be attributed to the effect of the increase on
the ia value on: (a) the restoration of Zn2+ concentration in the
vicinity of the cathode surface, (b) the change of the overpotential and
Fig. 5. XRD patterns of the Zn-TiO2 lms prepared, by pulsed electrolysis, under (c) the adsorption process due to the particles presence. However, it is
different pulse current densities: a) 0, b) 6 and c) 19 mA cm 2. difcult to assess how these variables, separately or in combination,
could be responsible for the observed transition in crystal orientation
where the second RTC higher value was obtained for the pyramidal [29,3133].
plane (103). The variation on the titania contents in the nanocomposite
To explain the (101) preferred orientation of the prepared lms, coatings was also estimated from the X-ray diffraction data. For all
the contribution of an inhibiting process during the deposition should the obtained electrodeposits, the (1 0 1) and (1 1 0) diffraction lines
be considered. In agreement with Vasilakopoulos [17], the (10X) as for anatase and rutile phases, respectively, were observed between
dominant plane might result from an electrochemically inhibited
process leading to a modication of the typical basal growth. Both, the
inuence of the boric acid adsorption and the formation of Zn(OH)2,
due to the progressive alkalinisation of the electrode interface during
the deposition, could selectively inuence the growth rates of the
various crystal planes, through changes in their crystallization
overpotential [17]. According to the literature for the Zn metal
coatings orientation, low cathodic overpotentials led to (002)
preferred orientation having high atomic packing. On the other

Table 3
Relative texture coefcients (RTC) of zinc from the different samples studied.

Sample type RTC (%)

Plane (hkl) (002) (100) (101) (102) (103) (110)

ia/mA cm 2

Zn electrodeposit 0 11.0 21.2 28.4 12.8 11.1 15.4

6 9.2 16.2 24.3 15.3 16.3 18.7
19 13.9 18.0 24.1 12.7 13.3 18.0
Zn-TiO2 0 13.3 19.2 24.8 13.0 14.3 15.5
nanocomposites 6 14.9 16.1 26.1 13.9 14.2 14.7
Fig. 6. Variation of the anatase (101) plane intensity with the anodic pulse current
19 10.5 14.6 26.4 16.5 17.3 14.7
T. Frade et al. / Surface & Coatings Technology 204 (2010) 35923598 3597

It is interesting to note that high amounts of particle incorporation

are not directly correlated with a small zinc crystallite size like
postulated in our previous work [13]. An analogous observation was
done by Thiemig et al. for the electrodeposition of Ni-Al2O3 composite
[37]. These authors concluded that the crystallite size depends upon a
variety of additional plating parameters particularly the plating
current density.

4. Conclusions

Zn-TiO2 nanocomposite coatings on titanium were successfully

prepared by pulsed-reverse current using a zinc plating bath with
dispersed TiO2 nanoparticles.
It was found that the anodic current pulse density (ia) plays a
remarkable inuence on the structure and morphology of the
nanocomposites. XRD and SEM results indicate that the increase on
the anodic current pulse promotes the incorporation of the nano-
particles into the deposit. When no anodic pulse is applied, both the
average zinc crystallite size and TiO2 content present the minimum
Fig. 7. Effect of the anodic pulse current density on the metallic matrix crystallite size. values. By contrast, the nanocomposites prepared with the highest ia
value, exhibit the highest values for, the zinc average crystallite size
24 and 28 2 [22]. As Fig. 6 shows, when the anodic current pulse and TiO2 content.
increases, the intensity of the (1 0 1) anatase diffraction line linearly For the zinc electrodeposits, the SEM results demonstrate that the
enhances, indicating that the content of the titania particles has pulse-plating parameters have a strong inuence on the deposit
increased in the nanocomposite coatings. This is one of the advantages surface morphology, due to changes on the growth mechanism.
of the use of pulsed-reverse deposition technique. According to Low et Moreover, an increase of the anodic current pulse leads to smoother
al. [3], this advantage can be linked with the partial dissolution of the electrodeposit surfaces.
metallic deposit during the anodic impulse, which favours the For all the coatings, the average zinc crystallite size increases with
nanoparticles to be entrapped. Skiba et al. [34] developed a model increasing anodic pulse current density however, a decrease is
for the inclusion of particles in the reverse pulse plating of Ni-Al2O3 observed in the presence of the TiO2 particles. As a nal remark, it
composite. It suggests that the majority of the particles captured may be concluded that the codeposition of particles perturbs the
earlier during the plating cycle stay in contact with the surface of the deposition process of the zinc matrix by either an increase in the
composite during the stripping cycle, and are then recaptured into the number of the nucleation sites or by a decrease of crystal growth and,
composite in the following plating cycle. In the anodic cycle, particles consequently a reduction in the crystallite size occurs in the
imbedded in the composite were re-exposed to the plating bath as the nanocomposite lms.
composite was stripped away. However, these newly exposed
particles are polarized due to induced polarization. The attracting
force between the particles and the composite, due to the electro-
chemical eld, may prevent them from being removed from the
The authors acknowledge nancial support from Fundao para a
composite's surface during the stripping cycles [34,35].
Cincia e Tecnologia (Portugal), under research project PTDC/CTM/
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density current pulse as Fig. 7 shows. As can be seen, the crystallite
size of the metallic matrix raises with increasing of the anodic pulse
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