Surface & Coatings Technology 272 (2015) 373379

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Surface & Coatings Technology

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Inuence of pulsed current on the aqueous corrosion resistance of

electrodeposited zinc
Nitin P. Wasekar , A. Jyothirmayi, Neha Hebalkar, G. Sundararajan
International Advanced Research Centre for Powder Metallurgy and New Materials, Hyderabad 500 005, India

a r t i c l e

i n f o

Article history:
Received 5 December 2014
Accepted in revised form 27 March 2015
Available online 2 April 2015
Keywords:
Zinc
Electrodeposition
Corrosion
Electrochemical impedance spectroscopy

a b s t r a c t
In the present study, the inuence of the mode of electrodeposition on the corrosion resistance of zinc (Zn) coating on mild steel substrate has been evaluated. Towards above purpose, Zn coatings were electrodeposited using
direct, pulsed and pulse reverse current (PRC). The corrosion resistance was analyzed using electrochemical impedance spectroscopy and potentiodynamic polarization in 3.5% NaCl. The inuence of pulse current mode on
coating structure and hardness has also been investigated. The results indicate that pulse reverse deposited Zn
coatings provide better protection against corrosion. The improved corrosion resistance has been attributed to
the microstructure of the PRC coating and also the formation of compact corrosion product.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Zinc (Zn) has been extensively adapted as a sacricial coating on ferrous components in automobile, construction and marine industries.
For Zn coating to be an effective sacricial coating it should exhibit a
corrosion potential much more negative than the underlying steel component but at the same time the Zn layer itself should corrode slowly so
that it has considerable durability.
The sacricial Zn coating on steel substrate can be applied by a wide
variety of techniques including hot dipping, metal spraying, cladding,
cementation and electrodeposition. Pulsed electrodeposition (PED) is
one of the simple yet economical methods of depositing porosity free,
bulk nanocrystalline materials with controlled physical properties. In
PED, the diversity of electrodeposition parameters allows the deposition
of coatings with tailored microstructure and properties. PED has been
utilized for deposition of nanocrystalline Zn coatings and these results
have suggested improved corrosion resistance of nanocrystalline Zn
over conventionally deposited Zn coatings [14]. The inuence of
various pulse parameters such as current density, duty cycle and other
parameters such as additive concentration, alloying addition on corrosion resistance is very well documented in literature [510]. In addition,
the Zn based electrodeposited oxide, carbide composite coatings and
their improved properties using direct current [11,12], pulsed current
[1,13] and pulse reverse current [14,15] have been documented. However, the inuence of deposition mode (especially in PRC) on the corrosion resistance in the case of pure Zn is rarely presented in open

Corresponding author. Tel.: +91 40 24452490; fax: +91 40 24442699.

E-mail address: nitin.arci@gmail.com (N.P. Wasekar).

http://dx.doi.org/10.1016/j.surfcoat.2015.03.038
0257-8972/ 2015 Elsevier B.V. All rights reserved.

literature. Therefore, the main objective of the present work is to investigate the inuence of direct current (DC), pulsed current (PC) and
pulsed reverse current (PRC) deposition modes employed for Zn coatings on their structural properties and aqueous corrosion resistance.
2. Experimental
The electrolyte bath employed to deposit Zn coatings is presented in
Table 1. In the bath, Zn sulfate, sodium sulfate, boric acid, sodium lauryl
sulfate and thiourea were used as a source of Zn, increasing conductivity, pH stabilizer, antipitting agent and stress reliever respectively. The
temperature and pH of electrolyte were maintained at 50 C and 3 respectively. Prior to deposition, mild steel substrates were ground and
polished to 0.08 Ra (m) (RMS surface roughness) and cleaned using acetone. The substrates were subsequently treated using dilute nitric acid
solution for improving the adhesion.
A pulse power generator (Dynatronix, USA) having capacity to
change pulsed current independently was utilized for electrodeposition
purpose. A schematic view of pulse waveform is illustrated in Fig. 1.

Table 1
Electrolyte composition for deposition of Zn using DC, PC and PRC waveform.
Chemical composition

Concentration (g/l)

ZnSO47H2O
Na2SO4
H3BO3
Sodium lauryl sulfate
Thiourea

160
90
45
0.1
5

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N.P. Wasekar et al. / Surface & Coatings Technology 272 (2015) 373379

Fig. 1. Pulse waveform applied for DC, PC and PRC deposition. (iavgaverage current
density).
Table 2
Pulse parameters employed for electrodeposition of zinc coatings on mild steel.
Deposition
mode

Pulse time
(ms)

Peak current
density
(A/cm2)

Forward Reverse

DC Zn
PC Zn
PRC Zn

ton

toff

trev toff

20
20
20

Average
Deposition
current density rate
2
(A/cm )
(m/h)

Forward Reverse

0.050
0.058
0.065

0.05

DC

0.05

130 10
140 10
150 10

Corresponding to Fig. 1, the pulse parameters utilized during electrodeposition are presented in Table 2. The average current density employed
was 0.05 A/cm2. The peak pulse current density in PC and PRC deposition was adjusted such that average current was the same as that of
DC deposition. The deposition rate is presented for each mode of deposition in Table 2. Using the deposition rate data, the time of deposition
was so adjusted that the nal coating thickness was maintained at
50 10 m.
The Zn coated samples were subjected to X-ray diffractometer (D8Advance, Brooker, Germany, Cu-K radiation, BraggBrenton geometry,
40 KV, 40 mA, 0.02/s scan rate) to identify the phase composition. A
scanning electron microscope (Hitachi Model S-4300SE/N, Japan) in
conjunction with EDAX was employed for analyzing the coating surface
morphology prior to and after the corrosion tests. An ESCA, X-ray photoelectron spectroscopy (XPS) (Omicron, United Kingdom) system
was utilized to characterize corrosion product using Al K monochromatic X-ray source. The colony size and grain size (using linear intercept
method) were determined from SEM micrographs using image analysis
software.
Micro hardness tests were carried out on cross section of cold
mounted and polished samples at a load of 25 g using UHL VMHT
micro hardness tester. The average of ve readings was recorded from
each sample.
The Zn coated samples, masked to reveal only 1 cm2 area, were immersed in deaerated 3.5 (wt.%) (~0.6 M) NaCl (pH 7) solution. The pH
value of model medium was not adjusted. The corrosion cell consisted
of Zn coated mild steel (working electrode), platinum (auxiliary
electrode) and saturated calomel (SCE, reference electrode).
All the corrosion tests were conducted after open circuit potential
(OCP) stabilization for 1 h, using Solartron 1260 Impedance/Gain
Phase analyzer with a Solartron 1287 Electrochemical Interface between a frequency range of 102 and 105 Hz at OCP using a sinusoidal
AC perturbation of 10 mV amplitude. The impedance data were analyzed and tted to get the circuit values using Z-plot, Z-view software.
The potentiodynamic polarization tests were conducted at a scan rate
of 1 mV/s between 1.5 and 0.9 V to generate E vs log(i) plots

PC

PRC

Zn

mild steel

DC

PC

PRC

Fig. 2. SEM micrographs depicting surface topography and the coating cross section for direct current (ab), pulsed current (cd), and pulse reverse current (ef) electrodeposited Zn coatings respectively.

N.P. Wasekar et al. / Surface & Coatings Technology 272 (2015) 373379

375

using CorrWare and CorrView software. All the tests were conducted at
room temperature (25 C).

3. Experimental results
3.1. Coating morphology, microstructure and phase composition
Fig. 2 illustrates the surface morphology and the cross section of Zn
coating deposited on mild steel. Fig. 2 (a, b) corresponds to direct current, (c, d) represents pulsed current while Fig. 2 (e, f) illustrates coating
deposited using pulsed reverse current method. A change in coating
morphology from slightly aky to globular is clearly evident as deposition mode was changed from DC to PC and PRC. The coating surface is
characterized by well developed colonies and the size of these colonies
was measured using image analysis software. The colony size so determined is presented in Table 3. The hardness of Zn coatings determined
using Vickers indenter (25 g load) is presented in Table 3. The same
table also gives the average porosity of the coatings as obtained from
unetched coatings cross section using image analysis software. Lastly,
the coating cross section was etched (using dilute NaOH) to reveal the
grains as illustrated in Figs. 3 (ac). Using this microstructure, the average grain size determined using linear intercept method is presented in
Table 3.
In general each colony contains many grains in electrodeposited
coatings [16]. Therefore, in the present study etched cross section was
utilized to measure the grain size of the coatings. The grain size for
PRC coatings was estimated from Fig. 3 is presented in Table 3. Thus, although DC coatings have smaller colonies, their grain size was larger
than PC and PRC coatings.
Table 3 reveals that PRC Zn coatings have the best properties in
terms of the highest hardness, lowest porosity and the ne grain size.
The PC Zn coatings exhibit marginally better properties than DC Zn
(Table 3).
The phase composition of the coatings is illustrated in Fig. 4. In this
gure, the X-ray diffraction pattern along with standard Zn (JCPDS
card number 00-004-0831) is presented. The analysis of pattern
suggests single phase Zn with well dened (101) orientation
irrespective of deposition mode.

3.2. Corrosion performance

3.2.1. (a) Potentiodynamic polarization tests
The corrosion performance of electrodeposited Zn coatings on mild
steel substrates and the inuence of deposition mode are presented in
potentiodynamic polarization curves as illustrated in Fig. 5. As expected
the bare mild steel exhibits a more noble corrosion potential compared
to Zn coated steel. A careful observation of the gure suggests that, the
PC and PRC deposited Zn coatings exhibit lower corrosion current compared to DC deposited Zn. Due to non linear Tafel slopes, the corrosion
current was estimated using polarization resistance as per Stern
Geary relation [17]. The polarization resistance was obtained using
Corr-View software from the slope of polarization plot (E Vs i) in the potential range of 10 mV at OCP. The corrosion current obtained from

Table 3
Variation of colony size, grain size, porosity and hardness of Zn coatings as a function of
deposition mode.
Deposition mode

Colony size
(m)

Grain size
(m)

Hardness
HV0.025
(kg/mm2)

Porosity
(%)

DC
PC
PRC

11 2
15 3
11 2

5.37 1.0
4.36 1.1
0.7 0.2

63 3
63 3
71 3

12.00
4.86
0.50

Fig. 3. SEM micrographs illustrating coating cross section after etching for (a) DC, (b) PC
and (c) PRC Zn coated mild steel.

polarization resistance methods is generally lower than Tafel method

since tting is carried out near OCP.
Thus, a more insight into corrosion behavior can be gained from
Fig. 6 (a&b) wherein corrosion current (a measure of corrosion rate)
and the corrosion potential are presented in the form of bar charts for
the Zn coatings obtained by three modes of deposition. Amongst the
electrodeposited coatings, pulse reverse electrodeposited Zn exhibits
the lowest corrosion rate and therefore effectively protects the underlying mild steel substrate for longer duration.

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N.P. Wasekar et al. / Surface & Coatings Technology 272 (2015) 373379

Fig. 4. X ray diffraction pattern for electrodeposited coatings deposited on mild steel.

Fig. 6. Variation of corrosion current (a) and corrosion potential (b) as a function of coating
deposition mode.

3.2.2. (b) Electrochemical impedance spectroscopy

Fig. 7 illustrates the impedance spectra (i.e. Nyquest plot) for Zn
coated mild steel. The spectra were obtained at the open circuit potential during exposure to NaCl solution. An analysis of Fig. 7 suggests dominant single time constant in all coatings except PRC deposited Zn
coatings. The Nyquist plot (Fig. 7) can be tted to a simple equivalent
circuit with a single time constant for DC and PC coatings as illustrated
in inset of Fig. 7. The circuit consists of electrolyte resistance (Rs) in

series with double layer capacitance (CPEdl) and charge transfer resistance (Rct) in parallel. The impedance of the constant phase element
(CPE) is obtained as [18],

where, C and n are frequency independent parameters with 1 n 1.

In this case, the CPE is an ideal capacitor for n = 1, an inductor when

Fig. 5. Potentiodynamic polarization curves for electrodeposited Zn coatings and mild

steel in 3.5% NaCl.

Fig. 7. Nyquist plot after impedance tests in 3.5% NaCl along with equivalent circuit model
(inset).


n 1
ZCPE C j

N.P. Wasekar et al. / Surface & Coatings Technology 272 (2015) 373379

377

Table 4
Electrochemical impedance circuit parameters obtained after tting equivalent circuit diagram (Fig. 7 insight).
Coating

PC Zn
PRC Zn

Rs
( cm2)

CPE-Qc
(1 sn/cm2) 105

CPE-n

Rcoat
( cm2)

CPE-Qdl
(1 sn/cm2) 105

CPE-n

Rct
( cm2)

1.16
1.81
1.59

4.33

0.80

341

3.71
4.41
98.2

0.88
0.90
0.62

325
326
387

n = 1 and a resistor when n = 0. The value of n is a measure of surface

roughness (it represents rough surface when n reaches 0.5 and smooth
when n nears 1) [19].
The equivalent circuit in the case of PRC deposited Zn coating is characterized by predominant two time constants (see inset of Fig. 7) and
includes an additional circuit elements compared to the DC and PC deposited Zn. It can be noted that, the rst time constant (Rct CPEdl) at
lower frequency corresponds to charge transfer at the electrical double

layer. The second time constant (Rcoat CPEcoat) can be attributed to

the presence of compact ZnO passive layer present on the surface of
the Zn (as discussed later). After tting the experimental data with
the equivalent circuits presented in Fig. 7, the values of Rs, CPE-n, Rct,
CPEdl, Rcoat and CPEcoat were obtained and are presented in Table 4.
The CPE (CPEdl in PC and DC CPEcoat in PRC) was not found to change
much with deposition technique. An increase in Rct in the case of PRC
Zn coatings compared to DC and PC Zn is clearly evident.

Fig. 8. SEM micrographs and corresponding EDS spectra depicting corrosion morphology and composition of corrosion product after polarization tests for (ab) DC, (cd) PC and (ef) PRC
Zn coatings. High magnication image is also provided in insight for better clarication.

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N.P. Wasekar et al. / Surface & Coatings Technology 272 (2015) 373379

3.2.3. (c) Corrosion surface morphology and composition of the corrosion

product
The surface morphology of coatings after polarization tests and EDS
spectra identifying the corrosion products are presented for Zn coated
mild steel in Fig. 8 for coatings obtained using DC (Fig. 8 (a&b)), PC
(Fig. 8(c&d)) and PRC (Fig. 8 (e&f)) as modes of deposition. The gure
illustrates composition of corrosion product on the surface of affected
area. The higher magnication images suggested dissolution of colonies
in DC (Fig. 8(c) inset) whereas oxide layer was evident for PRC coatings
(Fig. 8(e) inset). The EDS spectra obtained on corrosion product suggested the presence of zinc, oxygen along with chlorine in case of DC
and PC deposited coatings. However, the oxide layer on PRC coatings
was mainly composed of zinc, oxygen without chlorine.
X-ray photoelectron spectroscopy was carried out to further investigate the chemical composition of the corrosion products. Fig. 9 (ac)
shows the narrow scan for the Zn 2p 3/2, O 1s and Cl 2p respectively.
In both the samples, the Zn 2p 3/2 peak at 1021.0 eV is assigned to
ZnO [20]. It is very clear that sample PRC has majority ZnO than DC.
The other peak at 1022 eV in sample DC and 1022.5 eV in PRC can be
co-related to Zn bonded to OH or Cl or oxychloride formation. The presence of oxide and hydroxide species and their relative concentrations
are also supported by two components in O1s peak at 530.6 eV and
531.7 eV respectively. Although present in both the samples, the chlorine concentration in DC was higher than PRC as evident in EDS spectra
(Fig. 8). The presence of Cl at 198 eV in the sample also can be predicted
in the form of Zn\Cl or Zn\O\Cl bond.

4. Discussion
First and foremost, the Zn coatings obtained using PRC deposition
are virtually porosity free, have lower grain size in comparison with
DC and PC coatings. The size of colonies in all the coatings is similar
(1115 m). The XRD pattern suggests that, all the coatings are single
phase Zn coating and represent similar texture. Therefore, the inuence
of morphology, composition and texture on corrosion behavior can be
ruled out in the present study.
The improved corrosion resistance of PRC deposited coatings can
now be attributed to coating structure and formation of passive lm
due to corrosion on the surface. The PRC deposited Zn coatings were
found to be more compact and ne in structure compared to PC and
DC coatings. It is evident from improved hardness of PRC coatings compared to DC and PC Zn (Table 3).
According to theory of passivation for Zn in NaCl solution, the oxide
or passive layer due to corrosion consists of compact ZnO and porous
Zn(OH)2, ZnCl2 [21]. Thus in the case of PC and DC deposited coatings
(relatively porous), it is highly possible that porous zinc hydroxychloride (ZHC) [2224] forms as corrosion product as clearly evident
from EDS spectra (Fig. 8(d)) with Cl peak. This lm is less passive due
to its porous nature [21]. In contrast, PRC deposited coatings exhibited
mostly compact ZnO passive layer after corrosion as evident from XPS
analysis (Fig. 9).
Youssef et al. [1] observed that the oxide lm formed on nano
grained Zn was more protective than that on electrogalvanized steel

Fig. 9. XPS spectra for the Zn 2p 3/2 (a), O 1s (b) and Cl 2p (c) after corrosion in NaCl for DC and PRC Zn coatings.

N.P. Wasekar et al. / Surface & Coatings Technology 272 (2015) 373379

(EG) thereby leading to lower corrosion rate than that of EG steel. On

the similar view, the oxide layer formed on PRC Zn (with lower grain
size) is protective in nature. These observations are consistent with impedance test results (Fig. 7). It is clearly evident from prominent second
time constant (resistance and capacitance combination) at higher frequency in the case of PRC deposited Zn unlike in the case of DC and PC
coated Zn. The presence of second time constant is thus attributed to
compact ZnO passive layer in PRC coatings. In addition, CPE-n was
lower in case of PRC Zn indicating rough surface due to oxide formation.
The higher amount of porosity along with porous ZHC present in DC and
PC coatings could not separate out electrochemical reaction at the coating and interfacial reaction near coatingsubstrate interface. It is manifested in a single reaction. Therefore only single time constant is evident
in DC and PC Zn coatings.
Thus compact, hard Zn coatings can be deposited using PRC technique which is corrosion resistance due to the nature of its coating
structure and formation of dense passive lm.
One of the major advantages of this PRC technique is its simplicity
and cost effectiveness. The complex geometries with uniform surface
coating coverage can also be obtained under the PRC mode of deposition. Thus, given the vast application of galvanic Zn coatings, PRC
electrodeposition offers another option towards improved sacricial
protection of ferrous substrates.
5. Conclusions
(1) Zn coatings were electrodeposited on mild steel substrate utilizing pulse reverse electrodeposition in sulfate bath. These coatings were hard with relatively lower porosity than Zn coatings
deposited using pulsed and direct current electrodeposition. Zn
coatings illustrated similar texture irrespective of deposition
mode.
(2) The corrosion behavior of Zn coatings was compared in deaerated NaCl using potentiodynamic polarization and impedance
spectroscopy. The results indicated improved corrosion resistance of pulse reverse electrodeposited Zn coatings in comparison to that of PC and DC Zn coatings.
(3) The formation of compact ZnO corrosion product on the surface
of PRC Zn in contrast to porous zinc hydroxy-chloride on the surface of DC and PC Zn coatings was attributed to higher corrosion
resistance for PRC Zn coatings.

379

Acknowledgment
One of the authors, Mr Nitin P. Wasekar wishes to thank Director,
International Advanced Research Centre for Powder Metallurgy and
New Materials (ARCI) for granting permission to publish this paper.
The author would like to acknowledge Mr D. S. Rao for his cooperation
and assistance. The author would also wish to thank Mr. Ramesh
Reddy for XRD analysis and Mr. G. V. R. Reddy for SEM analysis.
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