Corrosion Science 59 (2012) 81–87

Contents lists available at SciVerse ScienceDirect

Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Study of corrosion performance of electrodeposited nanocrystalline Zn–Ni

alloy coatings
S.H. Mosavat, M.H. Shariat ⇑, M.E. Bahrololoom
Department of Materials Science and Engineering, School of Engineering, Shiraz University, Shiraz 71348–15939, Iran

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

Article history: The corrosion performance of nanocrystalline Zn–Ni alloy coatings electrodeposited from an alkaline bath
Received 12 August 2011 using direct current has been investigated using EIS and polarization curves technique. Performance of
Accepted 21 February 2012 these nanocrystalline alloy coatings with various Ni content was compared to that of microcrystalline
Available online 28 February 2012
Zn–Ni alloy. The corrosion product formed on the nanocrystalline Zn–Ni alloy coatings is stable and pro-
tective which proves to be better compared with microcrystalline. The nanocrystalline Zn–Ni alloy with
Keywords: 17.62 wt.% Ni and grain size 37 nm gives the best performance of the Zn–Ni alloy coatings tested. The cor-
A. Alloy
rosion resistance of nanocrystalline alloy coatings depends on the chemical compositions.
A. Nickel
A. Zinc
Ó 2012 Elsevier Ltd. All rights reserved.
B. EIS

1. Introduction
Nanocrystalline (NC) coatings offer great potential for various
applications due to their superior characteristics that are not typ-
ically found in conventional coatings [1–3]. In general, the corro-
sion resistance of nanocrystalline materials in aqueous solutions
is of great importance in assessing a wide range of potential for
future applications [4]. In the past, researches in this area were
scarce and relatively few studies have addressed this issue, but
researchers have become interested to study the electrochemical
corrosion behavior of nanocrystalline materials in recent years
[4–7]. Oguzie et al. found that the NC coating of low carbon steel
produced by magnetron sputtering technique (grain size about
40 nm) increased the dissolution rate compared to bulk steel with
the same chemistry [8]. Lu et al. [9,10] studied the electrochem-
ical corrosion behavior of Cu–Zr alloy NC coating produced by
magnetron sputtering (grain size 10–20 nm). The experimental
results indicated that the nanocrystallization decreased the disso-
lution rate of Cu–20Zr and Cu–70Zr alloys. According to the above
results, nanocrystallization significantly influences the electro-
chemical corrosion behaviors of metals/alloys in liquid system.
However, researchers suggest that nanocrystallization changes
the surface condition of metals/alloys, which can effectively in-
crease the activity of metallic atoms and accelerate the corrosion
reactions. Therefore, if the corrosion products are soluble, the cor-
rosion rate is increased by nanocrystallization. On the contrary, if
⇑ Corresponding author. Address: Department of Materials Science and Engi-
neering, School of Engineering, Shiraz University, Zand Boulevard, Shiraz 71348-
51154, Iran. Tel.: +98 711 6133071; fax: +98 711 2307293.
E-mail address: Shariat@shirazu.ac.ir (M.H. Shariat).
the corrosion products are insoluble, the corrosion rate is de-
creased because the corrosion products act as a barrier layer to
delay the dissolution [5,8–10].
Alloying with nickel is a common technique employed to aug-
ment zinc’s protective properties [11,12]. So, the electrodeposit-
ion of Zn–Ni has generated a great amount of interest in the
nineties [12–14]. Zn–Ni alloy electrodeposits are mainly used as
corrosion protective coatings for automobile steel bodies [15].
These coatings have been also considered for application in the
electronics industries [16], electrocatalytic water electrolysis
[17] and fasteners [18]. Cadmium plating is also being replaced
by Zn–Ni alloy plating due to its toxic nature [19]. Since the mar-
ket for corrosion resistance Zn–Ni alloy coatings is large, exten-
sive studies have been performed investigating the corrosion
properties of Zn–Ni alloy using the salt spray test [20], the
immersion test [21] and the potentiodynamic polarization test
[22]. Most of the literatures describing corrosion testing of Zn–
Ni alloy coatings have concluded that the best corrosion resis-
tance was obtained when the coatings consisted of only the c
phase. It has been argued that the best corrosion performance gi-
ven by the c phase results from the absence of local cells between
different phases that would be present in the case of the (c + g)
dual-phase structure, as a results of one phase being more noble
than the other. Attempts have been made to electrodeposit nano-
crystalline Zn–Ni alloy coatings [23,24], e.g. Alfantazi and Erb [25]
and Li et al. [26] have obtained nanocrystalline zinc–nickel coat-
ings from acid baths and alkaline baths, respectively. In a recent
study, the authors also produced nanocrystalline Zn–Ni alloy
coatings from alkaline baths [27]. But to date, there is no clear
report about study of corrosion performance of nanocrystalline
Zn–Ni alloy coatings.

0010-938X/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2012.02.012
82 S.H. Mosavat et al. / Corrosion Science 59 (2012) 81–87
It should be noted that corrosion is not a process that proceeds
by straightforward, uncomplicated active dissolution, especially
over extended exposure periods [28]. Electrochemical impedance
spectroscopy (EIS) is a powerful technique that can provide enough
insight on the film formation and protection mechanisms of a gi-
ven surface layer. In the present work, EIS measurements comple-
mented with polarizing curve tests were performed to study the
corrosion performance of electrodeposited nanocrystalline Zn–Ni
alloy coatings. As the corrosion performance of NC alloy coatings
depend on grain size, phase distribution, chemical composition
and morphology of deposits, these factors were studied.
2. Methods and materials
Nanocrystalline Zn–Ni alloy coatings were synthesized by elec-
trodeposition from an alkaline glycinate bath [27]. The alkaline bath
contained ZnO (10 g/l), NiSO46H2O (13 g/l), C6H15NO3 (18 g/l),
NH2CH2COOH (49 g/l), saccharin (5 g/l) as additive and sodium
dodecyl sulfate (0.3 g/l) as an anti-pitting agent (all analytical grade
chemicals). Commercially cold rolled carbon steel sheets were used
as the substrate and direct current (0.5, 2, 5 and 8 A dm2) was ap-
plied. The bath temperature was adjusted at 20 ± 2 °C. After plating,
the deposits were immediately rinsed with distilled water, dried by
cold air and then subjected to further characterization. A number of
microcrystalline Zn–Ni alloy electrodeposits were produced from a
chloride-based electrolyte containing ZnCl2, NiCl26H2O and boric
acid [29]. These samples were produced for comparing the corro-
sion performance of microcrystalline Zn–Ni alloy with NC Zn–Ni al-
loy coatings.
A Cambridge scanning electron microscope (SEM) was used to
observe the surface morphology of the coatings. The chemical com-
position of the NC Zn–Ni alloy coatings was determined by energy
dispersive X-ray spectroscopy (EDS). Their phase composition was
also determined by X-ray diffraction (XRD) analysis, using a diffrac-
tometer (model D8 Bruker) with Cu-Ka radiation (k = 0.15405 nm).
The 2h ranged from 20° to 100° and the scan rate was 0.02° per sec-
ond. The average grain size of the coatings was determined from X-
ray peak broadening by applying the Scherrer formula for (3 3 0)
reflections and peak broadening was measured by the integral
width method [30]. Peak broadening due to the instrument was
subtracted from the peak width before calculating the average grain
size using Jones equation [30]. The grain size of one sample was also
determined directly by a transmission electron microscope (TEM) to
verify the accuracy of the average grain size measurements.
Corrosion behavior and protection performance of NC Zn–Ni al-
loy coatings was studied by using electrochemical impedance spec-
troscopy (EIS) and electrochemical Tafel extrapolation in 3 wt.%
NaCl solution. The tests were performed using a potentiostat/galva-
nostat (lAutolab Type III Eco Chemie BV, The Netherlands)
equipped with a Frequency Response Analyzer 4.9 and a General
Purpose Electrochemical System 4.9 software. A three electrode cell
consisting a saturated calomel electrode as the reference electrode
and a platinized titanium rod as the auxiliary electrode were used
in the tests. The samples were immersed in a test solution for
approximately 12 h prior to each test, in order to establish a stable
open circuit potential. Electrochemical impedance spectroscopy
(EIS) measurements were obtained at the open circuit potential
(OCP) in a frequency range of 10 kHz–0.001 Hz, with an applied
AC signal amplitude perturbation of 10 mV. During the measuring
process of Tafel polarizing curves, the polarization curve scanning
rate was 5 mV/s, with a scanning range from 0.25 V of open circuit
potential to +0.25 V of open circuit potential. The electrochemical
measurement data were analyzed by Autolab electrochemical
software. Finally, the surface morphology of the corroded speci-
mens was examined by SEM.
3. Results and discussion
3.1. Phase and chemical composition of Zn–Ni alloy coatings
X-ray diffraction patterns of the coatings obtained at different
current densities are shown in Fig. 1, in which the peaks related to
the steel substrate are marked Fe. According to Zn–Ni phase dia-
gram and past researches [11,31], electrodeposited Zn–Ni alloys
have four main phases: a-phase, a solid solution of zinc in nickel
with an equilibrium solubility of about 30% Zn; c-phase, an inter-
mediate phase with a composition Ni5Zn21; d-phase, an intermedi-
ate phase with a composition Ni3Zn22; and g-phase, a solid solution
of nickel in zinc with less than 1% nickel. X-ray analysis was done for
all deposits and the results show that all coatings have only a single
cubic c-phase structure (Ni5Zn21). X-ray diffraction along with en-
ergy dispersive X-ray spectroscopy (EDS) was used to verify that
all electrodeposits obtained are of the single c-phase only. EDS anal-
ysis indicates that the Ni content of deposits ranged from 12.78 to
17.62 wt.%. On the basis of the phase diagram, Zn–Ni alloys with
9–17 wt.% Ni have a c-phase structure.
Fig. 2 shows the variation of chemical composition (Ni content
in wt.%) of the deposits as a function of current density. As shown,
the nickel content of deposits obtained from the alkaline bath does
not change significantly as the current density changes. In contrast,
the nickel content in the coatings obtained from the acid bath is
not constant [32]. Therefore, it is difficult to obtain a single-phase
coating from the acid baths. It has been reported that the coatings
from the acid bath were thought to be of g-phase and of c-phase
structures [33]. As the potentials of these two phases are different,
a corrosion cell tends to form in corrosive environments. Therefore,
the coatings from the alkaline bath may exhibit a better corrosion
protection, in general.
3.2. Grain size and surface morphology of nanocrystalline Zn–Ni alloy
coatings
The average grain sizes of the coatings obtained at different cur-
rent densities were measured by Scherrer equation. Since the dif-
fraction peak of the (3 3 0) plane is significant (see Fig. 1), the full
width at half maximum (FWHM) for only this plane was used for
grain size measurement. Table 1 summarizes the effect of current
density on grain size, chemical composition and phase composition
of the NC Zn–Ni alloy coatings. Fig. 3 shows a TEM micrograph of a
typical nanocrystalline Zn–Ni specimen produced at 0.5 A dm2. By
direct measurement on the TEM micrograph of the sample, the
grain size distribution is in the range 8–60 nm, and the average
Fig. 1. XRD patterns of NC Zn–Ni alloy coatings electrodeposited at: (a) 0.5 A dm2,
(b) 2 A dm2, (c) 5 A dm2, and (d) 8 A dm2.
 S.H. Mosavat et al. / Corrosion Science 59 (2012) 81–87 83

Fig. 3. TEM micrograph of the NC Zn–Ni alloy coating electrodeposited at

Fig. 2. Change in the deposit Ni content (wt.%) as a function of current density: 0.5 A dm2.
comparison between the acid and the alkaline baths.

Table 1
should be noted that the nodules, shown in Fig. 4, may include sev-
Effect of current density on grain size, chemical composition and phase composition eral grains. By considering the XRD results and TEM micrograph, it
of NC Zn–Ni alloy coatings. can be concluded that each colony consist of a number of nano-
Coating Current density Nickel content Phase Average grain
crystalline grains. By comparison, deposits produced at higher cur-
(A dm2) (wt.%) composition size (nm) rent densities have become larger and more uniform in size with
clearer boundaries. It seems that the deposits obtained at higher
Zn–13Ni 0.5 13.39 c-Phase 19
Zn–14Ni 2 13.50 c-Phase 55 current densities have larger colony size. Since the surface mor-
Zn–12Ni 5 12.78 c-Phase 13 phology can affect the corrosion performance, an attempt was
Zn–17Ni 8 17.62 c-Phase 37 made to syntheses NC Zn–Ni alloy coatings with similar morphol-
ogy (cauliflower-like).

grain size was calculated to be 22 ± 7 nm which is close to the
value obtained by the Scherrer method, 19 nm. This consistency
implies that XRD technique is a suitable method to evaluate the
average grain size of NC Zn–Ni alloy coatings in this study.
The surface morphology of NC Zn–Ni alloy coatings obtained at
0.5, 2, 5 and 8 A dm2 is illustrated in Fig. 4. According to this fig-
ure, the coatings are uniform, compact and covered the substrates
completely. The morphology of these coatings plated under differ-
ent current densities is rough and nodular on a micro scale. It
3.3. The EIS results
Figs. 5 and 6 illustrate the Nyquist and Bode plots of NC Zn–Ni
alloy coatings obtained at different current density, respectively.
As shown there is only one obvious extremum in the phase angle
curves, implying that there is only one time constant for each coat-
ing. Correct interpretation of the impedance spectra and so
representing a satisfactory model, depends on the good under-
standing of corrosion phenomena taking place. Shibuya et al. [20]

Fig. 4. Surface morphology of NC Zn–Ni alloy coatings electrodeposited at: (a) 0.5 A dm2, (b) 2 A dm2, (c) 5 A dm2, and (d) 8 A dm2.
84 S.H. Mosavat et al. / Corrosion Science 59 (2012) 81–87
Fig. 5. The Nyquist plots obtained for NC Zn–Ni alloy coatings electrodeposited at:
(a) 0.5 A dm2, (b) 2 A dm2, (c) 5 A dm2, and (d) 8 A dm2, in a 3% NaCl solution.
have reported that when Zn–Ni alloy is corroded, zinc begins to
dissolve preferentially. They have also observed Ni enrichment at
the surface corrosion products from preferential dissolution of
Zn. According to Eqs. (1)–(3), one of the cathodic reactions at the
zinc surface in the environment containing chloride ions at the po-
tential ranges > 1.3 V (SCE) is the reduction of dissolved oxygen
[34,35]. This reduction leads to local pH rise at the coating surface
and formation of a thin film of hydroxide on the coatings (see Eq.
(3)).
ZnðsÞ ! Zn2þ ðaqÞ þ 2e ð1Þ
1
O2 ðgÞ þ H2 OðlÞ þ 2e ! 2OH ðaqÞ ð2Þ
2
Zn2þ ðaqÞ þ 2OH ðaqÞ ! ZnðOHÞ2 ðsÞ ð3Þ
The hydroxide film is the basis for further growth of corrosion
products which depends on the solution pollutants [35]. The corro-
sion products may be formed by compounds such as ZnO, Zn(OH)2,
ZnCO3, Zn5(OH)6(CO3)2 (hydrozincite) and Zn5(OH)8Cl2H2O (zinc
hydroxy chloride), and probably by a mixture of these compounds
[36]. Barranco et al. [36] reported that due to low solubility, zinc
corrosion products precipitate on metallic surfaces exposed to a
sodium chloride solution. Therefore, these insoluble passive films
cover the corroded surface and as a result, electrochemical corro-
sion reactions become more difficult. Fig. 7 illustrates SEM micro-
graphs of the surface morphology of the corroded specimens. As
shown in Fig. 7, the surface of NC Zn–Ni alloy coatings is covered
completely with corrosion products that act as barriers against fur-
ther corrosion.
It should be noted that the coatings are nanocrystalline and
deposits with extremely low porosity or an interconnected net-
work of fine crystalline grain boundaries would be expected to
show some loss of phase shift at low frequencies (i.e. a less than
fully capacitative response) as the real resistance of the flaws be-
comes detectable [28] (Fig. 8). Finally, for fitting impedance spectra
considering surface conditions and impedance spectra, an equiva-
lent circuit which was introduced by Kelly et al. [28] was used to
characterize the influence of corrosion product deposits was used.
This equivalent circuit is also presented in Fig. 8, where Rs is the
solution resistance, Rp is the polarization resistance (also known
as charge transfer resistance) and CPE is the constant phase ele-
ment. The CPE value can be expressed in the form of P(ix)n in
which P is proportional to the capacitance, n is a parameter related
to surface roughness and cell configuration, and x is the angular
frequency. Applying CPE instead of pure capacitance improves EIS
data fitness of the experimental results [37]. Extracted fitted data
from the equivalent circuit is shown in Table 2.
Rs is determined by the conductance of the NaCl solution and
according to these results the solution resistance of all coatings
shows no significant difference. Generally, it is considered that
the impedance values measured at the low-frequency area in the
EIS spectra can reflect the corrosion resistance of the coatings
when the impedance values at the low-frequency area were inde-
pendent of the frequency. These impedance values corresponded
to the value of the Rp. Fig. 9 represent the variation of polarization
resistance (Rp) of NC Zn–Ni alloy coatings versus the Ni content and
grain size. According to this figure, the corrosion resistance of NC
Zn–Ni alloy with 17.62 wt.% Ni and grain size of 37 nm is the high-
est while the corrosion resistance of NC Zn–Ni alloy with
12.78 wt.% Ni and grain size of 13 nm is the lowest. Consequently,
by increasing the Ni content of deposits, in the nanometer range
(1–100 nm), the corrosion resistance of NC Zn–Ni alloy coatings
 S.H. Mosavat et al. / Corrosion Science 59 (2012) 81–87 85

Fig. 6. The Bode plots obtained for NC Zn–Ni alloy coatings electrodeposited at: (a) 0.5 A dm2, (b) 2 A dm2, (c) 5 A dm2, and (d) 8 A dm2, in a 3% NaCl solution.

Fig. 7. SEM micrographs of the surface morphology of the corroded specimens, electrodeposited at different current density, in a 3% NaCl solution.

increases. It is worth noting that the corrosion resistance of the al-
loy coatings is generally related to the grain size, surface morphol-
ogy and phase composition of the coatings, as well as the chemical
composition [29]. Since all the coatings have similar phase compo-
sition, surface morphology and nanocrystalline structure, so the
key factor would be then be mainly attributed to the chemical
composition not grain size in the nanometer range. This can be fur-
ther confirmed by the following polarizing curve tests.
3.4. The Tafel plot results
Tafel plots for microcrystalline Zn–Ni alloy and NC Zn–Ni alloy
coatings are shown in Fig. 10. The electrochemical parameters
(Ecorr, iCorr, ba, bc) for both NC Zn–Ni alloy and microcrystalline
Zn–Ni alloy coatings are summarized in Table 3. The corrosion cur-
rent was calculated by the Stern and Grey relationship (Eq. (4)).
ba bc
iCorr ¼
2:303Rp ðba þ bc Þ
The corrosion potential for all coatings tested remained nega-
tive with respect to the steel substrate (Fig. 10 and Table 3). Thus,
all of the tested coatings provide a certain degree of galvanic or
sacrificial protection to the steel substrate. It is also noted that
there is no significant difference in the corrosion potential of the
NC Zn–Ni alloy coatings and that the corrosion potential of micro-
crystalline Zn–Ni alloy is more negative than that of NC Zn–Ni alloy
coatings. Therefore, NC Zn–Ni alloy shows better corrosion perfor-
mance than microcrystalline Zn–Ni alloy. Such results were also
reported for NC Ni by Rofagha et al. [38] and Mishra and Balasubr-
amaniam [39] in which there was generally a progressive shift in
Ecorr towards noble direction for the NC Ni compared to bulk nickel.
The corrosion current density (i.e. the current density at the
corrosion potential) is another parameter used in the study of
corrosion performance. In the nanocrystalline alloys, the grain-
boundary volume represents up to 50% of the total volume. Since
grain boundaries and triple junctions could be good regions for
ð4Þ electrochemical reactions, it is expected that nanocrystalline alloys
have higher corrosion current density than microcrystalline alloys.
86 S.H. Mosavat et al. / Corrosion Science 59 (2012) 81–87

Fig. 10. Polarizing curves obtained for the alloy coatings in a 3% NaCl solution; (a)
NC Zn–17Ni alloy, (b) NC Zn–12Ni alloy, (c) NC Zn–14Ni alloy, (d) NC Zn–13Ni alloy,
and (e) microcrystalline Zn–18Ni alloy.

Table 3
The electrochemical parameters (Ecorr, iCorr, ba, bc) of the coatings samples in a 3% NaCl
solution.

Coating Ecorr iCorr ba bc

(mV vs. SCE) (lA cm2) (V/dec) (V/dec)
Microcrystalline 1080 47.6 0.063 0.173
Zn–18Ni alloy
Nanocrystalline 961 27.7 0.398 0.119
Zn–13Ni alloy
Nanocrystalline 936 23.6 0.109 0.363
Zn–14Ni alloy
Nanocrystalline 912 29.9 0.364 0.117
Zn–12Ni alloy
Nanocrystalline 927 23.2 0.363 0.140
Zn–17Ni alloy
Fig. 8. The impedance schematic model (a) and the equivalent circuit (b) of NC Zn–
Ni alloy coatings in a 3% NaCl solution.

comparison with the microcrystalline Zn–Ni alloy, nanocrystalline

Table 2 Zn–Ni alloy coatings show lower corrosion current density than
Extracted fitted data from the equivalent circuit of NC Zn–Ni alloy coatings in a 3% that of microcrystalline Zn–Ni alloy (Table 3). This is attributed
NaCl solution. to its nanocrystalline structure that enhances both the kinetics of
Coating Rs (X cm2) Rp (X cm2) Y (F cm2) n passivation and the stability of the passive film formed and is in
Zn–13Ni 3.43 1430 44.1  104 0.755
turn due to the higher grain boundary density in the coating with
Zn–14Ni 6.70 1540 20.6  104 0.830 respect to nanocrystalline structure that speeds up the formation
Zn–12Ni 5.49 1280 46.5  104 0.785 of a stable and protective passive film. Other researchers have also
Zn–17Ni 7.23 1890 65.9  104 0.651 reported a decrease in the corrosion rate of electrodeposited NC
Zinc [40], Ni–W alloy [41] compared to microcrystalline deposits
and have concluded that the oxide film formed on NC deposits
was more protective than that on microcrystalline deposits. Finally
it should be concluded that the key factor on corrosion perfor-
mance in nanometer range is the nickel content but when struc-
ture is change from microstructure to nanostructure, the grain
size is the key factor not Ni content. It should be also noted that
NC Zn–Ni alloy coating with 17.62 wt.% Ni has the lowest corrosion
current density among all NC Zn–Ni alloy coatings. Therefore, it
can be concluded that the Tafel plot results strongly supported
EIS results.

4. Conclusions

Fig. 9. The variation of polarization resistance (Rp) of NC Zn–Ni alloy coatings
versus the Ni content (wt.%) and grain size (nm).
On the other hand, the microcrystalline Zn–Ni alloy has 18 wt.% Ni
and its grain size is more than 1 lm. Although nanocrystalline Zn–
Ni alloy coatings have less Ni content and more grain boundaries in
The corrosion performance of nanocrystalline Zn–Ni alloy coat-
ings with an average grain size between 13 and 55 nm was inves-
tigated by EIS and Tafel plots. Nanocrystalline Zn–Ni alloy coatings
were synthesized by electrodeposition. The XRD and SEM results
indicate all NC Zn–Ni alloy coatings have similar phase composi-
tion (single cubic c-phase structure) and surface morphology (cau-
liflower-like). EIS results and the established equivalent circuit
 S.H. Mosavat et al. / Corrosion Science 59 (2012) 81–87
show that the corrosion products covered the surface of the NC Zn–
Ni alloy coatings and as a result, electrochemical corrosion reac-
tions become more difficult. EIS results also showed in the NC
Zn–Ni alloy coatings, the Ni content has a major effect on the pro-
tection performance of the coatings. This finding is confirmed by
Tafel plots technique through the corrosion current density. Tafel
plot results indicate that corrosion performance of NC
Zn–Ni alloy coatings is superior to microcrystalline Zn–Ni alloy
and this is due to the fact that the oxide film formed on NC Zn–
Ni alloy is more protective than that on microcrystalline Zn–Ni
alloy.
Acknowledgments
The authors thank Shiraz University Research Council for finan-
cial support through Grant No. 89-GR-ENG-8. The assistance given
in EIS interpretation by Mr. Babaiee (PhD student of Shiraz Univer-
sity) is also appreciated. Special thanks to Dr. S. Esmaili for valu-
able discussion.
References
[1] H. Gleiter, Nanocrystalline materials, Prog. Mater. Sci. 33 (1989) 223–315.
[2] U. Erb, Electroseposited nanocrystals, properties and industrial application,
Nanostruct. Mater. 6 (1995) 533–538.
[3] I. Gurrappa, L. Binder, Electrodeposition of nanostructured coatings and their
characterization – a review, Sci. Technol. Adv. Mater. 9 (2008) 1088–1099.
[4] U. Erb, K.T. Aust, G. Palumbo, Electrodeposited nanocrystalline materials, in:
C.C. Koch (Ed.), Nanostructured Materials, Noyes Publications, New York,
2002, pp. 179–215.
[5] L. Liu, Y. Li, F. Wang, Electrochemical corrosion behavior of nanocrystalline
materials – a review, J. Mater. Sci. Technol. 26 (2010) 1–14.
[6] W. Luo, Y. Xu, Q. Wang, P. Shi, M. Yan, Effect of grain size on corrosion of
nanocrystalline copper in NaOH solution, Corros. Sci. 52 (2010) 3509–3513.
[7] Sh. Hassani, K. Raeissi, M. Azzi, D. Li, M.A. Golozar, J.A. Szpunar, Improving the
corrosion and tribocorrosion resistance of Ni–Co nanocrystalline coatings in
NaOH solution, Corros. Sci. 51 (2009) 2371–2379.
[8] E.E. Oguzie, Y. Li, F.H. Wang, Effect of surface nanocrystallization on corrosion
and corrosion inhibition of low carbon steel: synergistic effect of methionine
and iodide ion, Electrochim. Acta 52 (2007) 6988–6996.
[9] H.B. Lu, Y. Li, F.H. Wang, Enhancement of the electrochemical behavior for Cu–
70Zr alloy by grain refinement, Surf. Coat. Technol. 201 (2006) 3393–3398.
[10] H.B. Lu, Y. Li, F.H. Wang, Improved corrosion behavior of nanocrystalline Cu–
20Zr film in HCl solution, Thin Solid Films 510 (2006) 197–202.
[11] D.E. Hall, Electrodeposited zinc–nickel alloy coatings – a review, Plating Surf.
Finish. 70 (1983) 59–65.
[12] G.D. Wilcox, D.R. Gabe, Electrodeposited zinc alloy coatings, Corros. Sci. 35
(1993) 1251–1258.
[13] K.R. Baldwin, M.J. Robinson, C.J.E. Smith, The corrosion resistance of
electrodeposited zinc–nickel alloy coatings, Corros. Sci. 35 (1993) 1267–1272.
[14] H. Park, J.A. Szpunar, The role of texture and morphology in optimizing the
corrosion resistance of zinc-based electrogalvanized coatings, Corros. Sci. 40
(1998) 525–545.
[15] D. Crotty, Zinc alloy plating for the automotive industry, Met. Finish. 94 (1996)
54–58.
87
[16] E.W. Brooman, Alternatives to cadmium coating for electrical/electronic
applications, Plating Surf. Finish. 80 (1993) 29–35.
[17] J. Divisek, P. Malinowski, J. Mergela, H. Schmitza, Improved components for
advanced alkaline water electrolysis, Int. J. Hydrogen Energy 13 (1988)
141–150.
[18] E. Budman, R.R. Sizelove, Zinc alloy plating, metal finishing guidebook, Met.
Finish. 93 (1995) 324–329.
[19] D.A. Wright, N. Gage, B.A. Wilson, Zinc–nickel electroplate as a replacement for
cadmium on high-strength steels, Plating Surf. Finish. 81 (1994) 18–21.
[20] A. Shibuya, T. Kurimoto, Y. Hoboh, N. Usuki, Development of Zn–Ni alloy plated
steel sheets, Trans. Iron Steel Inst. Jpn. 23 (1983) 923–929.
[21] S.R. Rajagopalan, Electrodeposition of nickel–zinc alloys, Met. Finish. 70 (1972)
52–58.
[22] R. Fratesi, G. Roventi, Corrosion resistance of zinc–nickel alloy coatings in
industrial production, Surf. Coat. Technol. 82 (1996) 158–164.
[23] P.L. Hansen, C.Q. Jessen, The microstructure of electrodeposited Zn–Ni
coatings, Scripta Metall. 23 (1989) 1387–1390.
[24] I. Brooks, U. Erb, Hardness of electrodeposited microcrystalline and
nanocrystalline c-phase Zn–Ni alloys, Scripta Mater. 44 (2001) 853–858.
[25] A.M. Alfantazi, U. Erb, Synthesis of nanocrystalline Zn–Ni alloy coatings, J.
Mater. Sci. Lett. 15 (1996) 1361–1363.
[26] G.Y. Li, J.S. Lian, L.Y. Niu, Z.H. Jiang, Investigation of nanocrystalline zinc–nickel
alloy coatings in an alkaline zincate bath, Surf. Coat. Technol. 191 (2005)
59–67.
[27] S.H. Mosavat, M.E. Bahrololoom, M.H. Shariat, Electrodeposition of
nanocrystalline Zn–Ni alloy from alkaline glycinate bath containing
saccharin as additive, Appl. Surf. Sci. 257 (2011) 8311–8316.
[28] R.G. Kelly, J.R. Scully, D.W. Shoesmith, R.G. Buchheit, Electrochemical
Techniques in Corrosion Science and Engineering, first ed., Marcel Dekker
Inc., New York, 2003.
[29] A.M. Alfantazi, U. Erb, Corrosion properties of pulse-plated zinc–nickel alloy
coatings, Corrosion 52 (1996) 880–888.
[30] L.V. Azaroff, Elements of X-ray Crystallography, McGraw-Hill, New York, 1968.
[31] L.S. Tsybulskaya, T.V. Gaevskaya, O.G. Purovskaya, T.V. Byk, Electrochemical
deposition of zinc–nickel alloy coatings in a polyligand alkaline bath, Surf.
Coat. Technol. 203 (2008) 234–239.
[32] M.S. Chandrasekar, S. Srinivasan, M. Pushpavanam, Properties of zinc alloy
electrodeposits produced from acid and alkaline electrolytes, J. Solid State
Electrochem. 13 (2009) 781–789.
[33] E. Beltowska-Lehman, P. Ozga, Z. Swiatek, C. Lupi, Influence of structure factor
on corrosion rate of functional Zn–Ni coatings, Cryst. Eng. 5 (2002) 335–345.
[34] I. Suzuki, The behavior of corrosion products on zinc in sodium chloride
solution, Corros. Sci. 25 (1985) 1029–1034.
[35] S.C. Chunga, J.R. Chengb, S.D. Chioub, H.C. Shiha, EIS behavior of anodized zinc
in chloride environments, Corros. Sci. 42 (2000) 1249–1268.
[36] V. Barranco, S. Feliu Jr., S. Feliu, EIS study of the corrosion behaviour of zinc-
based coatings on steel in quiescent 3% NaCl solution. Part 1: directly exposed
coatings, Corros. Sci. 46 (2004) 2203–2220.
[37] E. Barsoukov, J.R. Macdonald, Impedance spectroscopy, Theory, Experiment,
and Applications, second ed., John Wiley & Sons, New York, 2005.
[38] R. Rofagha, R. Langer, A.M. El-Sherik, U. Erb, G. Palumbo, K.T. Aust, The
corrosion behaviour of nanocrystalline nickel, Scripta Metall. 25 (1991)
2867–2872.
[39] R. Mishra, R. Balasubramaniam, Effect of nanocrystalline grain size on the
electrochemical and corrosion behavior of nickel, Corros. Sci. 46 (2004)
3019–3029.
[40] Kh.M.S. Youssef, C.C. Koch, P.S. Fedkiw, Improved corrosion behavior of
nanocrystalline zinc produced by pulse–current electrodeposition, Corros. Sci.
46 (2004) 51–64.
[41] A. Chianpairot, G. Lothongkum, C.A. Schuh, Y. Boonyongmaneerat, Corrosion of
nanocrystalline Ni–W alloys in alkaline and acidic 3.5 wt.% NaCl solutions,
Corros. Sci. 53 (2011) 1066–1071.