Surface & Coatings Technology 203 (2009) 18151818

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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

Inuence of electrodeposition parameters on the deposition rate and microhardness

of nanocrystalline Ni coatings
Jin-Xing Kang a,b,, Wen-Zhen Zhao a, Gao-Feng Zhang b
a
b

School of Materials Science and Engineering, Xi'an Jiaotong University, Xi'an 710049, China
The Engineering Institute, Air Force Engineering University, Xi'an 710038, China

a r t i c l e

i n f o

Article history:
Received 2 April 2008
Accepted in revised form 3 January 2009
Available online 22 January 2009
PACS:
81.15.-z
Keywords:
Nanocrystalline nickel
Coatings
Deposition rate
Hardness
Direct current deposition

a b s t r a c t
In this paper, nanocrystalline nickel (nc-Ni) coatings were prepared by a direct current electrodeposition
technique. Their microstructure and microhardness were investigated by a high-resolution transmission
electron microscopy and a microhardness tester. It is found that the electrodeposition parameters,
including content of C7H4NO3SNa2H2O, temperature and current density, have signicant inuences on
the electrodeposition rate and microhardness of nc-Ni coatings. The electrodeposition rate increases with
the current density stepwise. The largest electrodeposition rate is achieved at 60 C. It decrease when the
temperature is larger than 60 C. The electrodeposition rate decreases with the increased content of
C7H4NO3SNa2H2O. The microhardnesses of the nc-Ni coatings are higher on the condition of the larger
current density, lower temperature or higher content of C7H4NO3SNa2H2O. But, it remains stable when the
current density is in the range of 7001000 A m 2. The relationship between the mean grain sizes and
microhardness ts for the HallPetch function, approximately.
2009 Elsevier B.V. All rights reserved.

1. Introduction
The synthesis of nanostructured materials through electrodeposition has seen advances from a laboratory scale phenomenon to one
of practical industrial relevance. Potentially there are a very large
number of pure metals, alloys, composites, and ceramics which can be
electrodeposited with grain sizes less than 100 nm, for example, Ni,
Co, Pd, Cu, NiP, NiFe, NiW, ZnNi, NiFeCr and NiSiC [13].
Among the electrodeposited nanocrystalline materials, great attention
had been paid to nanocrystalline nickel (nc-Ni) coatings due to the
high brightness, high hardness and high corrosion resistance ability.
Erb et al. prepared nc-Ni coatings by a electropulsing deposition
method [4,5]. Imre et al. studied the nc-Ni coatings prepared by a
direct current deposition [6]. Because of the complex preparation
process, there are great differences in above investigations [714].
In order to obtain a nc-Ni coating with high quality, it is necessary
to control the electrodeposition parameters (such as, current density,
current efciency and time) and to understand the relationship between the electrodeposition parameters and the properties of nc-Ni

Corresponding author. School of Materials Science and Engineering, Xi'an Jiaotong

University, Xi'an 710049, China. Tel.: +86 29 82665183; fax: +86 29 82663453.
E-mail address: jxkang08@163.com (J.-X. Kang).
0257-8972/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2009.01.003

coatings. Therefore, the purpose of this paper is to study the effects of

the electrodeposition parameters on the electrodeposition rate and
microhardness of nc-Ni coatings.
2. Experimental procedure
The nc-Ni coatings were prepared by a direct current deposition.
The used reagents of the solutions were analytically pure. The main
components and contents are listed in Table 1. The remaining was
distilled water. The pH values of the solutions were kept at 4 by adding
the dilute solution of HCl. Ni plates (99.9%) were used as anode. The
sample was cathode, which was made of Ti6Al4V. The dimension of
the samples was 50 mm 30 mm 2.5 mm. Before the electrodeposition, the samples were sanded and polished. Then they were washed
by alkaline, acid and distilled water in turn. After the procedure, the
treated samples were put into the solutions. Two groups of experiments were made in present work. The temperature of the solution
was hold at 60 C for the rst group, the values of the current density
were 500, 700, 900, 1100, 1300 and 1500 A m 2. For the second group,
the current density was xed at 1300 A m 2, the temperatures were
50, 60, 70 and 80 C, respectively. During the experiments, all the
electrodeposition time was 90 min.
Microstructure of the nc-Ni coatings was observed by a JEM2100F high-resolution transmission electron microscope (HRTEM).
The thickness was measured after the coatings were peeled off from

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J.-X. Kang et al. / Surface & Coatings Technology 203 (2009) 18151818

Table 1
Composition of the electrodeposition solutions, the remaining is distilled water (unit:
g L 1)
Number

NiSO47H2O

NiCl26H2O

H3BO3

C12H25OSO2Na

C7H4NO3SNa2H2O

No. 1
No. 2

300
300

45
45

40
40

0.05
0.05

3
5

the matrix. The deposition rates were estimated by the ratio of the
thickness to the time. The hardness of the coatings was determined
by a MH-5 type microhardness tester. The applied load was 50 g and
the loading time was 5 s.
3. Results and discussion
3.1. Microstructure of nc-Ni coatings
Fig. 1(a) shows the mean grain sizes of nc-Ni coatings deposited
at different current densities. The deposition temperature is 60 C.
The grain size of nc-Ni deposited in No. 1 solution increases with the
increase of current density till 900 A m 2. Then the grain size decreases when the current density is greater than 900 A m 2. For No. 2
solution, the grain size decreases with the current density, similar to
Rashidi's results [15]. The decrease of grain size can be explained by
Tafel formula [1]. Overpotential of cathode increases with increase of
the current density. Therefore, the driving force of nucleation is en-

Fig. 1. (a) Mean grain sizes of nc-Ni at various current densities. The deposition
temperature is 60 C. (b)Relationships between the mean grain sizes of nc-Ni and
temperature of solutions. The current density is 1300 A m 2.

hanced and nucleation rate increases. As a result, the grain size decreases. Also, hydrogen evolution is inevitable in the cathode [2].
Hydrogen can provide more crystal nucleus during the reduction
reaction. It may lead to ne Ni grains. Fig. 1(b) illustrates the mean
grain sizes of nc-Ni at different temperatures. The current density is
1300 A m 2. It can be found that the grain size is larger at higher
temperatures. The temperature of the solutions is of particular importance in controlling the grain sizes. At higher temperatures, the
Ni ions can diffuse in longer distance. The growth rate of grain may
be larger than the nucleation rate. Therefore, the mean grain size
increases with the temperature [14]. According to the above results,
it can be concluded that the grain size of nc-Ni is in the range of 14
85 nm, no matter what electrodeposition condition was applied.
Furthermore, the effect of the temperature on the grain size is larger
than that of current density [1518].
Fig. 2(a) shows the a bright TEM eld image of a nc-Ni coating
through No. 1 solution on the condition that the applied current
density and temperature are 1300 A m 2 and 60 C, respectively. The
inserted gure is its diffraction image. It can be seen that the grain size
of the nc-Ni coating is about 30 nm. Fig. 2(b) is a HRTEM image. The
grain boundary of the grains is clear, characterized by a high-angle
boundary.

Fig. 2. A bright eld image and diffraction pattern (a) and a high-resolution electron
microscopy image (b) of a nc-Ni coating prepared through No. 1 solution, the current
density and temperature are 1300 A m 2 and 60 C, respectively.

J.-X. Kang et al. / Surface & Coatings Technology 203 (2009) 18151818

1817

Fig. 3. Relationship between the electrodeposition rates and current densities at 60 C.

3.2. Deposition rate of nc-Ni coatings

According to Faraday's law, the quantity of an electrochemical
reaction occurred on an electrode is proportional to the quantity
of electric charge. Taken the current efciency into account, the
thickness of the coating (d) can be derived from the ratio of the
product mass to the electro equivalent, that is,
d=

ik k tE

Where ik is current density, k is current efciency, t is time, E is

electro equivalent of Ni and is the density of Ni.
E and of Ni are equal to 1.095 g/(Ah) and 8.907 g/cm3. According
to Eq. (1), the deposition rate V can be estimated as Eq. (2):
6

V = 2:04910 k ik

Fig. 5. (a) Microhardness of the nc-Ni coatings deposited at various current densities.
(b) Relationship between microhardness of the nc-Ni coatings and temperatures.

Where the units of V and ik are mm min 1 and A m 2, respectively,

k is a dimensionless unit. According to above derivation, the
deposition rate is correlated with the current density and current
efciency [1].
Fig. 3 shows that the deposition rates of the nc-Ni increase with the
current density at 60 C. It can be seen that the deposition rate
increases stepwise. There are two terraces when the current density is
in the range of 500700 A m 2 and 13001500 A m 2 for No. 1 and No.
2 solutions.

At a constant current efciency, the relationship between the

deposition rate and current density should be linear according to
Eq. (2). In order to obtain nc-Ni grains, the additive of C7H4NO3SNa2H2O was added in the electrodeposition solutions, which can
accelerate the formation of crystal nucleus and inhibit the growth
of grains. But, at the same time, the deposition process was hindered with the increase of the additive content. In some range of
current density, Ni2+ in the solutions moves to the cathode, and
passes through the double electrode layer. Subsequently, Ni atom

Fig. 4. Electrodeposition rates of nc-Ni at various temperatures at 1300 A m 2.

Fig. 6. Relationship between the hardness and the mean grain sizes deposited at
different electrodeposition parameters.

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J.-X. Kang et al. / Surface & Coatings Technology 203 (2009) 18151818

forms and merges into the crystal lattice. Due to the obstructive
action of C7H4NO3SNa2H2O, overpotential increases when the current density increases. When the current density accumulates to
some extent, Ni2+ can break through an obstacle quickly. The process
can lead to the increase of the deposition rate. During the accumulation of current density, the current efciency decreases, and the
deposition rate keeps a constant for a while. As a result, some
terraces appear in the curve of current density vs deposition rate.
Fig. 4 shows the relationship between the temperature and the
deposition rate at 1300 A m 2. When the temperature is lower than
60 C, the deposition rate increases nonlinearly, and the acceleration
rate of the deposition rate becomes less. The deposition rate is the
largest at 60 C. When the temperature is higher than 60 C, the rate
begins to decrease.
According to Eq. (2), at a constant current density, there is a direct
relationship between the deposition rate and current efciency, rather
than temperature. When a higher current density was applied, the
solubility and electroconductivity of the salts in the electrodeposition
solutions increase with the temperature, if the temperature is lower
than 60 C. Ni2+ can diffuse to the cathode at a faster velocity. The
activity of the electrodeposition solutions enhances and the current
efciency improves. So the deposition rate increases. On the contrary,
when the temperature is higher than 60 C, the amount of evaporation
of the deposition solutions increase, and the nickel salt is easy to
decompose and nickel hydroxide is formed from the solutions. It can
result in the degradation of the cathodic polarization, the reduction
of the activity of the electrodeposition solutions and the current efciency, the decrease of the deposition rate. Therefore, the activity of
the solutions at 60 C is the largest.
From Figs. 3 and 4, the deposition rate of No. 1 is larger than that of
No. 2 at same current density and temperature. The results are caused
by different composition of the electrodeposition solutions. High
content C7H4NO3SNa2H2O can suppress the movement of Ni2+ and
reduce the activity of the solutions [1,14]. As a result, the deposition
rate decreases.

microhardness of nc-Ni, a linear relationship between the d 0.5 and

microhardness, present in Fig. 6. The relation ts for the HallPetch
relationship, approximately. The result agrees with the previous results [8,10,1922].
4. Conclusions
The dense nc-Ni coatings can be prepared by a direct current
electrodeposition technology. The grain boundary is clear, characterized by a high-angle boundary. The current density, temperature of
the solutions and content of C7H4NO3SNa2H2O have great inuences the electrodeposition rate and the microhardness of the nc-Ni
coatings. The results are concluded as follows:
(1) When the current density increases, the electrodeposition rate
and the microhardness of the nc-Ni coatings increases
stepwise.
(2) The electrodeposition rate of the nc-Ni increases rstly and
then drops, when the temperature of the solutions increases.
The value reaches the top at 60 C. But the microhardness of ncNi coatings decreases gradually.
(3) When content of C7H4NO3SNa2H2O increases, the electrodeposition rate of the nc-Ni decreases, but the microhardness of
the nc-Ni coatings increased.
(4) Current density and temperature have apparent effect on the
grain size of nc-Ni. The relationship between the grain sizes and
microhardness ts for the HallPetch function, approximately.
Acknowledgement
The authors would like to acknowledge Shengwu Guo and Ruihua
Zhu for the TEM and HRTEM experiments. Valuable comments and
kind suggestions from the reviewers are sincerely appreciated too.
References

3.3. Microhardness of nc-Ni coatings

Fig. 5(a) presents the microhardness of nc-Ni coatings deposited
at different current densities. The deposition temperature is 60 C.
C7H4NO3SNa2H2O content in No. 1 solution is less than that in No. 2.
The microhardness of the samples prepared through No. 1 decreases
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stable when the current density is in the range of 7001100 A m 2.
When the current density is higher than 1100 A m 2, the microhardness begin to increase. It can also be found that the microhardness of the samples through No. 2 is larger than that of No. 1. Fig. 5(b)
shows the microhardness of nc-Ni coatings at different temperatures when the current density is 1300 A m 2. The microhardness of
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From the above results, it can be concluded that the current
density, temperature and C7H4NO3SNa2H2O have great inuences
on the microhardness of the nc-Ni coatings. The effect arises from
different grain sizes, show in Fig. 1 According to the grain size and

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