Surface & Coatings Technology 330 (2017) 170–177

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Surface & Coatings Technology

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Microstructure and texture evolution of electrodeposited coatings of nickel MARK

in the industrial electrolyte
Xu Yang-tao, Dai Yu-jie, Zhang Wei, Xia Tian-dong⁎
State Key Laboratory of Advanced Processing and Recycling of Non-ferrous Metals, Lanzhou, Gansu 730050, China
School of Materials Science & Engineering, Lanzhou University of Technology, Lanzhou, Gansu 730050, China

A R T I C L E I N F O A B S T R A C T

Keywords: Nickel is an important strategic metal material, which has been widely used in modern industry. The different
Electro-crystallization electrolyte systems and main parameters have a great effect on microstructure and mechanical properties of
Nucleation and growth electrodeposited coatings. In order to investigate the evolution of texture and preferential orientation of nickel
Electrodeposited coatings of nickel electro-crystallization in sulfide nickel soluble anode/sulfate solution, and grain size, microstructure of elec-
Preferential orientation
trodeposited coatings of nickel were characterized by electrochemical workstation, XRD and SEM methods.
Microstructure
The results show that nickel electro-crystallization conforms to the classical nucleation theory and crystal
growth theory. The preferential orientation of electrodeposited coatings of nickel can be changed initially from
(111) and (200) planes to (220) plane after 16 h. The surface morphology changes slowly from pyramid to
cellular structure, while the growth mechanism changes from screw dislocation growth to cumulative growth
model. The cross sectional microstructure of electrodeposited coatings is non-uniform and mostly grains are
columnar and perpendicular to the sheet. The distribution of grains abides by stepwise distribution along the
thickness. The microstructure of electrodeposited coatings is fine equiaxed grain region and coarse columnar
grain region, which are perpendicular to starting sheet when the electrodeposition time is 144 h. Angle grain
boundary is related to grain size, whereas the coincidence site lattice (CSL) is associated with preferential or-
ientation. Therefore the grain boundary misorientation are mainly above 15°, being more than angle grain
boundaries and coincidence site lattice Σ3 appearing highest frequency.

1. Introduction principle. Nucleation-growth model has much impact on micro-

Due to its good corrosion resistance, plastic workability and weld-
ability, nickel is widely applied to electrical and electronic component
parts, petrochemical industry, aerospace and military industry.
However, the different electrolyte systems and electrodeposited con-
ditions have a great effect on nucleation and growth of electro-crys-
tallization process, microstructure, corrosion resistance, as well as the
mechanical properties of electrodeposited coatings of nickel.
As we know the metal electrodeposition contains a series of complex
and interconnected processes, such as crystal nucleus formed, atoms
agglomerated, recrystallized and crystal grew. Specifically, the metal
atoms are adsorbed on electrode surface, and new crystal can be formed
when crystal nucleus is larger than critical nucleation radius. The metal
electro-crystallization is a special crystallization process. Newly-gen-
erated the metal atoms generated with reduction reaction diffused to
crystal lattice or aggregated nucleation on surface of crystal nucleus
and then kept on growing in electro-crystallization process. Therefore,
nickel electro-crystallization is also abided by this complex reaction
structures and properties of electrodeposited coatings of nickel.
Fleischamann proposed the BFT model and Scharifker-Hills im-
proved a more accurate interpretation of nucleation model in metal
electro-crystallization [1–4]. It was found that nickel atoms began to
deposit on the electrode when the potential was around − 0.75 V in
ammonia complexes bath by cyclic voltammetry measurements [5].
When the potential was to − 0.95 V after the start of reverse scan, the
closed “inductive reactance current loop” was ranged from − 0.78 V to
− 0.6 V. Yang Xiao-wei's study on electrochemical behavior of nickel by
cyclic voltammetry further proved the nucleation existence in the
electrodeposition process of nickel [5–7]. Therefore, current-time (i-t)
curves in electrolytes are measured by electrochemical workstation, to
further study nucleation model in metal electrodeposition [8–9].
Literature [10–14] research suggests the temperature of sulfate and
chloride electrolyte may influence microstructure and texture of elec-
trodeposited coatings of nickel, which may be related to the adsorption
and desorption of Cl− and SO42 − on the coating surface [15]. Ac-
cording to theory proposed by JW Dini [16], grain size of

⁎
Corresponding author at: State Key Laboratory of Advanced Processing and Recycling of Non-ferrous Metals, Lanzhou, Gansu 730050, China.
E-mail address: lanzhouxuyt@163.com (X. Tian-dong).

http://dx.doi.org/10.1016/j.surfcoat.2017.09.078
Received 1 April 2017; Received in revised form 12 September 2017; Accepted 28 September 2017
Available online 29 September 2017
0257-8972/ © 2017 Elsevier B.V. All rights reserved.
X. Yang-tao et al.
electrodeposited coatings gradually increases with the rising tempera-
ture of electrolyte owing to the potential of nucleation [3,17]. Azizi
[18–19] explored pH of electrolyte had a great effect on nucleation and
electrodeposition mechanism of nickel with chloride and sulfate elec-
trolyte, which revealed that pH can affect nucleation density and grain
size of electrodeposited coatings [20]. In addition, some scholars have
found cathodic current density and additives impact the micro-
structures and properties of electrodeposited coatings of nickel as well
[21–32].
In present, there are mainly three growth models of metal electro-
deposition in the initial stage: Volmer-Weber (V-W model, the theory of
island growth), Frank-van Der Merwe (F-M model) and Stranski-
Krastanov (S-K model) [11]. According to the results of literature [33],
the main growth pattern of nickel is epitaxial growth and fiber texture
growth. Nickel atoms with power field have priorities over the existing
lattice locations on cathode surface in the initial stage of electro-
deposition, and form film of nickel completely consistent with crystal
orientation on cathode surface (epitaxial growth region). The epitaxial
growth region of electrodeposited coatings is about 100 nm. The
growth model can be eventually changed from epitaxial growth into
polycrystalline structure with irregular orientation of grains along with
the electrodeposition process. And the polycrystalline structure adopts
the preferential orientation growth of crystals and forms the columnar
crystal in new electrodeposited coatings. The columnar grain growth
direction is parallel to the thickness direction of electrodeposited
coatings of nickel, and the growth direction of high density twin in
columnar crystal is parallel to the growth direction of columnar crys-
tals.
The grain size of products in the domestic is larger than the foreign
product. The grain orientations are nearly at random, and mechanical
properties of electrodeposited coatings of nickel have a clear direc-
tionality [34–35]. However, these studies did not thoroughly in-
vestigate the nucleation and growth process, grain orientation of nickel
electro-crystallization in industrial electrolyte. As a result, this paper
attempts to explore microstructure evolution and texture of nickel
electro-crystallization in the industrial electrolyte.
2. Experimental method
The composition of industrial electrolyte was as follows: Ni2 + 75 g/
L, Na+ 35 g/L, Cl− 75 g/L, SO42 − 105 g/L, H3BO4 6 g/L, Cu2 + 3 mg/L,
Fe2 + 4 mg/L, Co2 + 20 mg/L, Zn2 + and Pb2 + 0.6 mg/L, organics <
0.7 g/L, pH = 4.8. A CHI 660E electrochemical workstation (CH
Instrument) was used for cyclic voltammetry (CV), cathodic polariza-
tion and current-time (i-t) measurements. All electrochemical studies
were performed with a conventional three electrode system. A satu-
rated calomel electrode (SCE) and a platinum electrode were used as
reference and counter electrodes, respectively. The glassy carbon
working electrode is electrode (GCE) with a diameter of 3 mm polished
carefully with 0.5 μm and 0.3 μm alumina particles on polishing cloth
before use. The potentials of current-time (i-t) curves of chron-
oamperometry (CA) were as below: − 1.08 V, − 1.10 V, − 1.12 V,
− 1.14 V and −1.16 V.
The electrodeposited coatings of nickel were prepared on self-made
experimental equipments. The starting sheet was used as substrate of
electrodeposited coatings of nickel. The main processing parameters of
nickel electrocrystallization in the electrolyte were as follows: the pH
was 4.8, temperature was 65 °C, current density of cathode was 220 A/
m2, and electrodeposition time was 0 s, 60 s, 5 m, 30 m, 1 h, 4 h, 8 h,
16 h, 144 h and 288 h, respectively.
The test samples were sanded and polished with 600# to 2000#
metallographic sandpaper. Then immediately the optimum composition
ratio of nitric acid/acetic acid was 1:1 in this experiment, which was
carried out electrochemical corrosion of specimen. Microstructure of
electrodeposited coatings was observed by JSM-6700F field emission
electron microscope. The crystal structure was characterized by D8-
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Surface & Coatings Technology 330 (2017) 170–177
ADVANCE type polycrystalline X-ray diffraction (XRD) with the scan-
ning range was 20°–100° and scanning speed was 2°/min.
The EBSD samples were mechanically ground and polished fol-
lowing the classical preparation route. Firstly, they were ground with
sandpaper up to 2000 grit, and then polished with a dilute solution of
H3PO4 containing 0.05 mm colloidal silica suspension to obtain a
mirror-like surface finish. The final step was a 20 s chemical etching in
a solution of 60% H3PO3, 20% HNO3, and 20% H2SO4 (vol%) at
80–85 °C for removing the deformation layer. After that, the samples
were chemically polished by ultrasonic cleaning with acetone and al-
cohol solutions, and then Quanta450FEG field emission scanning elec-
tron microscope (SEM) equipped with NordlyMax electron backscatter
diffraction analyzer for EBSD analysis was used. While the position of
scanning electron microscope, samples and diffraction patterns were
used to standard with Ge single crystal. Test parameters were as fol-
lows: accelerated voltage was 20 kV, working distance was 10.0 μm,
sample tilt angle was 70°, scanning step length was 0.5 μm, and scan-
ning area was 180 μm × 180 μm. The beam scanning mode was used to
collect electron back-scattering patterns (EBSP) after the condition was
set, and the computer data were automatically processed, stored and
output.
Two micro-areas of inner and outer sides of electrodeposited coat-
ings of nickel were tested with each sample, and then labeled with
micro-area I and micro-area II, respectively. The micro-area I are
transition zone of starting sheet (substrate) and electrodeposited
coating of nickel, and micro-area II are about 1 mm from surface of
electrodeposited coating of nickel. The calculation angle of grain mis-
orientation was 2° as the lower limit, and misorientation angle of grains
were ignored when the angle was < 2° (considered as the same grain),
only statistical calculation was conducted for the misorientation angle
of grain above 2° due to the factors such as equipment precision and
surface roughness of specimen.
3. Results and discussion
3.1. The electrocrystallization of nickel at initial stages
Fig. 1 depicts current-time (i-t) curves at different potentials in the
electrolyte. As can be seen from the figure, current-time curves have
similar varying trends: it rises to the maximum firstly, and gradually
decreases to the gentle stability at last. When the potential shifts gra-
dually to the negative, the electrodeposition overpotential of cathode
will gradually increase, and the relaxation time (tm, the time to reach
peak current) is reduced, while the peak current (Im) increases gradu-
ally. This trend of diversification shows that nucleation model of elec-
trodeposited coatings of nickel in electrolyte is a typical three-dimen-
sional nucleation growth model on basis of literature [6].
0.0030 E=-1.08V E=-1.10V
E=-1.12V E=-1.14V
E=-1.16V
0.0025
0.0020
I/A
0.0015
0.0010
0.0005
0.0000
0 2 4 6 8 10 12 14 16 18
t/S
Fig. 1. Current-time (i-t) curves at different potentials in the electrolyte.
X. Yang-tao et al. Surface & Coatings Technology 330 (2017) 170–177

-1.16V -1.14V

(200)
(111)
1.0 -1.12V -1.10V

(220)
16000
-1.08V 288h

144h
0.8 Instantaneous 12000
nucleation
16h

Intensity(a.u.)
0.6 Continuous
8000
(I/Im)2

nucleation 8h

0.4 4h
4000
1h
0.2
0 0h

0.0 40 50 60 70 80
0.0 0.5 1.0 1.5 2.0
t/tm 2θ/(° )
Fig. 3. XRD diffraction patterns of electrodeposited coatings of nickel at different de-
Fig. 2. The fitted nondimensional curves after data transformation from current-time
position time.
curve to (t/tm)-(I/Im)2.

According to Scharifker-Hills model theory, Fig. 2 shows the fitted
nondimensional curves after data transformation from current-time
curve to (t/tm)-(I/Im)2 [36]. It shows that nickel electro-crystallization
in the electrolyte basically adheres closely to the Scharifker-Hills
model. When potential is − 1.08 V and − 1.10 V, nucleation model is
continuous nucleation model during t < tm time frame. When potential
is − 1.12 V and − 1.16 V, the fitted nondimensional curves tend to
distribute between continuous nucleation model and instantaneous
nucleation model with theory curves. It is well known that the Schar-
ifker-Hills nucleation model is only a theoretical curve, and the domi-
nant trend is generally considered to be tendency of some nucleation
model [37]. Nucleation model of nickel electro-crystallization during
t < tm time frame in the electrolyte is continuous nucleation model.
The nickel electro-crystallization is instantaneous nucleation model
during tm < t < 2tm time frame. The change of nucleation mechanism
is related to state of electrode surface. The Ni2 + coverage on glassy
carbon electrode surface tends to saturation, and the nucleation parti-
cles cannot be continuously replenished in a short time. The nucleation
mechanism changes from three-dimensional continuous nucleation
model to three-dimensional instantaneous nucleation model [38].
3.2. Preferential orientation
The preferential orientation of grains is associated with not only the
velocity and direction of crystal growth but also competitions among
various growth models in electro-crystallization. The “epitaxial growth
mode” are preferential orientation of (110) crystal plane, and the
“lateral growth mode” of electrodeposition coatings are preferential
orientation of (100) or (111) crystal plane with face centered cubic
structures [39].
Fig. 3 exhibits XRD diffraction patterns of electrodeposited coatings
of nickel at different deposition time. As expected, when the electro-
deposition times increases, the preferentially growing direction of
grains of (111) and (220) crystal planes are normal direction. When the
deposition time is 16 h, the grains along (111) crystal plane are priority
Based on the texture theory of metal electrodeposition, the epitaxial
growth and lateral growth models can coexist, and preferential or-
ientation is (111) and (200) crystal planes in the initial stages of nickel
electro-crystallization. As the electrodeposition time increased, nickel
electro-crystallization enters transitional growth period.
Electrochemical activity and atomic arrangement are various at dif-
ferent crystal planes, there is also a different growth rate consequently.
In general, atomic density of crystal plane increases when its electro-
chemical activity decreases [40]. Therefore, the sequence of crystal
plane atomic density of electrodeposited coatings of nickel is
(220) < (200) < (111), the growth rates of crystal planes is
V(220) > V(200) > V(111), and the tendency of preferential direction of
crystal growth is (220) > (200) > (111) from the point of view of
crystallography [40]. Therefore, the (220) crystal plane has preferred
orientation growth, while the diffraction intensity of the other crystal
planes decrease gradually, as well as the growth patterns also change.
The average grain size of different crystal planes increase with the
increase of electrodeposition time (as shown in Table 1), and grain sizes
are also different from growth directions. When deposition time in-
creases from 1 h to 16 h, the average grain size increased from 36.0 nm
to 51.0 nm. The grain size of (111) plane is the largest. When deposition
time increases from 144 h to 288 h, the average grain size of electro-
deposited coatings of nickel has little changes.
3.3. Microstructure
Fig. 4 shows microstructure of electrodeposited coatings of nickel
with different electrodeposition time. It can be seen from the figure,
circular granular deposits with Ni2 + on cathode surface are uniformly
distributed with deposition 60 s, which may be formed by V-W
(Volmer-Weber) mechanism [10]. Therefore, nickel electro-crystal-
lization tends to be instantaneous nucleation at this time [41]. As the
Table 1
Effect of electrodeposition time on grain size of electrodeposited coatings of nickel.

growth, and the (220) crystal plane enhanced, but the (200) crystal Electrodeposition time (h) Grain size (nm)
plane weakened. When deposition time increases from 144 h to 288 h,
the preferentially growing direction of grains is mainly (200) crystal (111) (200) (220) Average grain
plane. The (111) crystal plane is hardly changed, but the growth of plane plane plane size
(220) crystal plane is gradually decreased. The preferentially growing 0 62.0 51.3 52.1 55.1
direction are gradually transformed from (111) and (200) crystal planes 1 36.0 35.4 36.5 36.0
to (111) and (220) crystal planes in nickel electro-crystallization. When 4 50.9 49.2 44.7 48.3
the deposition time is 288 h, the preferentially growing direction of 8 56.1 54.1 51.1 53.8
16 60.0 47.8 45.2 51.0
(200) plane was obviously related to the additives. The changes of
144 65.5 40.5 38.7 48.2
growing direction are relevant to surface energy and chemicals ad- 288 77.2 60.1 – 68.7
sorption/desorption of metal crystallization plane [10].

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X. Yang-tao et al. Surface & Coatings Technology 330 (2017) 170–177

Fig. 4. Microstructure of electrodeposited coatings of

nickel with different electrodeposition time (a) 0 h; (b)
60 s; (c) 5 m; (d) 30 m; (e) 1 h; (f) 4 h; (g) 8 h; (h) 16 h;
(i) 144 h; (j) 288 h.

173
X. Yang-tao et al.
deposition time increases, the adsorption atoms on cathode surface and
other diffusion atoms are randomly encountered, the circular granular
deposits will be reunited agglomeration and growth (Fig. 4c). Those are
completely covered on the cathode surface (Fig. 4d).
The surface topography of electrodeposited coatings of nickel is
“pyramid” [42], the ridge order is perpendicular to direction of growth
[43], and its size and shape distribution is uniform with deposition time
(Fig. 4e). Subsequently, the surface particles become large and uneven
due to aggregation (Fig. 4f and g). This is because the Ni2 + on cathode
surface will be immediately and homogeneously deposited on cathode
surface with reduction reaction occurring when potential is applied on
the cathode. At the same time, electrodeposited coatings of nickel have
metal-ions deficient layer (MIDL) near cathode surface because of the
induced effect discharge [10].The coatings thickness is mainly asso-
ciated with discharge degree of Ni2 + on cathode surface, and it also
affects uniformity of reduction and discharge reaction. The nickel ions
will be priority to deposit on cathode surface due to high electric field
density at the raised part on cathode surface. These raised parts produce
a lot of heat for reducing discharge reaction increased, which further
enhances movement and supply rate of Ni2 +. The more nickel atoms
have electrodeposited at the raised parts, and grain size locality of
nickel electro-crystallization has increased. The course of reductive
reaction is inhibited due to the relative abundance of the Ni2 +. The
growth of nickel electro-crystallization is hindered on the detection of
concave points around the convex part [10], which causes uneven
particles on surface electrodeposited coatings of nickel.
The “pyramid” particles on surface of electrodeposited coatings of
nickel gradually became “cellular” particles by fine grain aggregation
when electrodeposition time increase (Fig. 4h).This is associated with
the electrodeposition of nickel atoms are hindered by foreign impurities
[44]. These impurities affected screw dislocations are not exposed and
growth at the top of cone particles is gradually induced. The active sites
around cone particles continue to grow and form cellular structure,
which are in agreement with “island growth model” of electrodeposi-
tion. Therefore, the nickel growth mechanism changes from “spiral
dislocation growth mode” to “cumulative growth mode”, which is
consistent with the results of literature [11]. Accordingly, the growth
mechanism and surface morphology of electrodeposited coatings of
nickel in the electrolyte are changed with the increase of electro-
deposition coating thickness and electrodeposition time.
3.4. Cross section microstructure
3.4.1. Microstructure
The cross section microstructure of electrodeposited coatings of
nickel for 144 h and 288 h was labeled as shown in Fig. 5, respectively.
The microstructure and grain orientation of samples were analyzed by
EBSD. Test specimen were marked micro-area I as the inner side (near
starting sheet) and micro-area II as the outer side (near surface) of
electrodeposited coatings of nickel. Fig. 5(a), (b) and (c), (d) were grain
orientation distributions of the electrodeposited coatings of nickel.
From Fig. 5a & b we can see that micro-area I is fine grain equiaxed.
But the grain is coarser and fine equiaxed grains gradually transform to
columnar crystal away from micro-area I [45].The main direction of
columnar crystal is nearly perpendicular to the starting sheet. The
thickness of electrodeposition coatings of nickel is greater, and the
dendrite spacing in columnar grain region is larger Fig. 5c & d. The
microstructure of electrodeposition coatings can be broadly divided
into two parts: the equiaxed grain region formed in the initial growth
stage and the columnar grain region formed in the stable growth stage.
Two crystal region formation and width are related to direction and
intensity of electric field in the electrolyte, which is similar to solidi-
fication microstructure of typical alloy liquid forming process. This is
only the effect of undercooling degree and temperature gradient mag-
nitude on microstructure in the liquid forming process. According to the
theory of metal electro-crystallization, nickel electro-crystallization has
174
Surface & Coatings Technology 330 (2017) 170–177
experienced two complementary and inseparable intertwined stages of
“nucleation” and “growth”.
3.4.2. Nucleation and growth model
As is known to all, if the rate of nucleation is higher than the growth
of grain, the electrodeposited coatings of nickel can form fine grains in
nickel electro-crystallization process. On the contrary, it tends to form
coarse grains [46]. As a result, the growth model of nickel electro-
crystallization in the electrolyte was investigated systematically as
Fig. 6 shown. It can be seen from the figure, the nickel ions on the
cathode surface discharge and cooling can deposit on cathode surface in
the initial stages. At this time, the rate of nucleation is higher than the
growth of grain. The fine equiaxed grains without substrate orientation
can be formed by “nucleation growth model” on the cathode surface
[47–48]. The coatings encountered cannot form fine equiaxed grains,
and it tends to form columnar crystals on influence of electric field in
the electrolyte.
The Ni2 + in the vicinity around cathode reduction reaction oc-
curred and formed nickel atoms, which are deposited on cathode sur-
face. The Ni2 + concentration around cathode are rapidly decreased and
formed concentration difference (gradient). Because the entire cathode
has uneven tiny “peak” and “valley” surface from the microstructure
side, current density of the tip parts (the raised part) on cathode surface
is larger, as well as crystal growth rate is faster, the growth pattern is
mainly “discharge tip growth” [49]. As the process continues, dis-
tribution density of force field at the grain “tip” in the electrolysis cells
increased. The point discharge effect is enhanced; nickel atoms in the
grain tip parts are in continued formation and growth of crystal, which
inhibits fine grain crystallization. At this moment, the nucleation rate is
less than growth rate, and the columnar crystal keeps growing when
nickel ions continue to supply and electric field under the compre-
hensive action effect [50]. But the secondary dendrite crystal pre-
ferentially grown into columnar is no in lateral growth impacted by
adjacent columnar crystal barrier. Therefore, the microstructure of
micro-area II forms a columnar crystal region along the main direction
of the dendrite at last.
3.4.3. Characteristics of grain boundary distribution
Tables 2 & 3 are frequency and quantity distribution of grain
boundaries in different micro-area of electrodeposited coatings of
nickel. From the table we can see that a large number of grain
boundaries are above 15°. The frequency of high angle grain boundary
above 15° in micro-area II of two samples are 91.5% and 87.1%, re-
spectively. The boundary frequency below 15° is a lower frequency.
This is consistent with the results of literature [33].
Compared with microarea of the same sample, quantity and oc-
currence frequency of large angle grain boundaries above 15° in mi-
croarea I decreased, but frequency and quantity of grain boundaries
below 15° increased. This indicates that newly produced grain bound-
aries first come in large angle grain boundaries forms in the initial
stage. The proportion of low angle boundary of newly generated grain
boundaries has increased with thickness increase of electrodeposited
coatings of nickel, which mainly are large angle grain boundaries in
general.
Coincidence site lattice (CSL) is an important theoretical model to
describe microstructure of large angle grain boundaries. Table 4 is the
frequency distribution of ΣCSL grain boundaries in different microarea.
The Sigma value refers to density of corresponding points between
superlattice unit cell and actual lattice unit cell. Grain boundary low
energy of ΣCSL and less impurity segregation have higher mobility (Σ1
and Σ3 exception). The grain boundary of relatively low Sigma value
tends to lower grain boundary energy and higher mobility (Σ1 and Σ3
exception) [47].
Table 4 shows that coincidence site lattice (CSL) grain boundary of
electrodeposited coatings of nickel are mainly Σ3, Σ9 and Σ27. The
occurrence frequency of Σ3 boundaries appearing in two micro-areas
X. Yang-tao et al. Surface & Coatings Technology 330 (2017) 170–177

Fig. 5. The cross section microstructure of electrodeposited coatings of nickel for 144 h and 288 h. 1-electrodeposited coatings of nickel, 2-stating sheet. Panels a & c for grain orientation
distribution of sample A; panels b & d for grain orientation distribution of sample B.

Fig. 6. The growth model of nickel electro-crystallization in

the electrolyte.

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X. Yang-tao et al. Surface & Coatings Technology 330 (2017) 170–177

Table 2 between Σ3n and Σ3n + 1 of electrodeposited coatings are mainly car-
Grain boundary quantity of different orientations in different microareas. ried out with the formula (1). The re-excitation response of Σ3 can
promote the Σ3 grain boundary preliminarily formed, so the Σ3 grain
Misorientation Sample A Sample B
boundaries are accounted for the highest proportion of electrodeposited
Microarea II Microarea I Microarea II Microarea I coatings of nickel.

≤ 5° 10,046 13,213 19,503 20,338

4. Conclusions
5–15° 8532 15,043 12,579 8366
> 15° 198,039 126,342 215,733 64,129
(1) Nickel electro-crystallization follows nucleation and growth me-
chanism. The nucleation process basically follows Scharifker-Hills
Table 3 model. Nickel electro-crystallization in the electrolyte is dominated
Grain boundaries frequency of different orientations in different microareas (%). by continuous nucleation model during t < tm time frame. And
then the main nucleation model has transformed from continuous
Misorientation Sample A Sample B
nucleation to instantaneous nucleation model during
Microarea II Microarea I Microarea II Microarea I tm < t < 2tm time frame. Nickel electro-crystallization in the
electrolyte is experienced in the alternative process of nucleation
≤ 5° 4.6 8.5 7.8 21.9
and growth.
5–15° 3.9 9.7 5.1 9.0
> 15° 91.5 81.8 87.1 69.1 (2) The preferential growth orientation of crystal is gradually changed
from primary (111) and (200) plane at first to (220) crystal plane.
The surface morphology of electrodeposited coatings of nickel is
Table 4 slowly changed from pyramid to cellular structure, and the growth
Frequency distribution of ΣCSL grain boundary in different microareas. mechanism changes from the screw dislocation growth at first to
cumulative growth with electrodeposition time increase from 1 h to
Boundary type Σ Sample A Sample B
16 h. When electrodeposition time is 144 h, the preferential or-
Microarea II Microarea I Microarea II Microarea I ientation at all directions was not obvious.
(3) The cross section microstructure of electrodeposited coatings of
3 44.2 56.7 45.5 51.8
nickel is primary divided into fine equiaxed grain region and coarse
5 0.3 0.1 0.2 0.1
7 0.4 0.1 0.3 0.1 columnar crystal region. The grain size and distribution of co-
9 9.4 6.0 8.1 3.5 lumnar grain region increase along with the coatings thickness in-
11 0.5 0.2 0.5 0.1 crease. This process is similar to the solidification microstructure of
13 0.4 0.0 0.2 0.0 typical alloy liquid forming process.
15 0.2 0.1 0.2 0.0
(4) The high angle grain boundary is above 15° in nickel electro-crys-
17 0.2 0.1 0.6 0.0
19 0.5 0.3 0.6 0.3 tallization process, which is mainly the characteristic of low ΣCSL
21 0.3 0.0 0.2 0.1 grain boundary distribution structure. The Σ3 boundaries have the
23 0.1 0.0 0.5 0.1 highest frequency, which is related to twins and preferential
25 0.3 0.1 0.2 0.0
growth.
27 0.6 2.4 0.3 1.1
29 0.1 0.2 0.1 0.0
References

are > 40%. The occurrence frequency of Σ3 grain boundary in micro-
area I of two samples are greater than frequency in micro-area II, which
is consistent with the results of literature [50]. But beyond that, that
most frequent Σ3 twin boundary is associated with microstructure
misorientation of nickel electro-crystallization, because low ΣCSL grain
boundaries have to do with grains nucleation, grain boundary migra-
tion and anisotropy of grain orientation growth, which are not directly
affected by grain size. Therefore, the preferential growth of electro-
deposited coatings is characterized with Σ3 high frequency distribution
of grain boundary [47]. The characteristics of low ΣCSL can improve
mechanical properties and corrosion resistance of electrodeposited
coatings [52–54].
T. Watanabe has found that a great deal of heat would be released in
the ions discharge process, so nickel electro-crystallization process is
both a sort of metal material and a kind of “the super-cooled” solid.
That is to say, there exists rapid solidification from metal ions, atoms to
crystal in process of transformation in local atoms [11]. The “Σ3 ex-
citation model” shows that the following actions will occur due to grain
boundary migration when grain boundaries of Σ3n and Σ3n + 1 (n re-
presenting any positive integer) are encountered [55]:
Σ3n + Σ3n + 1 → Σ3
Σ3n + Σ3n + 1 → Σ3n + 2
The grain boundary energy and mobility of Σ3n + 2 according to
formula (2) are higher and smaller than grain boundary energy of Σ3
according to formula (1), respectively. The reaction on grain boundary
[1] E.A. Pavlatou, M. Raptakis, N. Spyrellis, Synergistic effect of 2-butyne-1,4-diol and
pulse plating on the structure and properties of nickel nanocrystalline deposits,
Surf. Coat. Technol. 201 (2007) 4571–4577.
[2] D. Grujicic, B. Pesic, Electrodeposition of copper: the nucleation mechanisms,
Electrochim. Acta 47 (2002) 2901–2912.
[3] E. Budevski, G. Staikov, W.J. Lorenz, Electrocrystallization-nucleation and growth
phenomena, Electrochim. Acta 45 (2000) 2559–2574.
[4] M. Fleischmann, J.R. Mansfield, H.R. Thirsk, H.G.E. Wilson, L. Wynne-Jones, The
investigation of the kinetics of electrode reactions by the application of repetitive
square pulses of potential, Electrochim. Acta 12 (1967) 967–982.
[5] L.F. Zheng, G.Q. Zheng, H.Z. Cao, J.Y. Zhang, Electrochemical nucleation of nickel
on vitreous carbon in leaching solution containing ammonia and chloride, J. Mater.
Sci. 21 (2003) 882–885.
[6] X.W. Yang, M.Z. An, Y.W. Zhang, L. Zhang, Electrodeposition behaviors of gold in
bath with DMDMH as a complexing agent, Chinese J. Inorg. Chem. 28 (2012)
1145–1150.
[7] L. Huang, R. Zhang, M. Gu, F.Z. Yang, S.K. Xu, S.M. Zhou, Initial stages of copper
electrodeposition on glassy carbon electrode, Electrochemistry 8 (2002) 263–268.
[8] Z.W. Tian, Electrochemical Methods, China Science and Technology Press, Beijing,
1984, pp. 273–278.
[9] L.J. Zhang, J.J. Fan, Z. Zhang, F.H. Cao, J.Q. Zhang, C.N. Cao, Study on the anodic
film formation process of AZ91D magnesium alloy, Electrochim. Acta 52 (2007)
5325–5333.
[10] Tohru Watanabe, Z.P. Chen, G. Yang (Eds.), Written, Nano-plating, Chemical
Industry Press, Beijing, 2007Translated.
[11] T. Watanabe, Structure control theory of plated film: part of surface morphology, J.
Jpn. Inst. Met. Mater. 66 (2002) 350–361.
(1) [12] A.M. El-Sherik, U. Erb, Synthesis of bulk nanocrystalline nickel by pulsed electro-
deposition, J. Mater. Sci. 30 (1995) 5743–5749.
(2) [13] X.T. Yuan, Y. Wang, D.B. Sun, H.Y. Yu, Influence of pulse parameters on the mi-
crostructure and microhardness of nickel electrodeposits, Surf. Coat. Technol. 202
(2008) 1895–1903.
[14] P.Q. Dai, H. Yu, Q. Li, Synthesis and characterization of electrodeposited nano-
crystalline nickel, T. Mater. Heat Treat. 25 (2004) 1283–1286.
[15] H.S. Karayannis, G. Patermarakis, Effect of the Cl− and SO42 − ions on the selective

176
X. Yang-tao et al.
orientation and structure of Ni electrodeposits, Electrochim. Acta 40 (1995)
1061–1069.
[16] J.W. Dini, Electrodeposits, the Material Science of Coatings and Substrates, Noyes
Publications, New Jersey, 1993, pp. 1–10.
[17] Alexander Milchev, Electrocrystallization: Fundamentals of Nucleation and Growth,
Kluwer Academic Publishers, New York, 2002, pp. 11–16.
[18] A. Azizi, A. Sahari, G. Schmerber, A. Dinia, Nucleation and structural properties of
nickel films electrodeposited from chloride and sulfate baths, Int. J. Nanosci. 7
(2008) 345–352.
[19] Darko Grujicic, Batric Pesic, Electrochemical and AFM study of nickel nucleation
mechanisms on vitreous carbon from ammonium sulfate solutions, Electrochim.
Acta 51 (2006) 2678–2690.
[20] F. Ebrahimi, G.R. Bourne, M.S. Kelly, T.E. Matthews, Mechanical properties of
nanocrystalline nickel produced by electrodeposition, Nanostruct. Mater. 11 (1999)
343–350.
[21] Young Rang Uhm, Keun Yung Park, Sun Ju Choi, The effects of current density and
saccharin addition on the grain size of electroplated nickel, Res. Chem. Intermed.
41 (2015) 4141–4149.
[22] E. Imre Bakonyi, Lajos Pogány Tóth-Kádár, Ágnes Cziráki, Imre Gerőcs,
Katalin Varga-Josepovits, Birgit Arnold, Klaus Wetzig, Preparation and character-
ization of d.c.-plated nanocrystalline nickel electrodeposits, Surf. Coat. Technol. 78
(1996) 124–136.
[23] I. Bakonyi, E. Tóth-Kádár, T. Tarnóczi, L.K. Varga, Á. Cziráki, Structure and prop-
erties of fine-grained electrodeposited nickel, Nanostruct. Mater. 3 (1993) 155–161.
[24] S.T. Aruna, S. Diwakar, A. Jain, K.S. Rajam, Comparative study on the effect of
current density on Ni and Ni-Al2O3 nanocomposite coatings produced by electro-
lytic deposition, Surf. Eng. 21 (2005) 209–214.
[25] A.M. Rashidi, A. Amadeh, The effect of current density on the grain size of elec-
trodeposited nanocrystalline nickel coatings, Surf. Coat. Technol. 202 (2008)
3772–3776.
[26] J.X. Kang, W.Z. Zhao, G.F. Zhang, Influence of electrodeposition parameters on the
deposition rate and microhardness of nanocrystalline Ni coatings, Surf. Coat.
Technol. 203 (2009) 1815–1818.
[27] Takeshi Sakamoto, Kazuhisa Azumi, Hiroto Tachikawa, Kei Iokibe, Masahiro Seo,
Nobuya Uchida, Yasunaga Kagaya, Effects of 2-buthyne-1,4-diol additive on elec-
trodeposited Ni films from a Watts-type bath, Electrochim. Acta 55 (2010)
8570–8578.
[28] Y. Nakamura, N. Kaneko, M. Watanabe, H. Nezu, Effects of saccharin and aliphatic
alcohols on the electrocrystallization of nickel, J. Appl. Electrochem. 24 (1994)
227–232.
[29] Krzysztof Mech, Influence of organic ligands on electrodeposition and surface
properties of nickel films, Surf. Coat. Technol. 315 (2017) 232–239.
[30] Do-Hwan Nam, Kyung-Sik Hong, Jong-Soo Kim, Jong-Lok Lee, Go-Eun Kim, Hyuk-
Sang Kwon, Synergistic effects of coumarin and cis-2-butene-1,4-diol on high speed
electrodeposition of nickel, Surf. Coat. Technol. 248 (2014) 30–37.
[31] E.A. Pavlatou, P. Gyftou, S. Spanou, Effects of cis-2-butene-1,4-diol additive and
pulse current imposition on production of Ni nanocrystalline coatings, Trans. Inst.
Met. Finish. 90 (2013) 267–273.
[32] A.P. Abbott, A. Ballantyne, R.C. Harris, J.A. Juma, K.S. Ryder, Bright metal coatings
from sustainable electrolytes: the effect of molecular additives on electrodeposition
of nickel from a deep eutectic solvent, Phys. Chem. Chem. Phys. 19 (2017)
3219–3231.
[33] Shibata Akinobu, Noda Homuro, Sone Masato, Higo Yakichi, Microstructural de-
velopment of an electrodeposited Ni layer, Thin Solid Films 518 (2010) 5153–5158.
[34] T.D. Xia, X.Y. Zhang, Y.T. Xu, W.W. Ding, W.J. Zhao, Comparison for
177
Surface & Coatings Technology 330 (2017) 170–177
microstructure and mechanical properties of electrodeposited nickel and rolled
nickel, Chin. J. Nonferrous Met. 25 (2015) 3133–3140.
[35] X.Y. Zhang, Comparison for Commercially Available Industrial Pure Nickels,
Lanzhou University of Technology, 2015.
[36] B. Scharifker, G. Hills, Theoretical and experimental studies of multiple nucleation,
Electrochim. Acta 28 (1983) 879–889.
[37] W. Zhang, Y.T. Xu, T.D. Xia, Effect of sodium saccharin on mechanism of nickel
electrodeposition in mixed acid salt, Electroplat. Finish. 34 (2015) 1145–1149.
[38] X.S. Zhao, C.Y. Tan, W.J. Chen, Y. Liu, J.F. Li, Z.Q. Zheng, Nucleation kinetics
analysis of Ni-SiC composite film during early electrocrystallization processes, Chin.
J. Nonferrous Met. 18 (2008) 823–828.
[39] C.S. Lin, P.C. Hsu, L. Chang, C.H. Chen, Properties and microstructure of nickel
electrodeposited from a sulfamate bath containing ammonium ions, J. Appl.
Electrochem. 31 (2001) 925–933.
[40] S.M. Zhou, Principles and Methods of Metal Electrodeposition, Shanghai
Scientific & Technical Publishers, Shanghai, 1987, pp. 140–145.
[41] M. Boubatra, A. Azizi, G. Schmerber, A. Dinia, The influence of pH electrolyte on
the electrochemical deposition and properties of nickel thin films, Ionics 18 (2012)
425–432.
[42] C. Zanell, M. Lekka, P.L. Bonora, Influence of the particle size on the mechanical
and electrochemical behavior of micro- and nano-nickel matrix composite coatings,
J. Appl. Electrochem. 39 (2009) 31–38.
[43] A.M. Rashidi, A. Amadeh, The effect of saccharin addition and bath temperature on
the grain size of nanocrystalline nickel coatings, Surf. Coat. Technol. 204 (2009)
353–358.
[44] A. Bund, D. Thiemig, Influence of bath composition and pH on the electro-
codeposition of alumina nanoparticles and nickel, Surf. Coat. Technol. 201 (2007)
7092–7099.
[45] Siddhartha Pathak, Marion Guinard, Martine G.C. Vernooij, Barbara Cousin,
W. Zhao, Johann Michler, Laetitia Philippe, Influence of lower current densities on
the residual stress and structure of thick nickel electrodeposits, Surf. Coat. Technol.
205 (2011) 3651–3657.
[46] Z.H. Ning, Y.D. He, W. Gao, Mechanical attrition enhanced Ni electroplating, Surf.
Coat. Technol. 202 (2008) 2139–2146.
[47] H.C. Sun, S.K. Li, Y.X. Hou, X.D. Lu, W. Guo, EBSD study of CVD-W grain or-
ientation and grain boundary, Chin. J. Stereol. Image Anal. 12 (2007) 286–288.
[48] A.M. El-Sherik, U. Erb, J. Page, Microstructural evolution in pulse plated nickel
electrodeposits, Surf. Coat. Technol. 88 (1997) 70–78.
[49] B. Lv, Z.F. Hu, X.H. Wang, B.S. Xu, Effect of relative moving speed on micro-
structure of flexible friction assisted electrodeposited Ni coating, Chin. J. Mater.
Res. 28 (2014) 255–261.
[50] Z.H. Ning, Y.D. He, The effect of mechanical attrition on the grain growth of
electrodeposition Ni coatings, Acta Metall. Sin. 44 (2008) 751–756.
[52] A. Godon, J. Creus, S. Cohendoz, E. Conforto, X. Feaugas, P. Girault, C. Savall,
Effects of grain orientation on the Hall-Petch relationship in electrodeposited nickel
with nanocrystalline grains, Scr. Mater. 62 (2010) 403–406.
[53] I. Roy, H.W. Yang, L. Dinh, I. Lund, J.C. Earthman, F.A. Mohamed, Possible origin of
superior corrosion resistance for electrodeposited nanocrystalline Ni, Scr. Mater. 59
(2008) 305–308.
[54] G. Palumbo, K.T. Aust, E.M. Lehockey, U. Erb, P. Lin, On a more restrictive geo-
metric criterion for “special” CSL grain boundaries, Scr. Mater. 38 (1998)
1685–1690.
[55] V. Randle, Mechanism of twinning-induced grain boundary engineering in low
stacking-fault energy materials, Acta Mater. 47 (1999) 4187–4196.