Surface & Coatings Technology 337 (2018) 186–197

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Surface & Coatings Technology

journal homepage: www.elsevier.com/locate/surfcoat

Synthesis and characterization of Ni-B/Al2O3 nanocomposite coating by T

electrodeposition using trimethylamine borane as boron precursor
⁎ ⁎
Baosong Lia, , Weiwei Zhangb, , Yuxing Huana, Jia Donga
a
College of Mechanics and Materials, Hohai University, Nanjing 211100, China
b
College of Mechanical and Electrical Engineering, Hohai University, Changzhou 213022, China

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

Keywords: A novel Ni-B/Al2O3 nanocomposite coating was synthesized through electrodeposition by reinforcing Ni-B
Electrodeposition matrix with Al2O3 nanoparticles using trimethylamine borane as boron precursor. The effects of trimethylamine
Ni-B/Al2O3 nanocomposite coating borane, Al2O3 nanoparticle, current density, thermal treatment on the properties of the electrodeposited coatings
Wear resistance were examined. The morphology, microstructure, corrosion behavior and wear resistance of the Ni-B/Al2O3
Corrosion behavior
coating in their as-deposited states were investigated by SEM, EDX, XRD and electrochemical techniques. It
Surface morphology
demonstrates that boron content has a beneficial effect on grain refinement and facilitates the formation of the
amorphous phase. The hardness and wear resistance of Ni-B coating can be improved by the addition of Al2O3
particles due to the dispersion hardening of the hard Al2O3 particles. Both the boron and Al2O3 nanoparticle
content in the deposited Ni-B/Al2O3 coating decreases as the current density increased from 1 to 7 A dm−2. The
incorporation of Al2O3 nanoparticles alters the chemical composition, enhances the microhardness, improves the
crystallinity of the Ni-B matrix. Owing to the grain refinement of Ni-B matrix, dispersion hardening of the added
nanoparticles, as well as the reduction in the active surface area of Ni-B matrix by the presence of inert particles,
Ni-B/Al2O3 nanocomposite coating with dense structure shows superior anti-corrosion and wear resistance than
Ni/Al2O3 or Ni-B coating.

1. Introduction utilize the synergistic effect based on the complementary advantages of

Presently, Ni-B alloy coating has been attracting substantial atten-
tion as promising protection material owing to their remarkable ad-
vantages such as high hardness, good tribological properties, decent
anti-corrosion performance and thermal stability [1]. These special
characteristics have made them convenient for widespread applications
as metallic matrix [2, 3]. Electroless deposition has been adopted to
deposit Ni-B coatings on a variety of substrates [4–6]. However, elec-
troless deposition is operated at high temperature (70–90 °C) with high
pH values (13–14) [7, 8]. Also, a strict control of pH value is essential as
nickel ions readily hydrolyze in the neutral or acidic environment [9].
Fortunately, Ni-B alloys can also be obtained by electrodeposition,
which can be easily controlled at the atomic scale in the deposition
process to synthesize nanocomposites [10]. However, till now, very
limited reports are available on the synthesis of Ni-B coatings through
electrodeposition process [11, 12].
Nowadays, most of the high-performance coatings are combined
with the advantages of second-phase reinforcing particles, and it is
becoming a hot research field increasingly [13, 14]. This strategy is to
the reinforcing nanoparticle phase and microstructure control [15].
During the co-deposition process, the reinforcing particles, such as
Al2O3 [16], TiO2 [17], SiO2 [18, 19], diamond [3], SiC [19], CNT [20],
MoS2 [21] and Si3N4 [22] are entrapped and embedded in the growing
alloy matrix either by electrophoresis, mechanical entrapment or ad-
sorption phenomena. This could also form amorphous or nanocrystal-
line structure due to the modified growth process [23, 24]. In harsh
condition, such as in the marine environment, the coatings are much
desired to have high hardness, high wear resistance, and good anti-
corrosion properties. Unfortunately, the as-deposited Ni-B alloy may
not possess all the above properties [25]. Since it combines the ad-
vantages of both Ni-B matrix and the reinforcing particles, the Ni-B
nanocomposite coatings have properties superior to the Ni-B alloys [26,
27]. Therefore, the imported of reinforcing particles into Ni-B matrix
was proposed in this study [28, 29].
Although the Ni-B/Si3N4 [22], Ni-B/diamond [11], Ni-B/SiC [13]
composite coatings have recently been reported on their electro-
deposition and corresponding characteristics, composite coatings using
Ni-B as the matrix material have rarely been reported [30]. Till now,

⁎
Corresponding authors.
E-mail addresses: bsli@hhu.edu.cn (B. Li), zdzdq@126.com (W. Zhang).

https://doi.org/10.1016/j.surfcoat.2018.01.018
Received 27 October 2017; Received in revised form 3 January 2018; Accepted 8 January 2018
Available online 10 January 2018
0257-8972/ © 2018 Elsevier B.V. All rights reserved.
B. Li et al.
the co-deposition mechanism of the suspended inert particles into me-
tallic matrix has rarely been reported conformably and is still not un-
derstood thoroughly [31]. It is still a very challenging task to elucidate
the co-deposition mechanism and the influencing factors. In addition,
the physical, mechanical and corrosion properties of nanocomposite
coatings do not only depend on the composition and microstructure of
the coating but also particle content, electrodeposition parameter in-
cluding deposition time and current density [3]. Therefore, it is ne-
cessary to examine the influence of deposition parameters such as na-
noparticle concentration, current density on the microstructure of the
deposited coating. Al2O3 nanoparticles are broadly used as second-
phase reinforcing particles in the composite coating to produce the hard
and wear resistant coating due to their good thermal stability, high
hardness, wear resistance, commercially available, inexpensive and
oxidation resistant [28, 32, 33]. Hence, it can be expected that the
Al2O3 nanoparticles could substantially enhance the properties of Ni-B
coating, including its mechanical, tribological and anti-corrosion be-
havior.
Based on the above background, in the present study, we report on
the co-deposition of Al2O3 nanoparticles in Ni-B metal matrix by a
conventional electrodeposition technique for high anti-corrosion per-
formance. Herein, the impacts of co-deposition parameters including
current density, trimethylamine borane (TMAB) and Al2O3 particles on
the composition, microstructure, morphology, and microhardness of
the Ni-B/Al2O3 nanocomposite coatings were investigated. The re-
lationship between Al2O3 incorporation and the final performance such
as the corrosion resistance and wear behavior of the deposited Ni-B/
Al2O3 coating was discussed. The corrosion resistance of the coating in
3.5% NaCl solution was investigated. We think this novel nano-
composite coating will be useful for applications in extreme wear and
corrosion environment.
2. Experimental
Ni-B/Al2O3 nanocomposite coating was prepared using Ni electro-
plating bath containing trimethylamine borane (TMAB), Al2O3 parti-
cles, sodium dodecyl sulfonate (SDS) and saccharin. The bath compo-
sition and electrodeposition parameters are listed in Table 1. All
chemicals were analytical grade and used without further purification.
Besides the Ni-B/Al2O3 coating, the Ni-B, Ni/Al2O3 coatings were pre-
pared for comparison using this bath only without Al2O3 particles or
TMAB, respectively. To disperse Al2O3 particles uniformly and maintain
it in the suspension state, the electrolytes containing Al2O3 particles
were premixed and stirred by a magnetic stirrer for at least 2 h in the
presence of surfactant just prior to electrodeposition. During electro-
deposition, the magnetic stirring was also employed at the cell bottom.
A nickel plate was used as anode. The cathodes were copper plates
masked with insulated tapes to leave 20 mm × 20 mm exposed area.
The electrodes were positioned vertically in a 200 mL electrodeposition
baths. The distance between anode and cathode was 25 mm. The sub-
strate cathodes were mechanically polished to 1200-grit finish with SiC
abrasive papers. After that, they were cleaned ultrasonically for 10 min
in acetone and ethanol consecutively, washed in distilled water and
Table 1
Chemical composition of electrodeposition bath and the operating parameter for Ni-B/
Al2O3 composite coating.
Electrolyte composition Operating parameters
NiSO4·6H2O 220 g L−1
pH 3.5
NiCl2·6H2O 40 g L−1 Temperature 50 °C
H3BO3 30 g L−1 Current density 0.5–7 A dm−2
Trimethylamine borane(TMAB) 3 g L−1 Agitation rate 400 rpm
Sodium dodecyl sulfate(SDS) 0.5 g L−1 Electrode distance 2.5 cm
Saccharin 1 g L−1 Deposition time 30 min
Al2O3 nanoparticles 15 g L−1 Anode Ni plates
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Surface & Coatings Technology 337 (2018) 186–197
then immersed immediately in the plating bath. Especially, the elec-
trodeposition parameters such as current densities 0.5, 1, 3, 5 and
7 A dm−2, Al2O3 particles 5 to 25 g L−1, and TMAB 3, 6, 9 g L−1, were
evaluated to investigate their effects on the properties of the nano-
composite coating. The pH of the electrolyte was 3.5, and the tem-
perature was kept constant at 50 °C. The coatings were cleaned in
double-distilled water for about 1 min after the electrodeposition to
remove the loosely adsorbed Al2O3 nanoparticles and electrolyte from
the surface.
The surface and cross-sectional morphologies were observed by
scanning electron microscope (SEM, model HITACHI-S3400 N). The
surface elemental analysis was confirmed by the elemental mapping
using Oxford INCA energy dispersive X-ray spectroscopy (EDS) coupled
to the SEM. The crystal structure, phase and preferred orientation of the
deposits were characterized by X-ray diffraction (XRD, D8 Advance
model) using a Cu Kα radiation. The microhardness in the cross-regions
of the coatings was measured using a Vickers's microhardness indenter
with a load of 50 g for 10 s, and the average value of 5 measurements
was reported as the microhardness of the deposits. The wear resistance
of specimens was evaluated on UMT-3 multi-function friction and wear
tester with a ball-on-disc configuration. Counterparts were SiC balls
with a diameter of 3 mm and a hardness of 17 GPa. Wear tests were
carried out with a frequency of 5 Hz and amplitude of 2.5 mm under
10 N for dry-sliding. Each specimen was tested three times under the
same condition to collect an average value. A surface profiler (Alpha-
Step IQ) was used to measure the wear track profile, and the wear rate
of specimens was calculated using the equation:
V
A=
F·L (1)
3
where V is the wear volume loss (mm ), L is the total sliding distance
(m), and F is the normal load (N).
All the electrochemical experiments were measured in 3.5% NaCl
solution without agitation at the room temperature (25 °C) with a three-
electrode cell, including a working electrode, a platinum plate counter
electrode and a saturated calomel electrode (SCE). The bath was
deoxidized 20 min by Nitrogen before the experiment. The electro-
chemical impedance spectroscopy (EIS) was carried out on CHI 660E
electrochemical working station, referring to a frequency range of
10−2–105 Hz and amplitude 10 mV. The polarization curves of the
electrolyte were recorded at a sweep rate of 1 mV/s in 3.5% NaCl so-
lution at room temperature, referring to a potential window of
−1.0–0.1 V.
3. Results and discussion
3.1. The internal stress and grain size of the co-deposited coating
To obtain smooth, dense Ni-B and Ni-B/Al2O3 coating without
cracks, in this study, saccharin and sodium dodecyl sulfonate (SDS) are
adopted as additives. It is well known that agglomeration of Al2O3
particles is one of the main challenges in this co-deposition. In the
electrochemical co-deposition process, one of the crucial factors is
suspending the reinforcements in the electrolyte. Another is the high
internal stress and cracks of the coating, which is a harmful defect that
we try to avoid. Therefore, in this work, saccharin, sodium dodecyl
sulfonate as well as continuously stirring at the rate of 400 rpm was
employed in the electrodeposition process to provide that the nano-
particles are successfully suspended in the electrolyte. Meanwhile, it is
expected to reduce the internal stress and retard the formation of
cracks.
Saccharin is frequently used in electroplating as leveling agents and
can reduce the internal stress of the coating during electrodeposition.
The mechanism of the leveling effect is that saccharin favors the de-
position process on the micro-grooves through absorbing at micro-
peaks on the surface of the coating, which increases the resistance to
B. Li et al.
the deposition current. As a common anion surfactant, SDS is used for
lowing the surface tension of the electrodeposition electrolyte. Then, it
eases the release of hydrogen from the cathode and reduces the pro-
pensity of pits on the coating surface. To some degree, saccharin and
SDS both have the effects of auxiliary brightener. Fig. 1 shows the
surface images of the Ni-B or Ni-B/Al2O3 coating electrodeposited
without additives, with SDS, and with SDS plus saccharin, respectively.
It can be seen in Fig. 1a that cracks emerged in Ni-B coating without
additives. It indicates large internal stress is accumulated in the de-
posited coating, which could promote the emergence of cracks and
deteriorate the corrosion resistance. As shown in Fig. 1b, in the pre-
sence of 0.5 g L−1 SDS, the surface of the Ni-B coating was homogenous,
uniform and grained structure. The cracks were disappeared, and the
grain size was refined. When the bath contains 0.5 g L−1 SDS plus
1 g L−1 saccharin, as shown in Fig. 1(c, d), it suggests that the grain size
becomes finer and the surface of the coating becomes smooth. It was
reported that SDS was not very effective in reducing Ni grain size.
However, the addition of 0.5 g L−1 saccharin resulted in approximate
40% reduction in grain size [3], which was also confirmed by Fig. 1.
Many factors such as saccharin concentration, current density, as
well as bath temperature, could affect the grain size of the coating. In
fact, the mechanism of these factors on the grain size has not yet been
fully understood, and huge research is needed for clarifying the me-
chanism of grain refinement. In this section, the effects of current
density and saccharin on the properties of Ni-B/Al2O3 nanocomposite
coating were investigated further. As shown in Fig. 2, initially, the grain
size of the deposits decreases rapidly as the saccharin concentration
increased up to 1 g L−1. The reason is related to the combined effects of
retarding the surface diffusion, blocking the crystalline growth and the
change in overpotential. Nevertheless, it was also found that the grain
size keeps almost constant by further increasing saccharin concentra-
tion. The grain size of the coating is approximately independent of
saccharin concentration when saccharin is beyond 1 g L−1. This phe-
nomenon can be attributed to the leveling off in the overpotential or
saturation of adsorption sites on the cathode surface with increasing the
saccharin amount in the bath. This behavior is consistent with the data
presented by Yuan et al. [34]. The observed refining effect of grain size
with the addition of saccharin is in agreement with the previous reports
[35]. Hence, a compact, pore-free coating was obtained with fine grain
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Surface & Coatings Technology 337 (2018) 186–197
Fig. 1. SEM images of the electrodeposited coating (a) N-B,
without additive; (b) N-B, 0.5 g L−1 SDS; (c) N-B, 0.5 g L−1
SDS plus 1 g L−1 saccharin; (d) N-B/Al2O3, 0.5 g L−1 SDS
plus 1 g L−1 saccharin.
Fig. 2. Grain size of Ni-B/Al2O3 coating electrodeposited at 1 A dm−2 as a function of
saccharin concentration in the electrolyte.
structure in the presence of saccharin and SDS. Furthermore, the for-
mation of dense and pore-free coatings retard the corrosion process by
preventing the penetration of the solution from attacking the substrate.
Thus, the physical shielding effect and corrosion resistance of the
coating was enhanced. Therefore, 0.5 g L−1 SDS plus 1 g L−1 saccharin
was employed for the high performance of the coating in the following
investigation.
Fig. 3 shows the effects of boron content in Ni-B/Al2O3 coating on
the internal stress and grain size of the deposit. The internal stress was
tensile and increased linearly with increasing boron content in the
coating. The tensile stress value of 60.22 kg/mm−2 in coatings con-
taining 18.3 at.% B was abnormally high and caused many cracks in the
coating. This high tensile stress will be closely connected with a high
hydrogen content of 400–1200 ppm in the coatings. Fig. 3 also shows
the variation in grain size of the Ni-B/Al2O3 coatings electrodeposited
at 1 A dm−2 as a function of boron content in the coating. It can be
observed that as B composition increases from 0 to 4 at.%, the grain size
decreases quickly. When the B content exceeds 4 at.%, the grain size is
almost invariable. Therefore, it can be concluded that the B content in
the coating affects not only the internal stress of the coating but also the
grain size of the deposits. These indicate that it is not necessary to
B. Li et al.
Fig. 3. Internal stress and grain size of Ni-B/Al2O3 coating electrodeposited at 1 A dm−2
as a function of boron content in the coating.
incorporate large amounts of boron in the coating to substantially in-
crease the performance of the coating.
3.2. Surface and cross-sectional morphology
According to previous reports [13, 36], many properties of Ni-B
coatings, such as texture, microstructure, and microhardness are af-
fected by current density. The morphologies of Ni-B/Al2O3 coatings co-
deposited at various current densities for 30 min are shown in Fig. 4. It
shows that current density has important influences on the growth and
microstructure of Ni-B/Al2O3 composite coatings. As seen in Fig. 4a, the
coating was smooth, compact, and fine-grained when current density is
1 A dm−2. The aggregations of the coating are attributed to the in-
sufficient dispersion of nanoparticles in the bath. With the increase of
current density from 1 A dm−2 to 7 A dm−2 (Fig. 4d), the composite
crystal grains become larger and larger. The agglomeration of Al2O3
particles is one of the main challenges. Herein, sodium dodecyl sulfo-
nate, stirring in the presence of surfactant before electrodeposition as
well as continuously stirring during electrodeposition process was em-
ployed to suspend Al2O3 particles uniformly in the electrolyte. How-
ever, besides these aspects, it was found that the current density also
influenced the incorporation and distribution of the reinforcement
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Surface & Coatings Technology 337 (2018) 186–197
particles. Therefore, it shows the huge role of operating parameters in
the co-deposition process.
However, only the surface morphology of the coating could not
demonstrate the incorporation and homogenous distribution of Al2O3
nanoparticle into the Ni-B matrix. It is possible that the nanoparticle is
just sitting and adheres on the top surface. The cross-sectional image of
the coating was also performed to show the distribution of Al2O3 par-
ticles in the bulk of the coating, which can be seen in Fig. 5. Fig. 5
demonstrates that the nanoparticles were uniformly distributed in the
deposited coatings. The cross-sectional images show that the coating
thickness is 5.8 μm, 10.5 μm, 28.9 μm, 47.4 μm corresponding to cur-
rent density of 0.5 A dm−2, 1 A dm−2, 3 A dm−2, 7 A dm−2, respec-
tively. In general, the electrodeposition process will be promoted with
the increase of current density. However, at the same time, a distinct
growth in grain size was observed due to the high reduction rate of
nickel ions on the cathode surface and the hasty inclusion of the na-
noparticle into Ni-B matrix. Therefore, rough and large grain surface
was formed at high current density. Also, internal stress is accumulated
due to the intense hydrogen evolution reaction at a high current density
which results in the formation of microcracks. Although the high
growth rate of the composite coating is much desired, the optimal
current density of co-deposition is not the highest value because more
internal stress will be accumulated at high current densities which leads
to cracks formation. The coatings obtained at different current densities
indicated that it is easy to get uniform, dense, fewer cracks and fine-
grained coating at low current density. Considering the current effi-
ciency, it could be concluded that the optimal current density is be-
tween 1 and 3 A dm−2.
3.3. EDS and X-ray diffraction analysis
The EDS spectra of Ni-B and Ni-B/Al2O3 nanocomposite coating are
presented in Fig. 6. The presence of Ni, B can be observed in Fig. 6. It
was also found that in addition to Ni and B peaks, the peak of aluminum
has also appeared in the EDS spectra which also confirms the co-de-
position of Al2O3 particles into Ni-B matrix. This result suggests that
Al2O3 particles can be successfully co-deposited in Ni-B coatings using
TMAB under acidic conditions.
Fig. 7 shows the comparison of XRD patterns of the Ni-B/Al2O3
Fig. 4. SEM images of N-B/Al2O3 composite coating elec-
trodeposited at current density (a) 1 A dm−2; (b) 3 A dm−2;
(c) 5 A dm−2 and (d) 7 A dm−2.
B. Li et al.
Fig. 7. XRD patterns of N-B/Al2O3 composite coating electrodeposited with different
TMAB concentration in the bath.
coating prepared in the bath containing 0, 3, 6 and 9 g L−1 TMAB, re-
spectively. It can be observed that X-ray diffraction pattern of electro-
deposited Ni-B/Al2O3 coating exhibits broad peak as clearly shown in
Fig. 9. As for the coatings without TMAB (Ni/Al2O3), the diffraction
peaks (111), (200), (220) and (311) of Ni corresponding to 44.7°, 52.0°,
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Surface & Coatings Technology 337 (2018) 186–197
Fig. 5. Cross-sectional SEM images of N-B/Al2O3 composite
coating electrodeposited at current density (a) 0.5 A dm−2;
(b) 1 A dm−2; (c) 3 A dm−2 and (d) 7 A dm−2.
Fig. 6. EDS spectra of (a) Ni-B and (b) Ni-B/Al2O3 com-
posite coating prepared with TMAB 3 g L−1, 1 A dm−2,
30 min.
72.4° and 87.7° were observed respectively. The sharp peaks of (200),
(111) indicate the coatings are crystalline or nanocrystalline. This is
because that the crystalline state was more easily formed in the absence
of TMAB.
Compared with the Ni/Al2O3, with the increase of TMAB con-
centration, the most obvious change in XRD patterns of Ni-B/Al2O3 is
the disappearing of Ni (200) peak at 52.0° and the decrease of Ni (111)
peak at 42.7°. It indicates that a series of new amorphous structures
were formed which lead to novel physical properties. In Fig. 7, there is
no extra peaks that could be attributed to the presence of the inter-
metallic phases Ni3B or Ni2B [37–39]. The presence of broad Ni (111)
peak is an indication of amorphous nature of the coating in its as-de-
posited state. The decrease of the (111) peaks indicates that there is a
direct correlation between the B content in the coating and the amor-
phous structure growth in the nanocomposites with increasing the
TMAB contents. It demonstrates that incorporation of B in the coating
resulted in an amorphous structure of the coatings.
Usually, the structure of Ni-B/Al2O3 coatings is highly influenced by
the coating composition. In their as-deposited state, the coatings are
nanocrystalline or quasi-amorphous depending upon the boron content.
The finer the grain size is, the more amorphous character of the coat-
ings is prevalent. This is well consistent with the surface morphology
analysis in Fig. 4 and the previous studies [40, 41]. Moreover, when the
B. Li et al.
Fig. 8. XRD patterns of N-B/Al2O3 composite coating electrodeposited at different current
density.
TMAB concentration is up to 9 g L−1, it was observed that the Ni (111)
peak was almost disappeared, which suggests that the main structure
was transformed to amorphous. The presence of a broad peak in as-
deposited Ni-B/Al2O3 coating can be further explained that Ni-B coat-
ings are solid solution of boron in fcc Ni lattice. The formation of
substituted solid solution can be indicative of the co-deposition of
boron in elementary form. According to the literature [7], the peaks of
(220) (311) reflections were completely disappeared in the XRD pattern
of the amorphous Ni-B alloy. In Fig. 7, the peaks of (220), (311) still
exist in the XRD patterns. This is associated with the influence of Al2O3
nanoparticles which could improve the crystallinity of the Ni-B matrix.
It demonstrates that increasing the boron content in the coating results
in decreasing of grain size, and the more amorphous structure was
produced.
Fig. 8 is the XRD patterns of the Ni-B/Al2O3 nanocomposite coating
electrodeposited at different current density 0.5, 1, 3, 5 and 7 A dm−2.
The Ni (111), Ni (220) and Ni (311) reflections in the XRD patterns of
the Ni-B/Al2O3 coating was observed corresponding to the phase angle
44.7°, 72.5°, 87.7°, respectively. It shows that the Ni (220) peak was the
main crystal orientation at 0.5 A dm−2. It was also found that with the
increase of current density, the much broad Ni (111) peak gradually
increased and narrowed. At the same time, the intensity of Ni (220) and
Ni (311) decreased. When the current density is below 1 A dm−2, the
existence of the broad peak of Ni (111) shows the coatings in their as-
deposited state are mainly amorphous. Intensities of (111) peaks in-
crease by increasing the current density while the intensity of (220) and
(311) peaks decrease, which indicates that the crystal orientation was
changed to (111) reflections. As seen in Fig. 8, the indexing of the peaks
shows that the major phase corresponded to Ni-B solid solution and the
minor phase was recognized as Al2O3 reinforcement. In addition to
crystalline structure, the preferred orientation of Ni-B films depended
on plating conditions; for example, the preferred orientation of elec-
trodeposited Ni-B films was changed from (220) to (111) by increasing
current density (Fig. 8), and finally (200) disappeared. In fact, the
crystal structure of Ni-B/Al2O3 can be crystalline or amorphous mainly
based on the amount of boron and Al2O3 particle content. Furthermore,
the reduction in grain size also leads to the amorphous character of the
coatings. The presence of additional peaks of Ni (220) and Ni (311) in
the XRD patterns suggests that the incorporation of nanoparticles of
Al2O3 has resulted in improvement in crystallinity of the binary Ni-B
coatings. This result indicated that high current density will change the
parent amorphous crystal structure into crystalline and enhances the
surface roughness with considerable grain size increases. The finer of
the coating grain is, the more amorphous structure was formed.
Therefore, it can be concluded that amorphous structure of the coating
is easily obtained at low current density. Crystalline will be promoted at
high current density. Thus, better Ni-B/Al2O3 coatings with good
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Surface & Coatings Technology 337 (2018) 186–197
corrosion resistance and anti-wear properties were expected to be ob-
tained at low deposition current density.
The X-ray amorphous structure of the Ni-B matrix implies two
possible reasons regarding its structural characteristics. One is the
formation of the amorphous Ni-B structure by randomly incorporating
B atoms into the FCC lattice of Ni. The other is the growth of small
nanocrystallites. The two structural changes could bring about positive
effects on strengthening the composite coatings. Ni-B/Al2O3 composite
coating shows the typical FCC lattice [42–44]. Ni-B deposits form solid
solution through B displaces a part of nickel atoms into the nickel
crystal lattice. With the increase of B content, Ni content in the deposits
slightly decreases which facilitates the formation of amorphous struc-
ture. Ni-B/Al2O3 composite coating consists of Ni-B alloy solid solution
and Al2O3 nanoparticles. As hardening element, Al2O3 can improve the
hardness of the coating and strengthen the Ni-B matrix which has better
wear resistance.
3.4. Effects of electrolyte composition on the properties of Ni-B/Al2O3
coating
3.4.1. The effects of TMAB concentration in the bath
Although wear resistance of the Ni-B/Al2O3 composite coating de-
pends on many factors, the hardness is one of the main influencing
factors for anti-wear performance. The hardness of the composite
coating is dependent on many factors such as B content, nanoparticle
content, heat treatment, bath pH, current density as well as the mi-
crostructure. Apparently, it is not easy to elucidate the effects of each
factor on the hardness of the deposited coating in this short section,
which affects the wear resistance of the coatings. Herein, the main
factors which affect the hardness and boron content of the co-deposited
coating were studied.
The boron content greatly affects the hardness of the Ni-B/Al2O3
composite coating. It is well known that the incorporation of TMAB into
the Ni electrolyte results in co-deposition of boron and Ni. Fig. 9 shows
the hardness values and boron content of Ni-B coatings deposited from
Ni-B/Al2O3 electrolyte at various TMAB concentrations. The coatings
were electrodeposited at 1 A dm−2 for 30 min. As shown in Fig. 9, the
coating hardness was drastically influenced by adding a small amount
of TMAB in baths. It can be seen that the hardness increases from 320 to
400 HV up to the highest level of 870 ± 20 HV with the TMAB con-
centration up to 2 g L−1. Then, continue to increase the TMAB con-
centration, the hardness of the composite coating decreased slightly to
840 ± 20 HV. However, considering the standard deviation, in this
concentration range, hardness is practically constant. Meanwhile, the
boron content in the Ni-B/Al2O3 coating increased with the increase of
the TMAB in the bath. It was found that co-deposited boron atoms had a
beneficial effect on the hardness of the coating. Nevertheless, it was also
observed that boron content increased when adding 2–10 g L−1 TMAB
Fig. 9. Hardness and boron content of Ni-B/Al2O3 coating as a function of TMAB con-
centration in the plating bath.
B. Li et al.
in the bath, but the coating hardness was stable in this range. Therefore,
by comparing the hardness and boron content, it seems that the re-
lationship between coating hardness and boron content is complex.
These results indicate that hardness of coatings is not only related to the
B content in the coating but also the crystalline structure, crystal size,
and other factors. The most important effect of the TMAB is the
transformation of the crystal structure of Ni to amorphous phase of Ni-B
which improves the corrosion resistance as well as microhardness. In
addition, the TMAB has the beneficial effect in grain refinement. As for
Ni-B/Al2O3 coating, in addition to the texture (111) orientation, the
peaks of (220) and (311) could also be noticed in the XRD patterns due
to the existence of Al2O3 particles. Then more work needs to be done to
investigate their influence on the hardness of Ni-B/Al2O3coatings.
The mechanism of co-deposition of boron in Ni-B coatings prepared
by electrodeposition technique is not yet fully understood. It is assumed
that boron is incorporated into Ni-B coating due to the adsorption of
TMAB on the surface of already formed nickel which is then decom-
posed to elemental boron. Therefore, the amount of boron co-deposited
with nickel can be determined by the distribution of TMAB and the
thickness of the diffusion layer at the cathode surface, regardless of the
electrode potential.
3.4.2. The effect of Al2O3 nanoparticle concentration in the bath
Firstly, it needs to be noted that Al2O3 content in the deposited
coating is dependent on many factors such as the Al2O3 concentration
in the bath, stirring rate, as well as current density. Due to the huge
workload, in this section, the constant value of Al2O3 concentration
(15 g L−1) and stirring rate (400 rpm) was adopted. Thus, the effect of
current density on the Ni-B/Al2O3 nanocomposite coating was in-
vestigated.
Fig. 10 shows the effect of current density on the Al2O3 content in
the Ni-B/Al2O3 nanocomposite coating. With the increase of the current
density, the Al2O3 content initially increases, then decreases with the
maximal value at 1 A dm−2 . It is believed that the amounts of particles
incorporated into the metal matrix are determined by the rate of the
particles and cations arrive at the cathode surface. The co-deposition of
Al2O3 particles starts with the adsorption of the Al2O3 particles on
electrodes, and then, the adsorbed Al2O3 particles are surrounded with
electrodeposited Ni-B. If the adsorbed Al2O3 particles drop off from the
electrodes by the effect of sedimentation or convection, the Al2O3
content will decrease. Therefore, a relatively high growth rate of Ni-B to
attach the Al2O3 particles onto the electrodes would be necessary to co-
deposit Al2O3 particles constantly.
The reason why Al2O3 content depended on current density could be
explained as follows. Since the rate of electrodeposition of Ni-B was
electron transfer controlled, the growth rate of Ni-B proportionally in-
creased with the current density. However, the co-deposition rate of
Al2O3 particles was irrelevant to current density because the co-
Fig. 10. Effect of current density on Al2O3 content in the Ni-B/Al2O3 coating.
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Surface & Coatings Technology 337 (2018) 186–197
deposition was initiated by the adsorption of particles on the electrode
surface. Thus, it is possible that the Al2O3 content was relatively in-
fluenced by current density because only the growth rate of Ni-B was
changed by current densities. With the increase of current density, the
deposition rate of Ni is faster than the rate of inert particle transfer to
the cathode surface. Thus, in a relatively lower current density range,
there is an increase in the flux of particles with increasing current
density and later a decrease in the higher current density region.
Although this explains the tendency at current densities above
1 A dm−2, it would not explain the changes in Al2O3 content at the
current density below 1 A dm−2. In this range, the effect of sedi-
mentation and convection on the Al2O3 particles adsorbed on the sur-
face of the growing coating would not be negligible.
It was reported that the increase in polarization caused by higher
current densities, results in intensification of hydrogen evolution which
may lead to the decrease of the incorporated particles [28]. In our
study, hydrogen evolution may significantly influence the incorpora-
tion of Al2O3 nanoparticles in case of the deposition process carried out
at the current density higher than 5 A dm−2. Intense hydrogen evolu-
tion process leads to the formation of large amounts of gas bubbles on
the cathode surface, which may prevent the adsorption of Al2O3 na-
noparticles on the growing deposit. As a result, composites with lower
nanoparticle content are obtained.
Fig. 11 shows the effect of Al2O3 particle concentration in baths on
the hardness and the Al2O3 content of electrodeposited Ni-B/Al2O3
composite coatings. The hardness of the Ni-B/Al2O3 composite coating
was measured before and after thermal treatment at 300 °C in the air for
1 h. At low Al2O3 concentration, microhardness increases significantly
with increasing Al2O3 content. However, further increasing Al2O3 to
above 20 g L−1 led to a decrease of microhardness, which is even worse
than that of Ni-B coating. Moreover, it was noticed that thermal
treatment drastically increased the hardness and the hardness was also
related to the Al2O3 content. Fig. 11 shows that the Al2O3 content be-
came higher as the Al2O3 particle concentration in the baths increased.
Several factors possibly determine the hardness of the Ni-B/Al2O3
composite coatings. The strengthening mechanism of composite coat-
ings can be mainly attributed to two factors. One is the amount of
second phase or hard particles incorporated into the coatings matrix,
which provides the dispersion strengthening effect. The other is the
microstructure change of coating matrix which caused by the em-
bedded second phase or hard particles. The effect of the thermal
treatment is explained by hardening of the Ni-B matrix. It is well known
that appropriate thermal treatments harden Ni-B coating because of the
phase transition from amorphous Ni-B alloy to hard Ni3B and Ni2B al-
loys. Al2O3 content leads to better dispersion strengthening, resulting in
a significant increase of mechanical property of the coating. However,
Al2O3 nanoparticles start to agglomerate when excessive Al2O3 were
added into the electrolytes, and tend to cause porous structure in the
Fig. 11. Hardness and Al2O3 content of Ni-B/Al2O3 composite coating as a function of the
Al2O3 concentration in the plating bath,1 A dm−2, TMAB 3 g L−1, Al2O3 15 g L−1.
B. Li et al.
grain boundaries. This decreasing trend might be linked to the Al2O3
nanoparticle agglomeration. It will reduce the effect of dispersion, ul-
timately lead to a deterioration of the mechanical property.
The effects of Al2O3 nanoparticle on the structure and property of
the Ni-B alloy were further investigated. The addition of Al2O3 nano-
particle in Ni-B electrolyte could influence the Ni-B electrodeposition in
many aspects, such as metallic luster, chemical composition, phase
structure, corrosion resistance as well as hardness of the Ni-B matrix
[32, 33, 40, 45]. Fig. 12a is the morphology of the Ni-B/Al2O3 coating
deposited with 10 g L−1 Al2O3 nanoparticles. It can be seen that the
nodular surface of the composite coating was smooth, uniform and fine-
grained. In addition, as shown in Fig. 12b, the cross-sectional images
show that the bulk of the nanocomposite is compact and uniform. The
interface between the substrate and coating has a good combination.
This suggests that excellent adhesion was obtained for the Ni-B/Al2O3
composite coating.
During electrodeposition process, many Al2O3 particles are in-
corporated into Ni-B matrix. The cross-sectional images of the coatings
were performed in larger magnification to observe the distribution of
Al2O3 particles in the bulk of Ni-B/Al2O3 composite coating. As shown
in Fig. 12c, the Al2O3 nanoparticles are uniformly dispersed and em-
bedded in the bulk of the Ni-B matrix without segregation. Vigorous
stirring is necessary to obtain a homogenous distribution of nano-
particles in the reinforced composite coating. In this work, stirring
speed of 400 rpm was employed to obtain high-performance Ni-B
composite coatings.
The embedded Al2O3 particles into Ni-B matrix play a significant
role in determining the chemical composition and microstructure, and
strengthen the microhardness of the composite coatings. XRD patterns
of Ni-B/Al2O3 coatings in as-deposited states deposited with different
concentration of Al2O3 nanoparticles in the bath are shown in Fig. 12d.
In the XRD patterns, only diffraction lines assigned to Ni metal were
observed; diffraction lines assigned to neither B nor Ni-B alloys (e.g.,
Ni3B and Ni2B) was noticed, implying that boron atoms are finely and
disorderly deposited into Ni matrix with face center cubic (fcc) struc-
ture. In Fig. 12d, it shows that with the increase of Al2O3 particles in the
bath, the formation of the crystalline structure was facilitated. How-
ever, it was observed that the preferred Ni (111) orientation increased
193
Surface & Coatings Technology 337 (2018) 186–197
Fig. 12. (a) surface morphology, (b, c) cross-sectional
morphology, (d) XRD patterns of Ni-B/Al2O3 nanocompo-
site coating prepared with different Al2O3 concentration in
the bath.
when Al2O3 particles surpass 20 g L−1. The preferred orientation of
electrodeposited metal films is significantly affected by adsorbed spe-
cies on the coating. It is possible that the adsorption of not only Hads, Ni
(OH)2, H2 molecules but also boron sources and their decomposition
products would exert an influence on the preferred orientation of Ni-B
films. Now, the change in the preferred orientation of electrodeposited
Ni-B films is still unclear. The addition of Al2O3 has resulted in the
transformation of amorphous structure to crystalline structure.
It was observed that the incorporation of nanoparticles of Al2O3 has
also resulted in significant grain refinement of the Ni-B matrix. At the
same time, this refinement in grain size is quite desired as the fine grain
structure of the coating leads to enhance the mechanical properties. The
mechanism of grain refinement can be explained that during the elec-
trodeposition process, Al2O3 particles adsorb cations in the bath under
the high potential gradient. They will then be transported to the
cathode surface by electrophoresis and then adsorbed on the cathode
surface [46]. This phenomenon increases electro crystalline potential
because the incorporated particles decrease the active cathode surface.
Secondly, the occurrence of new nuclei in the form of nanoparticles
limits the growth of the original crystal grains. It is considered that both
of the factors are favorable for fine grains and good surface morphology
of the Ni-B/Al2O3 [47, 48]. Moreover, the incorporation of Al2O3 na-
noparticles into the growing Ni-B matrix results in the decrease of ac-
tive cathode surface, which improves the corrosion resistance of Ni-B
coating. Increasing Al2O3 concentration in the electrolyte improves the
amount of adsorbed Al2O3 nanoparticles on the surface of the growing
deposit which results in more nanoparticles incorporation in the
coating.
3.5. Effects of operating parameters and heat treatment on the properties of
Ni-B/Al2O3 coating
3.5.1. Effect of bath pH value
The effects of bath pH on the hardness and boron content are also
investigated, as shown in Fig. 13. The coating hardness increased with
pH increasing and showed the maximum hardness at about pH 3.5.
Likewise, boron content in Ni-B/Al2O3 increased with the increase of
the pH value. When the pH is below 2, the boron precursor of TMAB
B. Li et al.
Fig. 13. Hardness and boron content of Ni-B/Al2O3 coating as a function of the bath pH,
1 A dm−2.
might decompose due to the acidic conditions. Therefore, the boron
content would be small in plating baths with low pH values. In general,
hydrogen evolution will be promoted in plating bath at low pH value.
However, at high pH conditions, the stability of plating bath will de-
crease. Taking into account the relevant literature and experiment re-
sults, pH 3.5 was adopted for electrodeposition of Ni-B/Al2O3 nano-
composite coating.
3.5.2. Effect of current density
Fig. 14 shows hardness and boron content of Ni-B/Al2O3 coatings
prepared under different current densities. As seen in Fig. 14, the
hardness of Ni-B/Al2O3 nanocomposite coating was hardly affected by
current density; the hardness gradually decreased with increasing cur-
rent density. As for boron content, the content of B in Ni-B/Al2O3 na-
nocomposite coating remarkably decreases from 12.3 at.% to 5.7 at.%
by increasing current density from 1 to 7 A dm−2. The maximum B
content (12.3 at.%) was achieved for the coating deposited at 1 A dm−2.
This is because the co-deposition rate of the Al2O3 particles is almost
the same while the deposition rate of Ni increased fast with the increase
of current density. Therefore, the amounts of incorporated particles are
determined by the particle flux to the cathode surface; more Al2O3
particles will co-deposited in the coating at low current density.
3.5.3. Effect of thermal treatment
The effect of thermal treatment on the hardness and grain size of Ni-
B/Al2O3 coatings are shown in Fig. 15. Compared to the hardness of
electrodeposited Ni-B coating in as-deposited condition, not much has
changed in hardness at the temperatures lower than 200 °C. With fur-
ther increase in temperatures, however, the hardness increases rapidly,
as the structure of the coatings begins to change. As shown in Fig. 15,
the hardness of as-deposited Ni-B/Al2O3 coating is 730 ± 30 HV, and it
Fig. 14. Hardness and boron content of Ni-B/Al2O3 coating as a function of current
density.
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Surface & Coatings Technology 337 (2018) 186–197
Fig. 15. Hardness and grain size of Ni-B/Al2O3 coating electrodeposited at 1 A dm−2 as a
function of heat-treatment temperature.
increases significantly as the treatment of temperature increases,
reaching its highest value (1100 ± 30 HV) after heat treatment at
300 °C for 50 min. Then, further increase the temperature of heat
treatment results in the obvious decrease of hardness. At higher tem-
peratures, hardness decreases gradually with the increase of tempera-
ture. Initially, at temperatures below 300 °C, the obvious increase in
hardness can be attributed to the fact that higher thermal treatment
temperatures favor the precipitation of nickel boride (Ni3B) and in-
crease the Ni crystal size. The Ni3B particles are so small that their
characterization peak can hardly be seen from the XRD spectrum. When
heat treatment temperature is less than or equal to 300 °C, the increase
of grain size is slight. However, beyond 300 °C, the grain size increases
considerably and exceeds the size of Ni3B phase. Then the hardness of
the Ni-B/Al2O3 coating was reduced. At temperatures above 300 °C, the
coating begins to soften as a result of coarsening of the Ni3B particles,
which thereby reduces the number of hardening sites. The formation of
hard Ni3B particles results in hardening of the coatings, and the grain
coarsening due to excess heat treatments decreases the hardness of the
coating.
3.6. Corrosion resistance of Ni-B/Al2O3 nanocomposite coatings
Few works have reported the corrosion properties of Ni-B matrix
containing Al2O3 nanoparticles. Therefore, the corrosion resistance of
the Ni-B/Al2O3 coating needs more careful discussion and analysis. The
corrosion behavior of Ni-B/Al2O3 deposited with different TMAB con-
centration and at different current density, were investigated in 3.5%
NaCl solution. Fig. 16 is the potentiodynamic polarization curves, and
Nyquist plots for the Ni-B/Al2O3 prepared at different conditions after
immersed in 3.5% NaCl solution for 10 days. As shown in Fig. 16a, it
can be seen that, with the increase of TMAB concentration in the plating
bath, the Ecorr of the Ni-B/Al2O3 coating shifts to negative potential.
This indicates that the inclusion of B is not necessary to improve the
corrosion resistance of the coating. It cannot draw such a conclusion
that the more incorporation of B in the deposits, the better corrosion
resistance of the coatings. It was also observed in Fig. 16a that icorr
slightly increases with the increase of the TMAB concentration. It is
probably because that increasing the boron content in the composite
coating, the brittle fracture will be promoted for the Ni-B matrix with a
high content of boron in the coating, which will deteriorate the cor-
rosion resistance of the coating. Another reason is related to the high
internal stress in the deposits due to the intense hydrogen evolution
reaction. High content of boron in the coating has deleterious effects on
the corrosion properties.
Fig. 16b shows the Nyquist plots of Ni-B/Al2O3 composite coating
prepared with different TMAB concentration after immersion in 3.5%
NaCl solution for 240 h. As shown in Fig. 16b, it was found that addi-
tion of 3 g L−1 TMAB have a beneficial effect on the improvement of the
B. Li et al.
Fig. 16. Tafel and Nyquist plots of N-B/Al2O3 coating obtained at different (a, b) TMAB concentration; (c, d) current density, after immersed in 3.5 wt% NaCl aqueous solution for 240 h.
anti-corrosion properties of the Ni-B/Al2O3 composites, which is con-
firmed by the largest radius of the capacitive semicircle in Nyquist plot
for the Ni-B/Al2O3 coating obtained with 3 g L−1 TMAB. It shows that
the radius of the capacitive semicircle in Nyquist plot for the Ni-B/
Al2O3 coating obtained with 3 g L−1 TMAB was the largest compared to
other coatings. It also indicates that more or less than 3 g L−1 TMAB
will decrease the corrosion resistance of the coating. It is associated
with the high internal stress and brittle fracture with high B content in
the coating. It is known that additional capacitance character can im-
prove the protective ability of the coating through hindering substance
transportation across the coating. The capacitive feature improves the
stability of the protective coatings. This enhanced corrosion resistance
is due to the formation of a compact protective oxide film on the metal
surface. The Ni-B coatings with a low boron content demonstrate the
maximum corrosion resistance which may be caused by a sharp de-
crease in grain size in comparison with boron-free Ni ones. This is be-
cause that the corrosion resistance of the electrodeposited coatings in-
creased significantly as the grain size decreased to nanocrystalline. This
effect can be explained by the more rapid formation of a compact
passive film on nanocrystalline Ni owing to a higher density of nu-
cleation sites for the passive film.
Electrodeposition current density has important influences on the
growth and properties of Ni-B/Al2O3 composites. The electrodeposition
process will be promoted with the increase of current density. In the
previous literature, it is generally that the same thickness of the coating
was employed to study the coating properties by regulating the other
deposition parameters, such as deposition time [49–51]. Fig. 16c shows
the Tafel and Nyquist plots of Ni-B/Al2O3 composite coating prepared
at different current density after immersion in 3.5% NaCl solution for
240 h. It was noticed that increasing the current density from 0.5 to
1 A dm−2, the Ecorr of the Ni-B/Al2O3 coating substantially shifts to a
positive potential, and the icorr decreases at the same time, which is an
195
Surface & Coatings Technology 337 (2018) 186–197
indicator of the improvement of corrosion resistance. It needs to be
pointed out that the same deposition time (30 min) was employed in
this section. Therefore, the coating obtained at different current density
has the different thickness which also means the different growth rate.
Although low current density could improve the properties of the de-
posits, the thickness of the coating obtained at low current density is
smaller than that prepared at the high current density under the same
deposition time. Thus, the Fig. 16c describes the coatings with different
thickness which prepared at different current density. So, it could not
exactly elucidate the effects of current density on the Ecorr and icorr of
the coatings under the extra influence of the thickness. Although the
high growth rate of the composite coatings is much desired, the optimal
current density is not the highest value because more internal stress will
be accumulated at high current densities which leads to cracks forma-
tion.
Fig. 16d is the EIS results of Ni-B/Al2O3 coatings prepared at dif-
ferent current density. As shown in Fig. 16d, when current density was
0.5 A dm−2, the capacitive arc radius of Ni-B/Al2O3 was small compared
to other samples. Increasing the current density to 5 A dm−2, it found
that the capacitive arc radius sharply increases to a maximum. How-
ever, continue to increase the current density to 7 A dm−2, the radius
gradually decreases. As for the 7 A dm−2, it is essential to notice that
the grain size is large compared to that of low current density due to the
high growth rate of the coating. In this case, considering that the same
deposition time was adopted which results in the different coating
thickness., it can be concluded that the corrosion resistance begins to
deteriorate when current density exceeds 5 A dm−2 . In brief, a better Ni-
B/Al2O3 coating can be obtained at a low current density in the case of
sufficient time, such as 1 A dm−2.
B. Li et al.
Fig. 17. Friction coefficient and wear track profiles of N-B/Al2O3 composite coating deposited at different (a, c) TMAB; (b, d) current density under the dry-sliding condition (10 N, 5 Hz).
3.7. Anti-wear performance of Ni-B/Al2O3 nanocomposite coatings
Fig. 17 comparatively shows the friction coefficient of different
coatings under dry-sliding condition (10 N, 5 Hz). It shows that the
stable friction coefficient of the Ni-Al2O3 coating is 0.42. As shown in
Fig. 16a, with the incorporation of B into the Ni-Al2O3 coatings, the
friction coefficient increases from 0.42 up to 0.48, 0.79, 0.39 corre-
sponding to the TMAB concentration of 3, 6 and 9 g L−1, respectively.
Nevertheless, when the TMAB is 9 g L−1, the friction coefficient of the
coating sharply decreased to 0.39. The effect of current density on the
friction coefficient can be found in the Fig. 17b. It indicates that the
friction coefficient of the Ni-B/Al2O3 ranges from 0.48 to 0.43 when the
current density is between 0.5 and 3 A dm−2. However, when the
current density is above 5 A dm−2, the friction coefficient greatly in-
creases to 0.59. As a result, the value of the friction coefficient is af-
fected by the B content, Al2O3 particle content in the coating and cur-
rent density of the electrodeposition.
The wear track profiles of different coatings under the dry-sliding
condition (10 N, 5 Hz) are also shown in Fig. 17(c, d), which is an in-
tuitive way to compare the wear rates of different coatings. The wear
track profiles were measured using a surface profiler (Alpha-Step IQ) to
measure, origin 9 software is used to calculate area size of the wear
track profile, the wear rates of specimens were calculated using the
equation of (1). Under the dry-sliding condition (10 N, 5 Hz), the wear
rate of as-deposited Ni-B/Al2O3 coatings is between 0.782 × 10−6 to
2.371 × 10−6 mm3/Nm when bath contains 3 g L−1 TMAB,
10–20 g L−1 Al2O3 particles. However, as for the coatings of Ni/Al2O3
or Ni-B, it was found that the wear rate was extremely high in com-
parison with Ni-B/Al2O3 composite coating. The Ni-B/Al2O3 composite
coating exhibits better wear resistance than that of Ni/Al2O3 or Ni-B.
Ni-B/Al2O3 coatings with higher hardness have superior anti-wear
performance. The presence of Al2O3 particles embedded into the metal
or alloy matrix increased the wear resistance of the composite coatings.
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Surface & Coatings Technology 337 (2018) 186–197
Meanwhile, the B content in the coating has great influence on the anti-
wear properties. As for the Al2O3 particles, it indicates that inclusion of
10 to 20 g L−1 Al2O3 particles in the bath can decrease the wear rate
and improve the hardness of the composites. Furthermore, low current
density, such as 1 A dm−2, will facilitate the improvement of wear re-
sistance due to the dense, uniform, fine-grained coating with high B and
Al2O3 particle content. Ni-B/Al2O3 composite coatings showed ex-
cellent mechanical properties such as hardness and anti-wear perfor-
mance because of the high hardness of both Ni-B matrix and Al2O3
particles. Therefore, it is expected that Ni-B/Al2O3 have a better pro-
tection performance and service life in harsh corrosion environment.
4. Conclusions
In summary, we have prepared a novel Ni-B/Al2O3 composite
coating by electrodeposition using TMAB as boron precursor in a
modified Ni-B electrolyte containing suspended Al2O3 nanoparticles.
The effect of TMAB, Al2O3, current density and thermal treatment on
the structure and properties of Ni-B/Al2O3 coatings were investigated.
It demonstrates that the addition of TMAB promotes the grain refine-
ment and results in the formation of uniform, fine-grained, dense and
amorphous structure. The content of boron in the coatings transforms
Ni to Ni-B matrix with the emerging of amorphous texture which has
better wear resistance. The mechanical properties of Ni-B coatings can
be improved by the addition of Al2O3 particles owing to the dispersion
hardening of the added hard Al2O3 nanoparticles and the grain re-
finement of Ni-B matrix. Moreover, the results confirm that the inclu-
sion of Al2O3 improves the corrosion resistance of Ni-B coating which
may be related to the dense structure and the reduction in the active
surface area of Ni-B matrix by the presence of inert Al2O3 particles.
Current density also affects the structure and hardness of the composite
coatings because both the boron and Al2O3 nanoparticle content in the
deposited Ni-B/Al2O3 coating decreases as the current density increased
B. Li et al.
from 1 to 7 A dm−2. At high current density, the Al2O3 content rela-
tively decreases because the co-deposition rate of Al2O3 particles was
irrelevant to current density because the co-deposition was initiated by
the adsorption of particles on the electrode surface, while the growth
rate of Ni-B proportionally increased with the current density. In
principle, we can also modify the microhardness of the Ni-B/Al2O3
coating by regulating the current density. Especially, the synergistic
effect of B, Ni-B alloy and Al2O3 nanoparticles which make full use of
the superiorities of each component and involved some transformation
of phase structure, makes a great contribution to enhancing the cor-
rosion resistance, increasing the hardness, and improving the practical
wear resistance. Due to the grain refinement of Ni-B matrix, dispersion
hardening of the added nanoparticles, as well as the reduction in the
active surface area of Ni-B matrix by the presence of inert particles, Ni-
B/Al2O3 with dense structure shows high anti-corrosion and wear re-
sistance than Ni/Al2O3 or Ni-B coating. The Ni-B/Al2O3 coating shows
superior anti-corrosion and wear resistance, and is expected to exhibit
high performance in harsh environment.
Acknowledgements
All the authors thank the following funds for the financial support:
National Natural Science Foundation of China (Grant No. 51679076,
51301061 and 51605137), Fundamental Research Funds for the Central
Universities of Hohai University, China (Grant No. 2013B32614).
References
[1] K. Krishnaveni, T.S.N. Sankara Narayanan, S.K. Seshadri, Electrodeposited Ni-B
coatings: formation and evaluation of hardness and wear resistance, Mater. Chem.
Phys. 99 (2006) 300–308.
[2] Y. Liang, Y. Li, Q. Yu, Y. Zhang, W. Zhao, Z. Zeng, Structure and wear resistance of
high hardness Ni-B coatings as alternative for Cr coatings, Surf. Coat. Technol. 264
(2015) 80–86.
[3] O.R. Monteiro, S. Murugesan, V. Khabashesku, Electroplated Ni-B films and Ni-B
metal matrix diamond nanocomposite coatings, Surf. Coat. Technol. 272 (2015)
291–297.
[4] H. Ogihara, K. Udagawa, T. Saji, Effect of boron content and crystalline structure on
hardness in electrodeposited Ni-B alloy films, Surf. Coat. Technol. 206 (2012)
2933–2940.
[5] F. Bülbül, L.E. Bülbül, Fabrication of antibacterial and hydrophilic electroless Ni-B
coating on 316L stainless steel, Appl. Phys. A Mater. Sci. Process. 122 (2015) 25.
[6] S. Eraslan, M. Ürgen, Oxidation behavior of electroless Ni-P, Ni-B and Ni-W-B
coatings deposited on steel substrates, Surf. Coat. Technol. 265 (2015) 46–52.
[7] Y.N. Bekish, S.K. Poznyak, L.S. Tsybulskaya, T.V. Gaevskaya, Electrodeposited Ni-B
alloy coatings: structure, corrosion resistance and mechanical properties,
Electrochim. Acta 55 (2010) 2223–2231.
[8] M. Romero-Romero, C. Domínguez-Ríos, R. Torres-Sánchez, A. Aguilar-Elguezabal,
Electroless Ni-B coating onto TiH2 powder: an approach for a simplified surface
preparation, Surf. Coat. Technol. 315 (2017) 181–187.
[9] K.H. Lee, D. Chang, S.C. Kwon, Properties of electrodeposited nanocrystalline Ni-B
alloy films, Electrochim. Acta 50 (2005) 4538–4543.
[10] J.R. López, J.R. López, P.F. Méndez, J.J. Pérez-Bueno, G. Trejo, G. Stremsdoerfer,
Y. Meas, The effect of boron content, crystal structure, crystal size on the hardness
and the corrosion resistance of electrodeposited Ni-B coatings, Int. J. Electrochem.
Sci. 11 (2016) 4231–4244.
[11] H. Ogihara, M. Safuan, T. Saji, Effect of electrodeposition conditions on hardness of
Ni-B/diamond composite films, Surf. Coat. Technol. 212 (2012) 180–184.
[12] H. Kwon, K. Kim, H. Ahn, Y. Kim, Electrodeposition and characterization of na-
nocrystalline Ni-B with low boron content for MEMS applications, Sens. Mater. 29
(2017) 225–234.
[13] H. Ogihara, H. Wang, T. Saji, Electrodeposition of Ni-B/SiC composite films with
high hardness and wear resistance, Appl. Surf. Sci. 296 (2014) 108–113.
[14] A.B. Radwan, R.A. Shakoor, A. Popelka, Improvement in properties of Ni-B coatings
by the addition of mixed oxide nanoparticles, Int. J. Electrochem. Sci. 10 (2015)
7548–7562.
[15] B. Li, W. Zhang, W. Zhang, Y. Huan, Preparation of Ni-W/SiC nanocomposite
coatings by electrochemical deposition, J. Alloys Compd. 702 (2017) 38–50.
[16] W. Sun, P. Zhang, K. Zhao, M. Tian, Y. Wang, Effect of graphite concentration on the
friction and wear of Ni-Al2O3/graphite composite coatings by a combination of
electrophoresis and electrodeposition, Wear 342 (2015) 172–180.
[17] S. Huang, Y. Hu, W. Pan, Relationship between the structure and hydrophobic
performance of Ni-TiO2 nanocomposite coatings by electrodeposition, Surf. Coat.
Technol. 205 (2011) 3872–3876.
[18] S. Sadreddini, A. Afshar, Corrosion resistance enhancement of Ni-P-nano SiO2
composite coatings on aluminum, Appl. Surf. Sci. 303 (2014) 125–130.
[19] Y. Yao, S. Yao, L. Zhang, Corrosion behavior of Ni-W/SiC nanocomposite coating in
NaCl solution, Surf. Rev. Lett. 13 (2006) 489–494.
[20] C. Guo, Y. Zuo, X. Zhao, J. Zhao, J. Xiong, The effects of electrodeposition current
density on properties of Ni-CNTs composite coatings, Surf. Coat. Technol. 202
197
Surface & Coatings Technology 337 (2018) 186–197
(2008) 3246–3250.
[21] Z. Huang, D. Xiong, MoS2 coated with Al2O3 for Ni-MoS2/Al2O3 composite coatings
by pulse electrodeposition, Surf. Coat. Technol. 202 (2008) 3208–3214.
[22] K. Krishnaveni, T.S.N. Sankara Narayanan, S.K. Seshadri, Electrodeposited Ni-B-
Si3N4 composite coating: preparation and evaluation of its characteristic properties,
J. Alloys Compd. 466 (2008) 412–420.
[23] F. Cai, C. Jiang, Z. Zhang, V. Ji, Synthesis and characterization of Ni-Al-Y2O3
composite coatings with different Y2O3 particle content, Ceram. Int. 40 (2014)
15105–15111.
[24] I. Tudela, Y. Zhang, M. Pal, I. Kerr, A.J. Cobley, Ultrasound-assisted electro-
deposition of thin nickel-based composite coatings with lubricant particles, Surf.
Coat. Technol. 276 (2015) 89–105.
[25] E. Correa, J.F. Mejia, J.G. Castano, F. Echeverria, M.A. Gomez, Tribological char-
acterization of electroless Ni-B coatings formed on commercial purity magnesium,
J. Tribol. 139 (2017) 051302.
[26] J.L. Wang, R.D. Xu, Y.Z. Zhang, Influence of SiO2 nano-particles on microstructures
and properties of Ni-W-P/CeO2-SiO2 composites prepared by pulse electrodeposi-
tion, Trans. Nonferrous Metals Soc. China 20 (2010) 839–843.
[27] Y.W. Yao, S.W. Yao, L. Zhang, H.Z. Wang, Electrodeposition and mechanical and
corrosion resistance properties of Ni-W/SiC nanocomposite coatings, Mater. Lett. 61
(2007) 67–70.
[28] D. Ekmekci, F. Bulbul, Preparation and characterization of electroless Ni-B/nano-
SiO2, Al2O3, TiO2 and CuO composite coatings, Bull. Mater. Sci. 38 (2015) 761–768.
[29] F. Madah, C. Dehghanian, A.A. Amadeh, Investigations on the wear mechanisms of
electroless Ni-B coating during dry sliding and endurance life of the worn surfaces,
Surf. Coat. Technol. 282 (2015) 6–15.
[30] A. Karabulut, M. Durmaz, B. Kilinc, U. Sen, S. Sen, Effect of H3BO3 on the corrosion
properties of Ni-B based electroplating coatings, Acta Phys. Pol. A 131 (2017)
147–149.
[31] L. Tarkowski, P. Indyka, E. Beltowska-Lehman, XRD characterisation of composite
Ni-based coatings prepared by electrodeposition, Nucl. Instrum. Methods Phys.
Res., Sect. B 284 (2012) 40–43.
[32] M. Ghaderi, M. Rezagholizadeh, A. Heidary, S.M. Monirvaghefi, The effect of Al2O3
nanoparticles on tribological and corrosion behavior of electroless Ni-B-Al2O3
composite coating, Prot. Met. Phys. Chem. Surf. 52 (2016) 854–858.
[33] R.A. Shakoor, R. Kahraman, U. Waware, Y. Wang, W. Gao, Properties of electro-
deposited Ni-B-Al2O3 composite coatings, Mater. Des. 64 (2014) 127–135.
[34] Y. Xuetao, W. Yu, S. Dongbai, Y. Hongying, Influence of pulse parameters on the
microstructure and microhardness of nickel electrodeposits, Surf. Coat. Technol.
202 (2008) 1895–1903.
[35] A.M. Rashidi, A. Amadeh, Effect of electroplating parameters on microstructure of
nanocrystalline nickel coatings, J. Mater. Sci. Technol. 26 (2010) 82–86.
[36] C. Cai, X.B. Zhu, G.Q. Zheng, Y.N. Yuan, X.Q. Huang, F.H. Cao, J.F. Yang, Z. Zhang,
Electrodeposition and characterization of nano-structured Ni-SiC composite films,
Surf. Coat. Technol. 205 (2011) 3448–3454.
[37] Y. Liang, X. Sun, A.M. Asiri, Y. He, Amorphous Ni-B alloy nanoparticle film on Ni
foam: rapid alternately dipping deposition for efficient overall water splitting,
Nanotechnology 27 (2016) 12LT01.
[38] Z. Liu, Y. Li, X. Huang, J. Zuo, Z. Qin, C. Xu, Preparation and characterization of Ni-
B/SiO2sol amorphous catalyst and its catalytic activity for hydrogenation of ni-
trobenzene, Catal. Commun. 85 (2016) 17–21.
[39] F. Madah, A.A. Amadeh, C. Dehghanian, Investigation on the phase transformation
of electroless Ni-B coating after dry sliding against alumina ball, J. Alloys Compd.
658 (2016) 272–279.
[40] R.A. Shakoor, U.S. Waware, R. Kahraman, A. Popelka, M.M. Yusuf, Corrosion be-
havior of electrodeposited Ni-B coatings modified with SiO2 particles, Int. J.
Electrochem. Sci. 12 (2017) 4384–4391.
[41] B. Li, W.W. Zhang, Electrochemical deposition of Ni-Co/SiC nanocomposite coat-
ings for marine environment, Int. J. Electrochem. Sci. 12 (2017) 7017–7030.
[42] E. Beltowska-Lehman, P. Indyka, A. Bigos, M. Kot, L. Tarkowski, Electrodeposition
of nanocrystalline Ni-W coatings strengthened by ultrafine alumina particles, Surf.
Coat. Technol. 211 (2012) 62–66.
[43] K.H. Hou, T.W. Han, H.H. Sheu, M.D. Ger, Preparation and wear resistance of
electrodeposited Ni-W/diamond composite coatings, Appl. Surf. Sci. 308 (2014)
372–379.
[44] L. Elias, A. Chitharanjan Hegde, Electrodeposition of laminar coatings of Ni-W alloy
and their corrosion behaviour, Surf. Coat. Technol. 283 (2015) 61–69.
[45] S. Wang, Y. Wang, X. Shu, S. Tay, W. Gao, R.A. Shakoor, R. Kahraman, Preparation
and property of duplex Ni-B-TiO2/Ni nano-composite coatings, Int. J. Mod. Phys. B
29 (2015) 1540022.
[46] A. Laszczyńska, J. Winiarski, B. Szczygieł, I. Szczygieł, Electrodeposition and
characterization of Ni-Mo-ZrO2 composite coatings, Appl. Surf. Sci. 369 (2016)
224–231.
[47] V. Niksefat, M. Ghorbani, Mechanical and electrochemical properties of ultrasonic-
assisted electroless deposition of Ni-B-TiO2 composite coatings, J. Alloys Compd.
633 (2015) 127–136.
[48] Y. Wang, S. Wang, X. Shu, W. Gao, W. Lu, B. Yan, Preparation and property of sol-
enhanced Ni-B-TiO2 nano-composite coatings, J. Alloys Compd. 617 (2014)
472–478.
[49] X. Wen, H. Dai, L. Wu, P. Wang, Electroless plating of Ni-B film as a binder-free
highly efficient electrocatalyst for hydrazine oxidation, Appl. Surf. Sci. 409 (2017)
132–139.
[50] C.A. García-Aguirre, C. Domínguez-Ríos, R. Torres-Sánchez, M. Román-Aguirre,
J.T. Holguín-Momaca, A. Aguilar-Elguézabal, Microstructure and transmission
electron microscopy characterization of electroless Ni-B thin films deposited on
MWCNTs, Surf. Coat. Technol. 282 (2015) 107–114.
[51] X. Fang, G. Jin, X.F. Cui, J.N. Liu, Evolution characteristics of residual stress in
metastable Ni-B alloy coatings identified by nanoindentation, Surf. Coat. Technol.
305 (2016) 208–214.