Mechanical and corrosion resistance properties of TiO

2
nanoparticles reinforced Ni coating by electrodeposition
W Shao
1
, D Nabb
2
, N Renevier
3
, I Sherrington
3
and J K Luo
1
1
University of Bolton, UK
2
MSC Copperflow Ltd,UK,
3
University of Central Lancashire,UK
Emails: W.Shao@bolton.ac.uk, J.Luo@bolton.ac.uk
Abstract. Coatings have been widely used in engineering and decoration to protect
components and products and enhance their life span. Nickel (Ni) is one of the most important
hard coatings. Improvement in its tribological and mechanical properties would greatly
enhance its use in industry. Nanocomposite coatings of metals with various reinforced
nanoparticles have been developed in last few decades. Titania (TiO
2
) exhibit excellent
mechanical properties. It is believed that TiO
2
incorporation in Ni matrix will improve the
properties of Ni coatings significantly. The main purpose of the current work is to investigate
the mechanical and anti-corrosion properties of the electroplated nickel nanocomposite with a
small percentage of TiO
2
. The surface morphology of nanocomposite coating was
characterized by scanning electron microscopy (SEM). The hardness of the nanocoating was
carried out using micromaterials nanoplatform. The sliding wear rate of the coating at room
temperature in dry condition was assessed by a reciprocating ball-on-disk computer-controlled
oscillating tribotester. The results showed the nanocomposite coatings have a smoother and
more compact surface than the pure Ni layer and have higher hardness and lower wear rate
than the pure Ni coating. The anti-corrosion property of nanocomposite coating was carried out
in 3.5% NaCl and high concentrated 35% NaCl solution, respectively. The results also showed
that the nanocomposite coating improves the corrosion resistance significantly. This present
work reveals that incorporation of TiO
2
in nickel nanocomposite coating can achieve improved
corrosion resistance and mechanical properties of both hardness and wear resistance
performances, and the improvement becomes stronger as the content of TiO
2
is increased.
1. Introduction
Incorporation of ceramic, polymer and metal nanoparticles within metal matrix produces composite
coatings which have many attractive properties such as wear resistance, corrosion resistance,
particularly useful for engineering [1]. Majority of the work has been concentrated on nickel (Ni)
coating. The reinforced particles could be SiC, Al
2
O
3
, titania (TiO
2
), carbon nanotubes (CNTs) and
polymers such as Polytetrafluoroethylene (PTFE) and Polyethylene (PE) [2-5]. Among these
reinforcements, TiO
2
is one of the most important used in the engineering materials. The titanium-
based material offers high strength, good corrosion and oxidation resistance [5], it is believed that
incorporation of nanoparticles can greatly improve the mechanical, tribological properties and
corrosion resistance, hence can be used in industry either in single layer or multilayer structure. In this
International Conference on Structural Nano Composites (NANOSTRUC 2012) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 40 (2012) 012043 doi:10.1088/1757-899X/40/1/012043
Published under licence by IOP Publishing Ltd 1
paper, we will report the mechanical properties and corrosion resistance for the TiO
2
nanoparticles
reinforced Ni coatings.
2. Experiments
2.1 Preparation of coatings
Mild steel plates with the dimension of 20mm20mm1mm were used as the substrates. Before
electroplating, the steel substrates were cleaned by alkaline cleaning solution and followed by an acid
etch process. De-ionized water was used to rinse after each step, and finally dried by dry N
2
gas. The
electrolyte used in this study is a standard Watts bath, containing up to 12 g/l TiO
2
nanoparticles
(Sigma, ~50nm) with suitable surfactant. Electrodeposition took place in the bath of 50

C and at a
current density of 3 A/dm
2
for 1hr.
2.2 Characterization of the coatings
A Philips XL30 ESEM (SEM) operating at an accelerating voltage of 15 KV was used to observe the
surface morphologies of the coated samples.
Hardness tests were carried out using a three-sided flat pyramidal diamond flat tip with an angle of
104.3 at room temperature. The indenter was lowered at a rate of 50 nm/s to indent the matrix up to a
depth of 500 nm and then to retrieve from the coating surface.
The wear tests were evaluated on a reciprocating ball-on-disk computer-controlled oscillating
tribotester. A tungsten carbide (WC) ball with diameter 6 mm was used as the counter body. All the
wear tests were performed using a load of 12 N at 12 mm/s sliding speed in dry condition at room
temperature. The total sliding distance is 10000 mm.
PG581 potentiostat system was used for electrochemical measurements with three standard
electrodes. The measurements were carried out in a 250 ml cell in 3.5 % NaCl solution at room
temperature. All the potentials were recorded with respect to saturated calomel electrode (SCE). Prior
to Tafel polarization, the specimens were allowed to immerse in the electrolyte while the open circuit
potential (OCP) was measured until it reached a stable value. Potentiodynamic polarization curves
were recorded from a starting potential of 500 mV below the OCP and were scanned towards the
positive direction at a scan rate of 1 mVs
-1
, until the potential reached 500 mV. Weight loss method
was used to assess the corrosion resistance of coatings. The specimens were immersion into 35 %
NaCl solution at room temperature in order to accelerate the corrosion rates. The weight differences
were recorded after 10 days and 20 days immersion.
3. Results and discussion
3.1 Characterization of Ni nanocomposite coatings
Figure 1 shows the SEM morphologies of Ni coating and Ni-TiO
2
nanocoating containing 12 g/l TiO
2
nanoparticles. The microstructures between pure Ni coating and Ni-TiO
2
nanocoating are different
significantly. The Ni coating has a rather regular structure with large grain size in the range of 2~4 m
(Figure 1a). The Ni-TiO
2
nanocoating shows smaller gain sizes of 0.1~1 m (Figure 1b), which
indicates that the co-deposited TiO
2
nanoparticles are much uniformly distributed in the Ni matrix. It
shows that Ni-TiO
2
nanocoating has fairly uniform, continuous and compact morphology.
3.2 Hardness of Ni nanocomposite coatings
Figure 2 shows the microhardness of Ni coating and Ni-TiO
2
nanocoatings with the different contents
of TiO
2
nanoparticles. It can be seen that the hardness of Ni-TiO
2
nanocoating increases with
increasing the content of TiO
2
nanoparticles, and that with 12 g/l TiO
2
nanoparticles has the maximum
hardness of 387 HV, clearly demonstrated its significant effect. This is because the co-deposited TiO
2
nanoparticles in the Ni matrix can restrain the growth of the Ni grains resulting in the very fine grain
International Conference on Structural Nano Composites (NANOSTRUC 2012) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 40 (2012) 012043 doi:10.1088/1757-899X/40/1/012043
2
structure and dispersive strengthening effects which leads to the microhardness of Ni-TiO
2
nanocoatings increase with increasing the TiO
2
nanoparticles content [6].
Figure 1. (a) SEM of Ni coating, (b) SEM of Ni-TiO
2
nanocoating.
3.3 Anti-wear properties of the coatings
Figure 3 shows that the effect of TiO
2
particles on the wear rate of Ni matrix nanocoatings. There is a
steadily decreasing trend with the increase of the content of the TiO
2
nanoparticles in the nanocoatings.
The wear rate of the Ni-TiO
2
nanocoating with 12 g/l TiO
2
is 9.09710
-9
mm
3
/Nm and that of Ni
coating is 14.87510
-9
mm
3
/Nm, improved about 48 %. The improvement is believed to be twofold:
firstly an increase in surface fraction of TiO
2
nanoparticles reduces the direct contact between the Ni
matrix and WC ball. When the TiO
2
co-deposited with the matrix metal, the fine smooth surface
morphology of the nanocoating will increase the load-carrying area and reduce the stress between the
friction couples which leads to the improvement of wear resistance of the nanocoating [2]. Secondly the
TiO
2
nanoparticle has a much high wear resistance, hence reduces the overall wear rate of the
nanocoating. Also the nanocoating is much denser with smaller grain sizes as it can be seen from Figure
1, this may also contribute to the improvement of the wear resistance. The SEM images of worn coating
surfaces are shown in Figure 4. Clearly, the width and depth of the worn track of the pure Ni coating
(Figure 4a) is much larger than that of the TiO
2
reinforced Ni nanocoating as shown in Figure 4b.
Figure 2. Hardness for Ni based nanocoatings. Figure 3. Wear rates for Ni based nanocoatings
3.4 Corrosion resistance of the coatings
Figure 5 shows the Tafel curves of Ni coatings (line 1), Ni-TiO
2
with 12 g/l TiO
2
(line 2) nanocoatings.
The electrochemical parameters such as corrosion potential (E
corr
), corrosion current (I
corr
) and the
calculated corrosion rates (R
corr
) are listed in Table 1. The corrosion rates of the 12 g/l TiO
2
nanoparticles reinforced Ni coating has improved 25 % compared with the pure Ni coating. With the
increase of TiO
2
content in the nanocoating, the corrosion current decreases and the corrosion potential
shifts to a more positive potential resulting in a decreased corrosion rate. Nanocoating has a much
denser and more compact surface and has much less pores and cracks than pure Ni coating, which are
International Conference on Structural Nano Composites (NANOSTRUC 2012) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 40 (2012) 012043 doi:10.1088/1757-899X/40/1/012043
3
attributed to contribute to the improvement of anti-corrosion property. Figure 6 shows the weight loss
results for different Ni based coatings immersed in 35 % NaCl solution for 10 days and 20 days,
respectively. It is evident that TiO
2
nanoparticles reinforced Ni has a good tendency for corrosion
resistance compared with pure Ni coatings.
(a) (b)
Figure 4. SEM of worn surfaces (a) pure Ni coating, (b) Ni-TiO
2
nanocoating.
Figure 5. Tafel curves of Ni and
Ni-TiO
2
nanocoatings.
Figure 6. Weight loss results after 10 days and
20 days in 35 % NaCl solution.
Table 1. Electrochemical parameters and calculated corrosion rates for tested coatings.
Samples E
corr
[mV] I
corr
[A] R
corr
[mpy]
Ni coating
Ni-TiO
2
(4 g/l)
Ni-TiO
2
(8 g/l)
Ni-TiO
2
(12 g/l)
-755
-742
-733
-727
333
314
296
258
15.3
14.4
13.6
11.5
4. Conclusions
TiO
2
nanoparticles reinforced Ni nanocomposite coatings revealed a much smoother surface
microstructure with excellent mechanical properties. The Ni-TiO
2
nanocomposite coatings exhibited
higher hardness and higher wear resistance in comparison with pure Ni coating. Meanwhile, the
corrosion resistance has been enhanced significantly.
5. Acknowledgement
The authors would like to acknowledge the financial support by Knowledge Transfer Partnership and
TSB (KTP007867) and The Knowledge Centre for Materials Chemistry under Grant No. of X00680PR.
International Conference on Structural Nano Composites (NANOSTRUC 2012) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 40 (2012) 012043 doi:10.1088/1757-899X/40/1/012043
4
[5] A.A.Aal: Mater. Sci. Eng., A, vol.474 (2008), p181
[6] L. Shi, C. Sun,P. Gao, F. Zhou and W. Liu: Appl. Surf. Sci., vol. 252 (2006), p. 3591
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[4] R.H. Cayton: NSTI-Nanotech, vol. 3 (2004), p.312
International Conference on Structural Nano Composites (NANOSTRUC 2012) IOP Publishing
IOP Conf. Series: Materials Science and Engineering 40 (2012) 012043 doi:10.1088/1757-899X/40/1/012043
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