Materials and Design 88 (2015) 278286

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Materials and Design

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

Preparation and coating of nano-ceramic on orthopaedic implant

material using electrostatic spray deposition
Suman Singh a,, Vijay Kumar Meena a,, Manisha Sharma a, Harpreet Singh b
a
b

Central Scientic Instruments Organisation (CSIR-CSIO), Chandigarh, India

Indian Institute of Technology (IIT), Roopnagar, Punjab, India

a r t i c l e

i n f o

Article history:
Received 17 June 2015
Received in revised form 27 August 2015
Accepted 28 August 2015
Available online 3 September 2015
Keywords:
Nano-hydroxyapatite
Electrostatic spray deposition
Coating
Orthopaedic implant material

a b s t r a c t
The objective of the present manuscript was the synthesis of nano hydroxyapatite (n-HA) and its coating on orthopaedic implant material. The synthesis of n-HA has been achieved using wet chemical method. The elemental
analysis and FTIR spectrum conrmed the formation of n-HA having a Ca/P ratio of 1.71. The AFM and XRD results
showed the nano dimensions of hydroxyapatite (HA) in the range of 2535 nm. Scanning electron micrographs
(SEM) showed a ake-like structure of n-HA having sharp edges. The n-HA was further coated on orthopaedic
implant material (titanium alloy, Ti6Al4V), using the electrostatic spray deposition (EDS) technique. The surface
roughness of Ti alloy increased from 2.34 m to 2.77 m after coating with n-HA and corrosion resistance
improved drastically. XRD pattern of n-HA coated Ti alloy however showed broadening of HA associated peak,
reecting change from crystalline to amorphous phase of n-HA.
2015 Elsevier Ltd. All rights reserved.

1. Introduction
For orthopaedic applications, generally, titanium or titanium alloy
such as Ti6Al4V are used as implant material due to their high mechanical strength, high biocompatibility, low density and high corrosion resistance. But being bio-inactive, it can't form bonding directly with the
living bones. Some surface modication of implant with bioactive material like hydroxyapatite (HA) will help to enhance implant xation by
favouring osseointegration. Hydroxyapatite constitutes an inorganic
phase of natural bone, embedded between the organic phase which is
formed by collagen bres, [1]. Being chemically and structurally similar
to the natural bone, the hydroxyapatite (HA), [(Ca10(PO4)6(OH)2)], is
exhaustively studied as bone substitute for number of clinical applications like orthopaedic devices, dental replacements [2], tissue engineering [3], and bioactive coatings [4].
Advancement in nanotechnology has ignited the research on the
formation of nano-sized hydroxyapatite, and this progress is reected in
several published reviews [3,5,6]. Dorozhkin in 2012, reviewed the state
of art and recent developments on synthesis and characterization of
nano-calcium orthophosphates, which included nano-hydroxyapatite
also for biomedical and clinical applications [7]. In their review, the
authors also covered the difference in properties of nanoscaled calcium
compounds with that of micro and sub-micron scaled counterparts. As
compared to bulk counterparts, the nano scaled ceramic material, HA in
particular, showed superior chemical and physical properties due to
Corresponding authors.
E-mail addresses: sumansingh01@gmail.com, ssingh@csio.res.in (S. Singh),
vijay.kumar.meena@csio.res.in (V.K. Meena).

http://dx.doi.org/10.1016/j.matdes.2015.08.145
0264-1275/ 2015 Elsevier Ltd. All rights reserved.

presence of large volume fraction of defects like grain boundaries, interphase boundaries and dislocations, large surface area, and more surface
energy. Anitha and Pandya presented comprehensive review on preparation methodologies of nano hydroxyapatite [8]. A review has been presented on the synthesis methods of nano-hydroxyapatite having diverse
structures [9].
The surface modications of implant surface by coating the nanomaterial might contributes to the enhancement of biocompatibility by
favouring the interaction of living cells with the material, especially by
their benecial effect on cell adhesion and proliferation. The research
conducted by Sun. et al. has shown that when hydroxyapatite nanocrystal was used as a bone substitute graft, rapid healing of critical size defect has been demonstrated in animal experiments and applications in
humans [10]. The nano-sized hydroxyapatite also favoured higher protein adsorption and enhanced osteoblast adhesion [11,12], thus helping
in the promotion of bone regeneration. Experimental and clinical studies have shown that as compared to metal substrates alone, hydroxyapatite (HA) coated implant surfaces promote implant xation better
due to its chemical bonding with nearby growing bone and its high
osteoconductivity [13]. The HA coated metallic implants combine
good strength and ductility of the metal with high biocompatibility
and bioactivity of HA [14]. The method of coating HA, and chemical
composition however play major roles in deciding the in vivo bony
response. Jimba et al. [15] coated implant material with nanohydroxyapatite and study showed that though both HA coated and
uncoated implants showed same level of bone to implant contact but
enhanced tissue quality was observed around HA-coated implants.
The osseointegration of titanium implants with and without the presence of hydroxyapatite (HA) nanocrystals was evaluated in vivo by

S. Singh et al. / Materials and Design 88 (2015) 278286

Breding et al. [16]. The study observed signicant differences for

osteoblast, osteoclast, and pro-inammation markers when HA nanocrystals were present.
Various techniques like solgel [17], plasma spray [18], thermal
spray [19] and electrostatic spray deposition (ESD) [20] have been
used for coating HA and other bioactive materials on implants for
their surface functionalization. Among them, ESD technique is a simple
and low energy process [2123]. In this technique, the suspension containing precursor material is sprayed onto the substrate under the inuence of a high electrical eld that creates an aerosol of similarly charged
micron-sized droplets [24]. By adjusting output voltage and ow rates,
different modes like dripping, cone-jet, and multi-jet mode can be generated to produce droplets of different sizes. The cone-jet mode is usually preferred because it produces mono-sized droplets in the range of
several micrometres [25,26]. Studies have shown that the ESD can be
used to deposit variety of ceramic materials using different process parameters. The hydroxyapatite (HA) has been coated on porous-surfaced
Ti compact using electrostatic spray deposition [27]. The coated substrate was then heated at 400900 C as a result of which the HA particles got melted and formed dense and homogeneous layer on the
substrate. The nano-sized silicon substituted hydroxyapatite was
deposited on glass and titanium substrate using electrostatic spraying
[28]. The SEM imaging showed presence of micro and sub-micro
metre-scaled islands of nSiHA on substrates and the surface roughness
was in the range 60 to 80 nm. Template-assisted electrostatic spraying
deposition was used to deposit composite of nano-hydroxyapatite and
silk broin (n-HA/SF) onto the Ti alloy substrates [25]. The study
showed that the morphological properties of nanocrystals remained intact even onto Ti alloy substrate when ESD was used for deposition.
Electrostatic spray deposition technique was used in combination
with radio frequency magnetron sputtering to deposit a calcium phosphate (CaP) coating on titanium alloy [29]. The study showed enhanced
osteogenic expression on ESD coating.
In the present work, nano sized hydroxyapatite (n-HA) has been deposited on orthopaedic implant material (titanium alloy; Ti6Al4V),
using ESD technique. The nano-hydroxyapatite is synthesized using
wet precipitation method. The n-HA powder and n-HA coated Ti alloy
substrate were characterized for morphology, roughness and corrosion
resistance. The novelty of the work lies in clean synthesis and indigenously designed and developed ESD deposition system. The efciency

279

of in-house developed ESD system has been tested by using it for coating
n-HA on titanium alloy.
2. Experimental section
2.1. Materials
Calcium hydroxide [Ca(OH)2] and orthophosphoric acid (H3PO4),
were obtained from Himedia and were of analytical grade. The Hank's
solution was procured from Sigma. Deionized (DI) water was obtained
from Millipore water purication system (Milli-Q Integral 3) and was
used for solution preparations and their dilutions.
The stirrer used for the synthesis of n-HA was from REMI 5 MLH Plus.
Atomic force microscopy (AFM) was used for grain size measurement of
n-HA using Park AFM system from Korea, Model-XE. The coating was
achieved using an electrostatic spray deposition system (customized)
and details are given in respective sub sections. The morphology of
n-HA and n-HA coated implant material (Ti6Al4V) was studied using
scanning electron microscope (SEM), JEOL 2, Model JSM6610LV,
coupled with Energy Dispersive X-ray Spectroscopy (EDS) (Oxford,
model-Incax-act, 51-ADD0013). Before SEM imaging, the samples
were gold sputtered to induce conductivity in samples. The XRD pattern
of n-HA and n-HA coated titanium alloy was recorded on X-ray diffractometer from PANalytical X'Pert Pro, operating with CuK radiation
over a 2 range of 10100. The Fourier transform infra-red (FTIR) spectrum of n-HA was recorded on a 670-IR system (Varian, USA). The surface roughness of n-HA coated and uncoated implant material
(Ti6Al4V) was measured using Talysurf PGI 120 prolometer, having
Gaussian based lter of 0.8 mm cut off. The prolometer is mounted
on an epoxy granite based anti-vibration mount, which provides a
rm support for the column and work piece. For measuring roughness,
Ra (the arithmetic mean of the departures of the roughness prole from
the mean line), and Rq (root mean square (RMS) of average roughness),
are considered. The corrosion studies of Ti alloy and n-HA coated Ti alloy
were carried out on CH Instruments (CHI 1100 series, US), using Hank's
solution as an electrolyte. The coated and uncoated Ti alloy were used as
working electrode, Pt wire as auxiliary electrode and Ag/AgCl as reference electrode. All studies were carried out at 37 C. From the polarization curve, the corrosion potential (Ecorr) and corrosion current density
(Icorr) were determined by Tafel extrapolation.

Fig. 1. ESD set up and pictorial representation of n-HA deposition.

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S. Singh et al. / Materials and Design 88 (2015) 278286

Fig. 2. AFM of n-HA.

2.2. Methods
2.2.1. Synthesis of nano-hydroxyapatite (n-HA)
The nano- hydroxyapatite (n-HA) has been synthesized using a wet
chemical method, which is also known as precipitation method. The
wet chemical precipitation, combined with the thermal treatment at
high temperatures results in the formation of crystalline phases. The
process involves drop-wise addition of aqueous solution of one reagent
to the aqueous solution of another reagent, under continuous stirring.
The product obtained after precipitation and centrifugation, is then
sintered at high temperatures. The detailed experimental protocol
used for n-HA synthesis is as follows: rst the calcium hydroxide
[Ca(OH)2] solution (0.5 M) and orthophosphoric acid (H3PO4) solution
(0.3 M) was prepared in deionized (DI) water, separately. Then, the
H3PO4 solution was added drop-wise to 100 mL solution of Ca(OH)2,
till the pH of solution reached 12.5. In this synthesis, maintaining the

pH was crucial step as the pH and temperature play important role in

deciding morphology and crystallinity of the product [30,31]. Manoj et
al. [32] studied the effect of processing parameters like temperature,
pH and stirring time on HA formation. At pH 7.0 and 9.0, a mixture of
calcium phosphate phases was observed and the rate of HA formation
was very poor. At pH 11.5, no calcium phosphate phases were present
and the reaction showed fast particle growth. At alkaline conditions,
the instable and amorphous CaP phases transform into a stable HA according to the following reaction [33]:

10CaHPO4 12OH Ca10 PO4 6 OH2 10H2 O 4PO3

4

PO34 ACP OH Ca10 PO4 6 OH2

Fig. 3. Scanning electron micrograph and ESD of n-HA.

S. Singh et al. / Materials and Design 88 (2015) 278286

281

temperature was maintained at 350 C. For n-HA deposition, rst the

n-HA suspension was prepared in ethanol using sonication for 15 min.
The suspension was then loaded to a syringe and mounted in the
syringe pump. The electrospray droplets of sample were targeted onto
the metal substrate (Ti alloy) to form a solid layer on it after solvent
evaporation. The picture of ESD set up and pictorial representation of
deposition is shown in Fig. 1.
3. Results and discussion
3.1. Electrostatic spray deposition (ESD)

Fig. 4. FTIR spectrum of n-HA.

After adjusting the pH, the solution was stirred at 60 rpm for 24 h at
room temperature, which resulted in the formation of a precipitate. The
stirring time can affect morphology, size and crystallinity of nal product. Murugesan and his team [32] studied the effect of stirring time on
crystallinity and observed that stirring time of more than 48 h results
in decreased crystallinity.The precipitate was centrifuged at 6000 rpm
for 30 min, washed with DI water 34 times and air dried. The powder
so obtained was calcinated at 700 C for 30 min. The powder was collected and used for further characterization and coating.
2.2.2. Electrostatic spray deposition (ESD) of n-HA
The ESD system used for deposition of n-HA has been designed and
developed at in-house. It consisted of a nozzle having stainless steel capillary of 1.2 mm outer diameter, a DC high voltage supply (make: Fug,
Model No: HCP 3520,000, range 020 kV), a heater, a temperature controller (Thermotech, TIC 4000 N), peristaltic pump (Cole Parmer), and
axis manipulators. The voltage supply was used to apply the voltage
across the nozzle and grounded substrate. The temperature controller
was used to control the temperature of the heater. The peristaltic
pump was used to feed the precursor solution to be atomized to the
capillary. The XY-Z manipulator was used to precisely control the movement of XY-Z stage for uniform deposition. (X and Y movement:
2.5 cm, Z movement: 015 cm). For present study, 5.6 kV has been
used as applied voltage, keeping the ow rate of 0.06 mL/min and the

The mechanism involved in electrostatic spray deposition method is

presented elsewhere [29]. With this technique, an organic solvent containing hydroxyapatite was pumped through a nozzle and voltage was
applied between the nozzle and substrate. The n-HA is electrically insulating in nature and can carry the static charge. But when it exits the
powder spray gun and is exposed to an electrostatic eld generated by
the pointed electrode, the particles get charged. As shown in Fig. 1, the
charged particles follow the electric eld lines towards the substrate
and form a lm on the substrate. After solvent evaporation, the sample
is washed with deionized water and was air dried. The quality of thin
lm formed on a substrate however depends on the size of particles
or droplets forming the layer, and their dispersity. Smaller the concentration, smaller the aggregates.
3.2 Morphological study of nano-hydroxyapatite (n-HA)
Fig. 2 shows atomic force microscopic (AFM) image of synthesized
nano scaled hydroxyapatite, which shows its size in nanometre range
of 2530 nm. The particle size again is however dependent on experimental process parameters, specically the temperature. The particle
size is reported to decrease with increased sintering or treatment temperature [34]. The line prole shows poly-dispersity in n-HA powder
and 3-D view also shows agglomeration at some places.
The SEM characterization also showed presence of n-HA along with
the agglomeration at some places (Fig. 3). The ESD has been used to
nd Ca/P ratio in n-HA, which is found to be 1.71. This ratio tends to
change with the synthesis protocols and boundary conditions of experiment like temperature and duration of annealing, etc. Abidi and
Murtaza synthesized nano-hydroxyapatite and sintered it at temperatures varying from 100 C to 800 C and an optimum temperature was

Fig. 5. XRD of n-HA.

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S. Singh et al. / Materials and Design 88 (2015) 278286

Fig. 6. SEM and ESD of uncoated Ti alloy.

found to be 600 C. The study showed Ca/P ratio dependency on the

calcination temperature [35].
3.3 Structural study of nano-hydroxyapatite (n-HA)
Fig. 4 shows the FTIR spectrum of n-HA. The two absorption bands at
566 cm1 and 601 cm1 are ascribed to the anti-symmetric (4) PO
bending modes of the phosphate groups (PO3
4 ), a characteristic of crystalline hydroxyapatite [18]. Freund and Knoble studied the distribution
of uoride ion in hydroxyapatite structure [36] and found that these
two mentioned bands remained unaffected by uoride substitution.
The band at 962 cm1 is for symmetric stretching mode of PO (1)
and band at 456 cm 1 corresponds to vibrational mode 2 [37]. The
band at 1035 cm1 originated from the antisymmetric stretching
mode of PO (3), in orthophosphate [38]. The existence of PO4 related
bands conrm the presence of apatite structure [39]. The band at
3440 cm 1 is due to O-H group. Peaks at 873 cm 1 and 1452 cm 1
are due to adsorption bands for CO2
3 (2). The presence of characteristic band at 1452 cm1 conrms the formation of type-B carbonated hy3
droxyapatite where CO2
3 ions substitutes PO4 ions. The reason can be
the reaction between hydroxyl groups and atmospheric CO2, thus
resulting in the formation of carbonate ion. lsarczyk et al. studied
the carbonated hydroxyapatite using FTIR and in their study, two
band were observed at 1415 cm 1 and 1450 cm 1 which were
ions [38]. The
ascirbed to originate from stretching vibrations of CO2
3
peak at 1629 cm1 is for O-H.
The synthesized nano hydroxyapatite was also characterized using
XRD and the graph is shown in Fig. 5. The XRD pattern is well matched
with JCPD reference card of standard HA (JCPDS: 9432) and can be well
indexed to the hexagonal geometry Ca10 (P04)6(0 H)2. The crystal
growth has been prominent along b211 N plane. The hydroxyapatite
crystal structure contains PO4 tetrahedrons layer along c-axis and

the Ca2+ is located between the 3 tetrahedrons in upper layer and 3 tetrahedrons in bottom layer [40]. The Ca (I) atom connects with 9 oxygen
atoms at the corner of the tetrahedrons and three oxygen atoms are relatively far from the Ca (II) atom. These connections form a channel that
gets parallel to the c-axis. The OH groups ll in the channel and connect with six Ca (I) atoms, forming a [OH-Ca6] octahedron. The Ca (II)
atoms at [OH-Ca6] octahedron connect with six O2 at [PO4] tetrahedron
and an OH group. The connections form a hexagon symmetry with hexagonal loop having c-axis as symmetry axis.
In XRD pattern, along with the peaks for pure n-HA, additional peak
for -TCP phase is also observed. However, the -TCP and CaO phases
are expected to come when hydroxyapatite is sintered at temperatures
above 800 C [41]. Feng et al. [42] observed small amount of -TCP
and TTCP in HA when the temperatures were 1150 C and 1200 C, respectively. Another group of researchers [43] sintered their ceramic pellets at temperatures of 650 C, 850 C, 1050 C and 1250 C, respectively.
At all the temperatures, except 1250 C, formation of pure crystalline
nanometre scaled HA was observed. Their XRD pattern recorded for
1250 C conrmed the presence of -tricalcium phosphate (-TCP),
with reduced HA component, small amounts of potassium calcium hydrogen phosphate and potassium calcium phosphate. The appearance
of -TCP phase can be due to the loss of OH radical, also known as dehydroxylation, from HA structure during the sintering process [44], thus
forming oxyapatite, according to the following equation [42].
2OHO H2 O

Ca10 PO4 6 OH2 2Ca10 PO4 6 O:X H2 O

where Ca10(PO4)6(OH)2 is HA, Ca10(PO4)6O is oxyapatite, and X is a

non-charged vacancy.
During dehydroxylation, the lattice sites that were occupied initially
by two OH groups in a HA unit cell are now being occupied by an

Fig. 7. SEM and ESD of n-HA coated Ti alloy.

S. Singh et al. / Materials and Design 88 (2015) 278286

283

by /180 [33], is the wavelength of Cu target = 0.15406 nm, and is

the Bragg angle. The diffraction peak at 2 = 25.9 was used for crystallite
size calculation, and was found to be 45.7 nm. The peak widths are
inversely proportional to the average crystallite size average, D and if
we see the XRD pattern, peaks are wide, and hence indicate smaller crystallite size. The relationship between crystal plane index and inter-planar
2

1
2 2

spacing d1 3a42 h k hk cl 2  has been used to calculate the

hkl

lattice constants 'a' and 'c' and are found to be 0.94 nm and 0.685 nm,
for a and c lattice constant respectively. In hexagonal geometry, a =
b c. The micro-strain (g) was calculated using the relation g = Cos
, where g is micro-strain, is FWHM and the value is 0.179.
3.4 Characterization of n-HA coating
Fig. 8. XRD of n-HA coated Ti alloy.

oxygen atom while leaving the other vacant. This leads to lattice contraction. At high sintering temperatures, the HA decomposes to tri
calcium phosphate (TCP) and tetracalcium phosphate (TTCP) phases
through following process:
Ca10 PO4 6 OH2 2Ca3 PO4 2 H2 O

where Ca3(PO4)2 is TCP and Ca4P2O9 is TTCP.

The crystallinity (c) of n-HA has been determined using the relationship:
X
Ac
X
Xc X
Ac
Aa

where, Ac and Aa is the total area under crystalline and amorphous phase in the pattern respectively and is calculated by integrating
the curve over the desired phase. The synthesized n-HA has 86% crystalline and 14% amorphous phase. The crystallinity is reected from the
sharpness of peaks of XRD pattern as well. Pang and Bao [30] reported
increase in crystallinity of n-HA upto 53% after calcination. Barbosa
and his group [45] studied the effect of ultrasonic irradiation (UI) on
the crystallinity of nano-hydroxyapatite synthesized via wet chemical
method. Their analysis conrmed strong connections between UI and
crystal growth properties.
The crystallite size was calculated using the Scherer's formula D = k
/ Cos , where D is the crystallite size, k = 0.9 is a correction factor to
account for particle shapes, is the full width at half maximum
(FWHM) (radian), and is obtained by multiplying the (degree)

Figs. 6 and 7 show morphology and elemental studies of uncoated Ti

alloy and n-HA coated Ti alloy, obtained from SEM imaging and EDS
analysis. The SEM of uncoated Ti alloy shows needle like morphology,
with pores of different size in it. After coating with n-HA, surface of Ti
alloy became dense and algal type, which might be due to the embedment of n-HA akes onto the pores. The of n-HA coated Ti alloy
conrmed the presence of calcium (Ca), carbon (C), and oxygen
(O) elements, though phosphorus is not observed in this EDS spectrum,
due to overlapping of energy of phosphorus with other elements.
The n-HA coated Ti alloy was characterized using XRD also. The XRD
pattern of n-HA coated Ti alloy (Fig. 8) showed peaks associated with nHA, titanium (Ti), and aluminium (Al), Ti and Al being the constituent of
the alloy. As compared to the peaks of powder n-HA, peaks in coating
are less intense and are broad. Such broadened weak peaks in coatings
are attributed to the small grain size and poor crystallinity of the coatings [46,47]. Prevy et al. also observed the broadening of the n-HA associated peak after its coating and attributed this behaviour to the
presence of nano-crystalline HA [48].
Since the surface roughness in nanoscale range is one of the important factors affecting the cell-material interaction, and interfacial biology, the change in surface roughness after n-HA deposition was also
studied. The surface roughness helps to increase the dissolution rate of
apatite [49]. Also, the bone forming cells generally attach themselves to
the rough nano-surfaces, resulting in high osseointegration. Khang et al.
investigated the cell adhesion behaviour on submicron, and nanometre
structured titanium surface and compared their results with a at smooth
titanium surface [50]. The study demonstrated that both the nanometre
and submicron surfaces have very high surface energy and adhesion of
bone cells is very high on these surfaces. Thomas et al. also observed

Fig. 9. Roughness measurements of uncoated Ti alloy.

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S. Singh et al. / Materials and Design 88 (2015) 278286

Fig. 10. Roughness measurements of n-HA coated Ti alloy.

increased osteoblast adhesion on novel surface topography created by

carbon bres with nanometre dimensions [51].
Figs. 9 and 10 show the surface roughness prole of bare and n-HA
deposited Ti alloy substrate and the results presented are average of
three experiments. The surface roughness parameters Ra (the arithmetic mean of the departures of the roughness prole from the mean line),
and Rq (root mean square (RMS) of average roughness) for uncoated Ti
alloy are 2.34 m and 2.94 m respectively. The n-HA coated Ti alloy, exhibited Ra value of 2.77 m and the Rq value was 3.86 m. The roughness
of Ti alloy surface increased after coating with n-HA.

3.4.1 Electrochemical passivity study of n-HA coated Ti alloy

The presence of hydroxyapatite layer helps to improve the bioactivity and increases osteoconductivity during initial period after implantation. But the stability of layer depends on its electrochemical passivity
[52]. The electrochemical passivity of n-HA layer has been determined
using corrosion studies. Electrochemically, the corrosion rate measurement is based on the determination of oxidation current, which is also
called as corrosion current at the corrosion potential. For the study,
open circuit potential (OCP) and tafel plot were used. OCP is the potential measured when no [net] current is owing. The OCP was performed
for coated and uncoated Ti alloy, in Hank's solution at room temperature

and experiment was run for 400 s (Fig. 11). The OCP of uncoated Ti alloy
showed initial potential at 0.045 V, and with passage of time, it reached
at 0.041 V. For n-HA coated samples, the initial OCP was 0.015 V, and it
continued to increase till the protective air-oxide lm reached its protective capacity. This shows that n-HA coated Ti alloys are robust
towards corrosion resistance.
The tafel plot can provide a direct measure of the corrosion current,
which can be related to corrosion rate. The Tafel plot extrapolated to the
zero current/potential gives a set of co-ordinates relating to Ecorr (x axis)
and Icorr (y axis). Figs. 12 and 13 show tafel plot for uncoated Ti alloy and
n-HA coated Ti alloy. The calculated corrosion parameters are shown in
Table 1, deduced directly by the instrument software. As compared to
the uncoated substrate, Ecorr value of n-HA coated Ti alloy substrate
got decreased on moving towards the noble potential. The corrosion
current also decreased in n-HA coated Ti alloy sample, thus indicating
corrosion resistant behaviour of n-HA coated Ti alloy. The apatite layer
plays role of a barrier to the transport of electrons and ions between
substrate and the electrolyte, thus reducing the electrochemical reaction rate. The improved corrosion resistance of n-HA coated Ti alloy
sample is also attributed to the combined effect of the semi-insulating
HA coatings and TiO2. One important observation is that none of the polarization curves showed hysteresis loop, which conrms no passivity
breakage in both coated and uncoated Ti alloy samples.

Fig. 11. Open circuit potential (OCP) measurement of (i) n-HA coated Ti alloy and (ii) uncoated Ti alloy.

Fig. 12. Tafel plot of uncoated Ti alloy for corrosion studies.

S. Singh et al. / Materials and Design 88 (2015) 278286

Fig. 13. Tafel plot of n-HA coated Ti alloy for corrosion studies.

Table 1
Corrosion parameters of uncoated and n-HA coated Ti alloy, derived from Tafel plot.
Parameters

Uncoated Ti alloy

n-HA coated Ti alloy

Corrosion potential (V)

Corrosion current (A)
Linear polarization resistance
Corrosion rate (mil/year)
Corrosion rate (Angs/min)
Corrosion rate (gm/h)

0.140
1.17 102
195.2
2.51 105
1.21 105
2.1 101

0.098
3.9 106
8371
8.3 101
4.03 101
7.2 105

4. Conclusion
The paper presents wet synthesis of nano hydroxyapatite (n-HA)
and its coating on orthopaedic implant material. Due to resemblance
in structure, composition, and biocompatibility of HA with natural
bone, it has been widely used as a coating material for dental and orthopaedic implants. The nano HA, on other hand, has its own advantages of
high surface area and favoured osseointegration. The size and morphology are prone to the synthetic parameters like pH and temperature. The
n-HA exhibited Ca/P ratio of 1.71. The electrostatic spraying deposition
method has been used to coat n-HA on Ti alloy and the method is a
single-step, low-energy, and low-cost material processing technology.
The corrosion studies showed high corrosion resistance in n-HA
containing Ti alloy. The surface roughness also got enhanced after coating Ti alloy with nano hydroxyapatite. These properties show the application potential of n-HA for being used in biomedical sector.
Acknowledgement
Authors would like to appreciate nancial support received from
Council of Scientic and Industrial Research (CSIR), New Delhi, under
its network project BIOCERAM, Project No. Esc 0103, in XIIth ve year.
Authors also acknowledge Ms. Sudeshna Bagchi, Scientist, CSIR-CSIO,
for helping in electrostatic spray deposition and Ms. Neha Khatri, Scientist, CSIR-CSIO, for roughness measurement studies. The authors acknowledge the help of Mr. Amardeep Bharti in XRD data analysis.
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