Surface & Coatings Technology 200 (2006) 4720 – 4730

www.elsevier.com/locate/surfcoat

Hydroxy apatite coatings on Ti-6Al-4V from seashell

R. Narayanan*, Sraboni Dutta, S.K. Seshadri
Department of Metallurgical and Materials Engineering, Indian Institute of Technology Madras, Chennai-600 036, India

Received 31 December 2004; accepted in revised form 7 April 2005

Available online 2 June 2005

Abstract

Electrochemically deposited hydroxy apatite (HA) coatings were produced on Ti-6Al-4V substrates using aqueous electrolytes. Different
coatings were produced by varying the time periods and the source of calcium. Commercially available calcium nitrate and calcium nitrate
produced from calcined sea shell were used as sources of calcium in the electrolysis. Various phases of the coatings were characterised by
XRD, TEM and FT-IR. Corrosion tests were performed on the coatings by exposing them to uniform corrosion in Simulated Body Fluid
(SBF) for 1 month as well as by electrochemical polarization and ac impedance techniques. These tests indicate that HA coatings produced
from sea shell source are superior having rough surface and long-term stability in SBF.
D 2005 Elsevier B.V. All rights reserved.

Keywords: Titanium; Hydroxyapatite; Cathodic deposition; Carbonate; SBF; Corrosion

1. Introduction surface treatment techniques like plasma spraying [9 – 11],

Calcium phosphate ceramics (CPC) are widely used for
clinical applications because of their good biocompati-
bility (osseophilic nature). Various types of these
ceramics, such as tetracalcium phosphate, hydroxyapatite
(HA) and h-tricalcium phosphate (h-TCP) are incorpo-
rated in bone tissue [1]. HA coated specimens achieve
bone mineralization directly on the surface of coating [2].
There appears to be better bone growth and penetration,
and greater direct contact between the tissue and the
implant surface. Samples without HA coating show lack
of direct bone deposition on the surface of titanium [3].
However, HA has lower fracture toughness compared to
the human bone [4] and very low reliability under tensile
loads.
Titanium and its alloys are widely used as implant
materials for failed hard tissue because of excellent
corrosion resistance and good compatibility with bone [5–
8]. To coat HA on the surface of titanium alloys, many
* Corresponding author. Tel.: +91 044 22578591.
E-mail address: rnarayan69@hotmail.com (R. Narayanan).
0257-8972/$ - see front matter D 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.surfcoat.2005.04.040
immersion in physiological fluid [12 –14], sol – gel method
[15 – 17], electrophoretic deposition [18 – 20], cathodic
deposition [21 – 26], ion-beam techniques [27 – 29] and
sputtering techniques [30,31] have been used.
Sea shell is the hard rigid outer calcium carbonate
covering of certain animals. The shell is usually made of
outer layers of proteins, followed by an intermediate layer of
calcite and a smooth inner layer of platy calcium carbonate
crystals. These sea shells are just laid to waste and are
abundantly available in nature. This can be effectively re-
used for the production of HA powder or coating.
Electrochemical cathodic deposition is one such inex-
pensive process wherein calcium phosphate or HA can be
obtained as a coating directly at room temperature. Calcium
phosphate is coated on the titanium alloy substrate from
electrolytes containing dissolved calcium and phosphorus
and can be further treated to get HA. Alternately, by
maintaining a molar ratio of calcium and phosphorus at 1.67
in the electrolyte and a steady pH of 4.2, it is possible to
obtain HA directly on the titanium alloy cathode.
This paper describes cathodic deposition of HA on to Ti-
6Al-4V substrate using calcium and phosphorus compounds
in the electrolyte. Two sources of calcium namely, a)
 R. Narayanan et al. / Surface & Coatings Technology 200 (2006) 4720 – 4730 4721

Table 1
Nomenclature of the coatings
Electrolyte Electrolysis conditions Further treatment Nomenclature
2
0.042 M/l inorganic Ca(NO3)2 and 0.025 M/l (NH4)2HPO4 20 mA/cm 30 min – IS1
0.042 M/l inorganic Ca(NO3)2 and 0.025 M/l (NH4)2HPO4 20 mA/cm2 60 min – IS2
0.042 M/l organic Ca(NO3)2 and 0.025 M/l (NH4)2HPO4 20 mA/cm2 60 min 0.1N NaOH 24 h OS1
0.042 M/l organic Ca(NO3)2 and 0.025 M/l (NH4)2HPO4 20 mA/cm2 60 min SBF (pH 7.4) 1 week OS2

commercial inorganic calcium nitrate and b) calcium nitrate 2. Experimental procedure

obtained by reaction of nitric acid with calcined sea shell
powder, are used. Structural features and long term The electrolyte used in this work contains 0.042 M/l of
corrosion properties in physiological solution simulating Ca(NO3)2 and 0.025 M/l of (NH4)2HPO4. This solution has
body fluid are reported. a molar ratio of Ca to P as 1.67 and a pH of 4.1.

a Ti Ti
800
(002) (101)

700
Ti
Ti (110)
600 HA
HA
(102)
Intensity (arbitrary units)

(211) IS1
(002)
500

400

300

200
IS2

100

0
0 15 30 45 60 75 90
2 theta

b
1200
Ti
(002)

1000

HA
Intensity (arbitrary units)

800 (112) HA
(410)
OS2

600

400

OS1

200

0
0 15 30 45 60 75 90
2 theta

Fig. 1. a) XRD pattern of IS1 and IS2 showing peaks for HA and the base material; b) XRD pattern of OS1 and OS2 showing peaks for HA and the base
material.
4722 R. Narayanan et al. / Surface & Coatings Technology 200 (2006) 4720 – 4730

Rectangular samples of Ti-6Al-4V of area 2  3 cm2 Electron diffraction pattern (Fig. 2a) of IS1 shows
were used as the cathode, and 304 stainless steel plate was diffraction rings characteristic of the fine-grained
used as the anode to complete the electrolytic cell. structure of the HA coating (Fig. 2b). Fig. 3a and b
Coatings were obtained by applying current at the rate of shows that the coating IS1 is dense and uniform
20 mA/cm2 for 30 min and 60 min. The sequence of without any discontinuities. Similar to IS1, OS1 is also
operations involved are: mechanical polishing, etching in a uniform and contains no porosity as can be seen from
solution containing 1 part HF, 4 parts HNO3 and 5 parts Fig. 3c and d.
H2O followed by cathodic deposition. Coatings obtained Fig. 4 gives the cross section of the coatings. The
by this method contained HA. coating edge was protected by copper deposition and
Sea shell is powdered and calcined for 1 h at 900 -C. One observed under microscope. HA formed was sandwiched
part of this powder is treated with two parts of HNO3 and between base material and copper layer. Table 2 gives the
the product is washed in water and dried. This yields values of thickness for all the coatings. It can be seen from
calcium nitrate which is termed as Forganic calcium nitrate_ Table 2 that thickness of IS1 was highest, followed by IS2,
in this paper. This is used as source of calcium in the OS1 and OS2.
electrolysis and coatings are obtained as described earlier. Coatings produced from inorganic calcium source
Coatings obtained from this source do not contain HA. In (namely IS1 and IS2) directly yielded HA. The cathodic
order to obtain HA, these coatings are further treated either
in a) 0.1N NaOH for 24 h, or in b) SBF for 1 week. Care is
taken to maintain the pH of SBF at 7.4 throughout the week.
Once HA is obtained, the coatings were subjected to
corrosion tests.
Philips (Model XD-D1) microprocessor controlled X-
ray diffractometer was used to identify the various phases
using Cu Ka incident radiation (k = 1.5481 Å). Philips
(Model CM 12 STEM Unit) TEM using electron energy
of 120 kV, was used to obtain the structural features.
Coatings were analysed for the functional groups using
FTIR of Perkin-Elmer to make Spectrum-One of reso-
lution 4 cm 1. Uniform corrosion behaviour of these
coatings was studied in a buffered physiological solution
simulating body fluid condition. This solution contained
NaCl 8.74 g/l, NaHCO3 0.35 g/l, Na2HPO4 0.06 g/l and
NaH2PO4 0.06 g/l [32] and pH was maintained at 7.4.
Loss of weight of the coatings is taken as the measure of
corrosion of the coatings. Electrochemical polarization of
the coatings was carried out using microprocessor con-
trolled ACM corrosion testing unit. The coating formed
the working electrode and graphite was the auxiliary
electrode. Polarization was carried out in the range  700
to 4000 mV (vs. SCE) at a scan rate of 300 mV/min.
Impedance test was conducted in the frequency range 104
to 10 2 Hz.

3. Results and discussion

3.1. Nomenclature

Nomenclature of the coatings is given in Table 1.

3.2. Structural features

Fig. 1a and b gives the XRD pattern of the coatings

produced from inorganic calcium nitrate and organic
calcium nitrate, respectively. These diffractograms indi- Fig. 2. a) SAED pattern of IS1 showing characteristic rings for HA. b)
cate the presence of HA along with the base material. Structure of IS1 showing fine grains of HA.
 R. Narayanan et al. / Surface & Coatings Technology 200 (2006) 4720 – 4730 4723

Fig. 3. Morphology of coatings: a) morphology of IS1, b) dense uniform IS1, c) morphology of OS1, d) dense uniform OS1.

Fig. 4. Cross section of coatings: a) cross section of IS1 showing coating of thickness about 45 Am; b) cross section of OS1 showing coating of thickness about
0.70 Am.
4724 R. Narayanan et al. / Surface & Coatings Technology 200 (2006) 4720 – 4730
Table 2
Coating thicknesses
Coating Thickness (Am)
IS1 45
IS2 20
OS1 0.70
OS2 0.50
reactions occurring in this electrolysis, according to [23]
are:
O2 þ 2H2 O þ 4e Y 4OH
2Hþ þ 2e Y H2
 coatings increases in the order—OS2 < OS1 < IS1 < as-
2HPO2 3
4 þ 2e Y 2PO4 þ H
2
2H2 O þ 2e Y H2 þ 2OH
The phosphate ions formed react with calcium cations
to form HA and deposit on the cathode, at the acidic pH
of 4.1.
Coatings produced from organic source produced cal-
cium phosphates. These calcium phosphates are treated
further in 0.1N NaOH for 24 h to obtain OS1 or in SBF for 1
week (pH7.4) to obtain OS2. These two treatments convert
the calcium phosphates completely to HA.
Prado Da Silva et al have reported similar cathodic
deposition wherein monetite (CaHPO4) deposited on tita-
nium cathode was completely converted to HA by
immersion of the coated sample in 0.1 M NaOH solution
for 24 h at 60 -C. Through subsequent dissolution of the
monetite coating, enrichment of Ca2+ and PO43 ions in the
solution occur and thermodynamic equilibrium is reached.
As a consequence of this, the surface is completely covered
with HA [33].
The inorganic source reported in this study, resulted in
HA being formed directly on Ti-6Al-4V substrate and the
HA deposited was very thick compared to that produced
from organic source. Calcium phosphates formed from
organic calcium nitrate, dissolve during the subsequent
NaOH or SBF treatments, making the solution saturated
with calcium and phosphorus. From the supersaturated
NaOH or SBF, HA is precipitated as thin layer completely
covering the surface. HA has lower solubility in water than
any other calcium phosphate, i.e., it is the most stable form
of calcium phosphate in aqueous media around pH7.4 [34].
Of all calcium phosphates, HA has the highest driving force
for precipitation from solutions saturated with calcium and
phosphorus at pH7.4 [35].
FT-IR analysis, in the transmittance mode, for the
coatings shows the presence of carbonate group at around
1430 cm 1, hydroxide group at around 3410 and 1640
cm  1 and phosphate group at 600 or 565 cm  1
representing r4 O-P-O bending vibration. Carbonate group
shown in IS1 (Fig. 5a) must have come from the
atmosphere as it has been reported earlier that CO2 and
CO can be produced on the coatings from CO2 molecules
of the air adsorbed on the sample surface and these in turn
can form CO32 groups on the coating [36 –38]. Carbonate
group in the Fas-deposited coating produced from organic
calcium nitrate (before the NaOH or SBF treatments)_
must have come from the seashell source (Fig. 5b).
Carbonate contents in OS1 (Fig. 5c) and OS2 (Fig. 5d)
were lower than IS1 or the Fas-deposited coating from
organic calcium nitrate_. To get a rough idea about the
amount of carbonate in the coatings, transmittance mode is
changed to absorbance mode and area covered by the
peaks indicative of carbonate group is measured and
tabulated in Table 3.
It can be seen from Table 3 that the carbonate in the
deposited coating from organic calcium nitrate. It can be
observed that the presence of carbonate is not indicated
by X-ray diffraction (Fig. 1a and b) or by electron
diffraction (Fig. 2a and b). The presence of carbonate in
the apatite lattice was shown to cause a decrease in
crystallinity [39], higher efficiency of densification, higher
presence of newly formed bone and an increase in
solubility in both in vitro and in vivo tests [40].
Carbonate ions bring about structural disorder and
crystallographic defects in the apatite lattice which
subsequently favours biological apatite nucleation [41].
Carbonate is known to nucleate [35] but inhibit crystal-
lization of HA [42]. Carbonate content in the as-deposited
coating using organic calcium nitrate is higher than in
other coatings (Table 3) and this condition leads to a
decrease in HA crystallinity and the absence of HA in
diffraction patterns. It cannot be said with certainty that
crystalline HA is totally absent in this case. When this
coating is subjected to subsequent NaOH or SBF treat-
ments, the carbonate in the coating helps in the
dissolution leaving a thin residual coating (OS1 or OS2)
containing less carbonate and crystalline HA.
3.3. Corrosion in SBF
Fig. 6 gives the corrosion rate expressed in milligrams/
sq. decimeter/day (mdd) of the coatings exposed to SBF
for 1 month. It can be seen that the coatings IS1 and IS2
show higher corrosion rates than coatings produced from
organic source. The outer layers of the thick HA coating
from inorganic source, dissolved easily leading to a
greater weight loss. The lower corrosion rates in case of
the coatings OS1 and OS2 could be attributed to the
presence of a thin HA coating which does not dissolve
easily.
By the reaction between the calcium and phosphate ions
from the SBF, apatite precipitates are formed on the
coating surface [43]. During the first week of immersion,
large amounts of loosely held HA in the thick IS1 and IS2
coatings dissolve in SBF, leaving the Ti-6Al-4V surface
exposed to the surrounding fluids, which is undesirable.
 R. Narayanan et al. / Surface & Coatings Technology 200 (2006) 4720 – 4730 4725

a Carbonate
group
100.1
98
96 1742.48
94
1421.44
92
1651.65 1384.55
90 2853.36
88
86 2924.03 562.16

84
82
Phosphate
80 3421.70 group
78
%T
76
74
72
70
1031.54
68
66
64
62
60
58

55.4
4000.0 3000 2000 1500 1000 450.0
cm-1

wave number (cm-1)

Carbonate group

b
100.1
465.76
95

90
902.60
85 868.61

80 672.42
1642.94
75 1464.64 601.89
2852.33
70
%T
65 2922.45

60 Phosphate
group
55
3409.94 1046.83
50

45

40

35
32.5
4000.0 3000 2000 1500 1000 450.0
cm-1

wave number (cm-1)

Fig. 5. a) FT-IR spectra of IS1; b) FT-IR spectra of Fas-deposited coating from organic calcium nitrate_; c) FT-IR spectra of OS1; d) FT-IR spectra of OS2.
4726 R. Narayanan et al. / Surface & Coatings Technology 200 (2006) 4720 – 4730

c Carbonate
group
100.2

873.78 670.66
95 1636.66 470.02
2852.58 1461.36

90 2922.76 1420.47

3428.93
85 602.86
566.96

80 Phosphate
group
75
%T

70

65

1037.56
60

55

50

46.3
4000.0 3000 2000 1500 1000 450.0
cm-1

wave number (cm-1)

Carbonate group

d
100.1

99

98
1425.94

97
2852.55 1631.98

96
600.62

2923.10 561.11
95

94
Phosphate
%T 93 group
3432.46
92

91

90

89

88 1035.57

87

86.0
4000.0 3000 2000 1500 1000 450.0
cm-1

wave number (cm-1)

Fig. 5 (continued).
 R. Narayanan et al. / Surface & Coatings Technology 200 (2006) 4720 – 4730 4727

OS1
Table 3
Area under the curve for carbonate species in the absorbance mode 2000
Coating Area
(A cm 1)

IS1
As-deposited coating produced from organic calcium nitrate
(before NaOH or SBF treatment)
OS1
OS2
After two weeks of soaking, however, small globular
crystals start to precipitate on the coating surfaces. More
crystals would be formed after 4 weeks of soaking
covering the coating surface completely, with no further
dissolution taking place after that. In case of OS1 and
OS2, HA is formed as thin but tightly held coating and its
outer layers do not dissolve with the result that the weight
loss in both these coatings is less leading to lower
corrosion rates.
Results of potentiodynamic polarization are given in Fig.
7, while values for corrosion current and impedance are
given in Table 4.
An equivalent circuit for modeling the corrosion
behaviour during the application of ac signal is given in
Fig. 8. The circuit consists of one R-C element connected
in series with a Warburg element and in parallel with a
constant phase element. The constant phase element
(CPE) corresponds to electron transfer at the interface
dominated by the porous nature of the oxide film and is
the impedance provided by the roughness and inhomoge-
neity of the porous and passive layers. Warburg impe-
dance accounts for the diffusion process, namely, transfer
of ions across the coating (porous and passive layers)
[44].
High frequency regions (frequency exceeding 103 Hz)
yield the value of electrode ohmic resistance, R sol, which
includes electrolyte resistance, cell geometry, impedance
of the conductors and the reference electrode. The
intermediate frequency region 103 – 10 Hz describes the
dielectric properties of the electronically conducting sur-
face film. The low frequency region (< 10 Hz) detects the
4
Corrosion rate (mdd)
Potential (mV)
1000 IS1
2.03
3.83 IS2
0
0.98
0.82
-1000
OS2
10-8 10-7 10-6 10-5 10-4 10-3
2
Current (mA/cm )
Fig. 7. Potentiodynamic polarization curves of the coatings.
electron charge transfer process, the mass transfer (dif-
fusion or migration) processes or other relaxation pro-
cesses taking place at the film-electrolyte interface or
within the pores of the film. Coatings containing lower
carbonate content exhibit a beneficial corrosion protection
effect on the substrate and those containing greater amount
of carbonate showed a marked change in impedance due
to degradation of the coating, upon prolonged exposure to
SBF [45].
Impedance of a constant phase element {CPE}, denoted
as Z CPE is given by Z CPE = [ Q(jx)n ] 1 where Q is the
capacitance, n is the roughness factor and ù is the angular
frequency [46]. Q and n are frequency independent
parameters and n can vary from  1 to 1. CPE describes
an ideal capacitor when n = 1, Warburg element when
n = 0.5, an ideal resistor when n = 0 and pure inductor when
n =  1 [47].
The results of ac impedance are given in Table 5. It
can be seen from Table 5 that roughness values of
coatings produced from organic calcium nitrate are lower
than those of coatings produced from inorganic calcium
nitrate. Coatings produced from organic source have
higher values for constant phase element than those of
coatings produced using inorganic calcium nitrate. Unlike
the inorganic calcium nitrate, it is possible that the
calcium nitrate prepared by reaction of nitric acid with
calcined sea shell powder is impure leading to the
contamination of the deposit. Though this can result in
deterioration of coating properties, NaOH and SBF treat-
ment appears to enhance the corrosion resistance of the
coatings. This can account for the difference in corrosion

properties of HA coatings produced from these diverse

3
sources.
2

Table 4
1 Results of corrosion tests
Coating mdd values icorr (AA/cm2) Impedance (ohm cm2)
0
IS1 3.21 0.185 1.01 103
IS1 IS2 OS1 OS2
IS2 2.55 0.061 5.48  103
Coating type OS1 1.15 0.016 1.58  104
Fig. 6. Corrosion rate of cathodic HA. OS2 0.77 0.001 2.06  105
4728 R. Narayanan et al. / Surface & Coatings Technology 200 (2006) 4720 – 4730

Fig. 8. Equivalent circuit depicting the corrosion model.

To ascertain their effectiveness for long time usage, the
coatings were exposed to SBF and ac impedance data were
recorded after 3, 6, 9 and 12 h of exposure. Variation of total
impedance (of the equivalent circuit shown in Fig. 8) with
soaking time is shown in Fig. 9 with the results tabulated in
Table 6.
It can be seen from Table 6 that the total impedance of
coating OS2 is the highest followed by OS1, IS2 and IS1
under the conditions of F0 hour of soaking_. Soaking for 3 h
increases the total impedance of OS2 and IS2; with further
increase in time to 6 h, the impedance of OS2 decreases and
that of IS2 increases steeply followed by a further steep
decrease thereafter. It can be seen in Fig. 9 that the change in
impedance of IS2 is rapid and this coating is unstable
compared to OS2.
The impedance of OS2 and IS2 is higher than the other
two coatings; and the change in impedance of IS2 is rapid
compared to the change of impedance of OS2. OS2 is
prepared by exposing the calcium phosphate coating to SBF
for 1 week. This long-term immersion in SBF helps in the
formation of thin layer of stable HA on the surface of OS2
(Table 2) with lower carbonate content (Table 3). It has been
reported by other workers [48,49] that, with increase in
immersion time in SBF, islands of apatite grow and coalesce
on the titanium surface. Immersion in SBF for 1 week
completely covers the surface of OS2 with HA crystals and
improves its long-term corrosion resistance. Also, coatings
containing lower carbonate content exhibit a beneficial
corrosion protection effect on the substrate and those
containing a greater amount of carbonate showed a marked
change in impedance due to degradation of the coating upon
prolonged exposure to SBF [45]. Hence it is to be expected
that IS1 shows inferior corrosion resistance and OS2 shows
higher corrosion resistance.
Coatings IS1 and IS2 are thicker than the other two and
hence their outer layers dissolve leading to attack by SBF as
was observed in immersion, potentiodynamic polarization
and ac impedance tests. While OS1 and OS2 were thin
coatings deposited from exposure to NaOH and SBF,
respectively, it is possible that the hydroxide groups from
NaOH or SBF promote the precipitation of calcium and
phosphorus and improve interaction with osteoblasts. It is
suggested that the coatings OS1 and OS2 would show better
biological performance than IS1 and IS2. NaOH treatment
may incorporate small quantities of sodium in OS1 which
could affect the cell adhesion onto that surface. Inflamma-
tion and cell death occur if tissues experience high alkaline
conditions. Na+ increases the degree of external alkalinity
and therefore it would be beneficial to decrease the release
of Na+ into the surrounding tissue. Titanium with lowest
content of Na+ is more suitable for implantation in the
human body because the released amount of alkali ions (if

Table 5
Results of ac impedance
Coating Roughness CPE (ohm cm2) 1 Warburg impedance R ct (ohm cm2) C dl (F) Total impedance
factor Fn_ (ohm cm2) (ohm cm2)
IS1 0.79 1.01 103 2.97  107 2.53  105 2.61 10 4 1.01 103
IS2 0.86 5.48  103 6.33  108 4.96  104 2.61 10 4 5.48  103
OS1 0.74 1.58  104 5.57  107 1.84  109 2.61 10 4 1.58  104
OS2 0.44 2.06  105 5.38  109 8.6  105 2.61 10 4 2.06  105
 R. Narayanan et al. / Surface & Coatings Technology 200 (2006) 4720 – 4730 4729

700000
OS2 shows roughness values of almost close to 0.5 and
with further increase in time, the roughness decreases and
600000 then increases steeply to values closer to 1 approaching a
IS2
capacitive behaviour. This indicates that the surface of
500000 OS2 has smoothened after 9 h. OS1 shows roughness
values of almost close to 0.75 and with further increase
Impedance (ohm-sq.cm)

400000 in time, the roughness increases to values closer to 1

300000
200000
100000
0 implant applications. It is also expected to show better
-100000
0 3 6 9
Soaking time (hours)
Fig. 9. Variation of total impedance with time of soaking.
there is any release) in the surrounding tissue is lower and
the rate of apatite formation is the same as that for the
titanium with the highest content of Na+ in the surface layer
[14].
Roughness values indicate the tendency for increased cell
adhesion and activity. Greater surface roughness results in
greater number of adhered osteoblasts and higher cell
activity [50]. Rough, textured and porous surfaces could
stimulate cell attachment and formation of extra-cellular
matrix. Presence of surface roughness provides initial
stabilization until bone can grow and attach to the implant
surface to provide further improvement in implant bonding
[51].
Roughness values lower than 0.5 indicate a rough
surface and such surfaces behave like resistors. Rough-
ness value of 0.5 indicates Warburg diffusion process;
roughness more than 0.5 or close to 1 indicates that
smoothening process takes place and such surfaces
behave like capacitors. It can be seen from Table 6 that
coatings IS1 and IS2 show maximum and minimum
values of roughness exhibiting no conclusive pattern.
approaching a capacitive behaviour. This indicates that
OS2
the surface of OS1 has also smoothened after 9 h. The
roughness values for IS1, IS2 and OS1 obtained in this
study are comparable to those obtained for titanium
alloys exposed to buffered saline solution reported earlier
[46]. The coating OS2 has low roughness values and
IS1
highest impedance values with no Frapid change with
exposure time_ and is found to be a better candidate for
biological performance than the other coatings because of
its rough surface with a lot of bioactive hydroxyl groups
12 in it.
Attempts are now being made to purify the organic
calcium nitrate source. Experiments are being done to
ascertain whether the purified organic calcium nitrate can
directly yield HA, so that the intensive soaking treatments
become redundant.
4. Conclusions
Coatings IS1 and IS2 are produced from inorganic
commercial source of calcium. They are thicker, contain
more carbonate and dissolve more easily leading to attack
by SBF. Calcium phosphate coatings are prepared from
calcium nitrate source prepared from sea shell. Coatings
OS1 and OS2 are produced by further treatment of these
coatings in NaOH and SBF, respectively. These coatings
are thin, contain lower amounts of carbonate and show
good resistance to corrosion in SBF medium. The coatings
OS1 and OS2 had low roughness values exhibiting
Warburg type of impedance. OS1 may contain some
amount of sodium which is unsuitable for body implant
application. OS2 is a rough coating containing lot of
bioactive hydroxyl groups and is expected to show better
biological performance.

Table 6
Impedance data after soaking in SBF
Coating Parameters Time of soaking in SBF
0h 3h 6h 9h 12 h
2 3 3 3 4
IS1 Impedance (ohm cm ) 1.01 10 8.26  10 4.47  10 2.05  10 5.5  103
Roughness factor 0.79 0.54 0.62 0.44 0.59
IS2 Impedance (ohm cm2) 5.48  103 1.81 105 6.09  105 1.73  104 8.03  103
Roughness factor 0.86 0.46 0.30 0.73 0.82
OS1 Impedance (ohm cm2) 1.58  104 1.46  104 4.23  103 3.74  103 2.33  103
Roughness factor 0.74 0.75 0.89 0.90 0.96
OS2 Impedance (ohm cm2) 2.06  105 3.51 105 9.2  104 3.47  103 1.79  103
Roughness factor 0.44 0.38 0.53 0.91 0.98
4730 R. Narayanan et al. / Surface & Coatings Technology 200 (2006) 4720 – 4730
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