MA TE RI A L S CH A R A CT ER IZ A TI O N 61 ( 20 1 0 ) 7 8 6–7 9 5

available at www.sciencedirect.com

www.elsevier.com/locate/matchar

Effects of pulsed current and H2O2 amount on the composition

of electrodeposited calcium phosphate coatings

R. Drevet a,⁎, H. Benhayoune a , L. Wortham a , S. Potiron a , J. Douglade b , D. Laurent-Maquin a

a
INSERM UMR-S 926 URCA CHU, 1 rue Maréchal Juin 51096 Reims Cedex, France
b
L.A.C.M.-D.T.I. EA 4302 URCA, Moulin de la Housse BP 1039 51687 Reims Cedex 02, France

AR TIC LE D ATA ABSTR ACT

Article history: Calcium phosphate coatings on Ti6Al4V substrates were elaborated by pulsed
Received 11 May 2009 electrodeposition with hydrogen peroxide (H2O2) into electrolyte. The surface morphology
Received in revised form and the chemical composition of the coatings were characterized by scanning electron
26 February 2010 microscopy (SEM) associated to Energy Dispersive X-ray Spectroscopy (EDXS) for X-ray
Accepted 29 April 2010 microanalysis. The obtained results were systematically confirmed at the nanometre scale
analysis using scanning transmission electron microscopy (STEM). Moreover, X-ray
Keywords: diffraction (XRD) was performed in order to identify the coatings phases. The results
Electrodeposition showed that pulsed electrodeposition without H2O2 into electrolyte followed by heat
Stoichiometric hydroxyapatite treatment favoured coatings made of two phases which are stoichiometric hydroxyapatite
Hydrogen peroxide (HAP) and β-tricalcium phosphate (β-TCP). On the other hand the addition of an optimized
Tricalcium phosphate H2O2 amount into electrolyte led to adherent and uniform coatings mainly made of
Electron microscopy (SEM–STEM) stoichiometric hydroxyapatite (HAP).
© 2010 Elsevier Inc. All rights reserved.

1. Introduction has been tested, it consists of performing electrodeposition

Titanium and its alloys are widely used as implant materials
in orthopaedic surgery because of their good biocompatibility
with bone. However, a way to make them bioactive is to coat
them with calcium phosphate ceramics, especially hydroxy-
apatite (HAP) which is able to form a real bond with the
surrounding bone tissue in vivo [1–4]. Many methods are
developed and used to prepare HAP coatings onto implant
surfaces, for example, plasma spray [5–7], sol–gel [8–10],
pulsed laser-deposition [11,12], electrophoretic method [13–
15] and electrochemical deposition [16–20]. This last method
has a variety of advantages: the coating process occurs at low
temperature, thickness and chemical composition could be
controlled. However, it also presents some disadvantages:
high production of H2 bubbles at the surface linked to the
applied current and a decreasing amount of ions at the vicinity
of the cathode. This phenomena lead to non uniform and
deficient coatings. In order to solve these problems, a method
under air atmosphere by stirring the electrolyte [21,22].
Unfortunately, the coating adhesion and reproducibility were
not satisfactory. Another method has been proposed by Wang
et al. [23] who studied the morphology of calcium phosphate
coatings deposited on a Ti–6Al–4 V substrate by an electrolytic
method under vacuum. They mainly showed that electrolytic
deposition at 80 Torr improves bubble removal in the vicinity
of the cathode surface and encourages the deposition of
calcium phosphates. However, this method is difficult to be
carried out. Thus, pulsed electrodeposition may be used as an
alternative process. Indeed, the relaxation time between two
deposition times (pulse cycle) strongly reduces H2 bubbles
emission and allows ions to diffuse from the solution to the
cathode surface.
Legeros et al. [24] used pulse time electric fields in
electrochemical deposition (ECD) to obtain uniform and
adherent calcium phosphate coatings to titanium alloy
substrate.

⁎ Corresponding author.
E-mail address: richard.drevet@univ-reims.fr (R. Drevet).

1044-5803/$ – see front matter © 2010 Elsevier Inc. All rights reserved.
doi:10.1016/j.matchar.2010.04.016
 M A TE RI A L S CH A RACT ER IZ A TI O N 61 ( 20 1 0 ) 7 8 6 –7 9 5
Chen et al. [25] used pulsed electrodeposition associated with
H2O2 into electrolyte to obtain hydroxyapatite coatings with
improved adhesive strength between coating and substrate.
However, the H2O2 amount has not been optimized and its effect
on coating composition has not been demonstrated.
Thus, in the present work, calcium phosphate coatings are
prepared by pulsed electrodeposition current with H2O2 into
electrolyte. The pulse parameters and the H2O2 amounts are
examined in order to evaluate their effects on the composition
of electrodeposited coatings.
2. Materials and Methods
2.1. Pulsed Electrodeposition Current
The experimental setup used for electrodeposition consists of
a three-electrode system: cathode (Ti6Al4V substrate), counter
electrode (Pt) and reference electrode SCE (saturated calomel
electrode). The distance between cathode and platinum
counter electrode is about two centimetres.
The electrolyte is prepared by mixing a solution of 0.042 M
Ca(NO3)2 4H2O and 0.025 M NH4(H2PO4) with varied amounts of
hydrogen peroxide (H2O2): 0%, 3%, 6%, 9%, 12% and 15% in
volume. The pH value is adjusted to 4.4 by adding 0.1 M NaOH
solution and the temperature fixed at 60 °C.
The flat Ti6Al4V substrate has 10 mm × 10 mm × 0.6 mm size.
Its surface is blasted with alumina particles for an average
roughness of 2–3 μm. Prior to coating, the substrate is etched
during 1 min in a mixture of acids consisting of nitric acid (HNO3,
6% in volume) and hydrofluoric acid (HF, 3% in volume). Next, the
sample is ultrasonically cleaned in acetone and demineralised
water during 10 min in order to remove alumina residues.
Electrodeposition is performed with a potentiostat/galvano-
stat instrument (Voltalab PGP 201 Radiometer Analytical —
VOLTAMASTER software) by pulsing the current as indicated in
Fig. 1. A time deposition td = 1 min with a current density
jd = 15 mA/cm² followed by a break time tb = 2 min (jb = 0 mA/cm²).
In these conditions, the average current density is:
jd ⋅td
ja = = 5 mA=cm2 ð1Þ
td + tb
Fig. 1 – Schematic representation of pulsed current during
electrodeposition (5 cycles).
787
Five pulse-cycles are used during deposition, which
corresponds to a total deposition time of 15 min.
2.2. Microscopy Study
2.2.1. Scanning Electron Microscopy (SEM)
The morphology of the coating is observed using a LaB6
electron microscope (JEOL JSM-5400LV) operating at 0–30 kV.
This microscope is associated to an ultra-thin window Si(Li)
detector for X-ray measurements. The specimens are coated
with a conductive layer (Au–Pd for SEM micrographs and
carbon for X-ray microanalysis). The X-ray spectra are
acquired at 15 kV with an acquisition time of 100 s. For the
quantitative analysis, commercial software (GENESIS, Eloïse
SARL, France) associated with an original procedure for
coating analysis developed in our laboratory is used [26–28].
Moreover, several measurements are carried out to calculate
mean value of Ca/P atomic ratio and coating thickness (t) with
standard deviation.
2.2.2. Scanning Transmission Electron Microscopy (STEM)
A LaB6 scanning transmission electron microscope (Philips
CM30) operating from 100 to 300 kV is used to study the
morphology of samples at a nanometre level. Thus, a specific
specimen preparation is carried out using EPON resin (Kit
AGAR 100 RESIN, Oxford Instruments France). The preparation
process consists of several steps schematically sketched in
Fig. 2. First, the coating is impregnated by the resin without
hardener (Fig. 2b). Next, the specimen is immersed in liquid
nitrogen (Fig. 2c) which leads to the removal of the Ti6Al4V
substrate by thermal shock. At this stage, the sample is only
calcium phosphate coating embedded in resin. The ultra-thin
section (∼ 100 nm) is cut with diamond cutter using an
ultramicrotome and collected on copper grids (Fig. 2d). Finally,
the sections are coated with a conductive layer of carbon and
they are observed at a voltage of 250 kV.
2.3. X-ray Diffraction Analysis
Calcium phosphate powders are scratched from electrode-
posited coatings. Their phase composition is investigated
using X-ray diffractometer (Bruker D8 Advance). The X-ray
pattern data are collected from 2θ = 10 to 45° using a
monochromatic CuKα radiation with a step of 0.04° every 12 s.
XRD analysis is carried out before and after the heat
treatment in air atmosphere at 1000 °C during 15 h to determine
the phase percentage following French Norm (NF S 94-066,
AFNOR, France). The procedure consists of calculating the
summed intensities ratios of several peaks for each phase.
These ratios are compared to those obtained from standards
biphasic samples with known percentages. Then, Ca/P atomic
ratio is deduced, considering the percentage of the two phases.
2.4. Bonding Strength Test
The bonding strength of the coatings is examined using a
Material Testing System MTS 810 (CRITT-MDTS, Charleville-
Mézières, France) according to ASTM norm F1147-05. Ti6Al4V
cylinders (25 mm in diameter by 25 mm in height) are coated
and bonded to uncoated cylinders surface with epoxy
788 MA TE RI A L S CH A R A CT ER IZ A TI O N 61 ( 20 1 0 ) 7 8 6–7 9 5
Fig. 2 – Sketch of the sample preparation for STEM observations.
adhesive. Five tests (n = 5) of adhesion strength are conducted
for the same type of coating in order to obtain an average value
of bonding strength measurements.
3. Results
3.1. Pulsed Electrodeposition Current without H2O2
Before deposition, X-ray microanalysis results of Fig. 3 clearly
show that no residues of alumina particles are observed after
etching treatment of the surface substrate.
Fig. 4 shows the chrono-potentiometric curve obtained in
pulsed current mode. The five cycles are observed and each
cycle is well represented by 2 min break (j = 0 mA/cm² and Efree
≈ + 350 mV vs. SCE) and 1 min time deposition (j = 15 mA/cm²)
in which the onset potential is about −2.2 V vs. SCE. The
potential variation as function of time for each cycle is similar
to chrono-potentiometric curve obtained by direct electrode-
position current at j = 5 mA/cm² [29].
The SEM micrograph of the obtained coating shown in
Fig. 5a indicates that the coating is composed of small needles
and crystallites. The STEM micrograph (Fig. 5b) confirms these
observations and shows that the needles size is less than
0.2 μm. Quantitative analysis from X-ray spectrum of Fig. 5c
gives a Ca/P atomic ratio of 1.60 ± 0.02 and a thickness t = 3.9 ±
0.3 μm as confirmed by SEM cross-section (Fig. 5d). The
presence of Ti and Al peaks is due to penetration range of
primary electrons R = 5 μm at E0 = 15 keV, which is greater than
coating thickness.
XRD pattern of Fig. 5e shows that the coating is composed
of an apatitic phase of low crystallinity with typical diffraction
peaks at 2θ = 25.9° – 31.8° – 32.2° – 32.9° – 34° – 39.8°
corresponding to hydroxyapatite (JCPDS 09-0432).
After heat treatment, XRD analysis (Fig. 5f) clearly indicates
that the coating is composed of two well crystallized phases,
stoichiometric hydroxyapatite (HAP) and β-tricalcium phos-
phate (β-TCP). The β-TCP has characteristic diffraction peaks
at 2θ = 27.8° – 31.1° – 34.4° (JCPDS 09-0169). The calculated
percentage of each phase is 52% HAP and 48% β-TCP. Thus, the
 M A TE RI A L S CH A RACT ER IZ A TI O N 61 ( 20 1 0 ) 7 8 6 –7 9 5
Fig. 3 – EDXS spectra of the Ti6Al4V substrate: (a) untreated
surface, (b) blasted surface with alumina particles, (c) etched
surface.
corresponding Ca/P atomic ratio is 1.59 in agreement with the
value obtained from X-ray microanalysis. The measured
adhesive strength is 9.3 ± 0.5 MPa.
3.2. Pulsed Electrodeposition Current with H2O2
3.2.1. Optimization of the H2O2
In order to optimize the H2O2 percentage into electrolyte,
cathodic polarization curves were carried out at different
values: 0, 3, 6, 9, 12 and 15% H2O2 (Fig. 6).
789
Fig. 4 – Chrono-potentiometric curve obtained in pulsed
electrodeposition current.
One observes that at 15 mA/cm² current density, the
potential values corresponding to electrolyte prepared with
3% or 6% H2O2 are less important than the potential value of
electrolyte with 0% H 2 O 2 . And the potential values
corresponding to electrolyte prepared with 9%, 12% and 15%
H2O2 are greater than the one prepared with 0% H2O2.
When H2O2 percentage is greater than 9%, the potential
value is higher leading to the increase of H2 production that
highly prevents nucleating and growing of coating on the
surface of cathode (Fig. 7e–f). When H2O2 percentage is 3%, the
potential value is so weak that hydrolysis reactions almost do
not take place that leads to non uniform coating (Fig. 7b).
Consequently, the H2O2 amounts retained in the present
work are 6 and 9%.
3.2.2. Electrodeposition with 6% H2O2 Electrolyte
Fig. 8 shows the obtained chrono-potentiometric curve in that
case. For each cycle, the onset potential is about − 1.6 V vs. SCE
and its variation as a function of time is different from that
one of Fig. 4. During deposition time (td) the potential value
increases to −1.5 V vs. SCE then decreases continually until
the break time. These different electrochemical behaviors
could be attributed to the simultaneous reduction of two
species, hydrogen peroxide and water, during the deposition
time instead of only water.
The morphology of the obtained coating is shown on the
micrograph of Fig. 9a. The needles are agglomerated in
crystallite spheres (∼2 μm size diameter) and some porosity
is observed. These observations are confirmed by STEM
micrograph of Fig. 9b where the section of this coating exhibits
spheres formed by needles agglomeration. The X-ray micro-
analysis (Fig. 9c) give a Ca/P atomic ratio of 1.65 ± 0.02 and a
thickness t = 3.5 ± 0.3 μm as confirmed by SEM cross-section
(Fig. 9d).
The corresponding XRD pattern after heat treatment is
shown on Fig. 9f. It clearly indicates that the coating is
composed of two well crystallized phases: stoichiometric
hydroxyapatite (HAP) as majority phase and β-tricalcium
phosphate (β-TCP) as minority phase. Indeed, the calculated
percentage of each phase is 80% HAP and 20% β-TCP. The
corresponding Ca/P atomic ratio was 1.63 in agreement with
the value deduced from X-ray microanalysis. The measured
adhesive strength is 11.2 ± 0.6 MPa.
790 MA TE RI A L S CH A R A CT ER IZ A TI O N 61 ( 20 1 0 ) 7 8 6–7 9 5

Fig. 5 – Characterization of the obtained coating in pulsed electrodeposition current: (a) SEM micrograph (magnification ×5000),
(b) STEM micrograph of needles (magnification ×20,000), (c) EDXS spectrum, (d) SEM cross-section, (e) XRD pattern before heat
treatment, (f) XRD pattern after heat treatment (1000 °C, 15 h).

3.2.3. Electrodeposition with 9% H2O2 Electrolyte
Fig. 10 shows the obtained chrono-potentiometric curve in
that case. During each cycle, the onset potential is about
−2.3 V vs. SCE, its variation as a function of time is similar to
that of the 6% H2O2 electrolyte. SEM micrograph of Fig. 11a
shows that the morphology of the obtained coating seems to
be similar but less porous than the one obtained with 6% H2O2.
However, the Ca/P atomic ratio and the thickness deduced
from X-ray microanalysis (Fig. 11b) are respectively 1.67 ± 0.02
and 3.3 ± 0.2 μm.
 M A TE RI A L S CH A RACT ER IZ A TI O N 61 ( 20 1 0 ) 7 8 6 –7 9 5
Fig. 6 – Evolution of the potential as a function of current
density for different H2O2 amounts.
The corresponding XRD pattern after heat treatment is
shown on Fig. 11c. It clearly indicates that the coating is
composed of only well crystallized stoichiometric hydroxyap-
atite (HAP) with Ca/P = 1.67. The adhesive strength in these
conditions is improved since the measured value reaches 16.5
± 0.9 MPa which is in accordance with required norms (15 MPa)
in orthopaedic implant industry [30].
Fig. 7 – Photography of the specimens at different H2O2
amounts, (a) 0%, (b) 3%, (c) 6%, (d) 9%, (e) 12%, (f) 15%.
791
Fig. 8 – Chrono-potentiometric curve obtained in pulsed
electrodeposition current with 6% H2O2 into electrolyte.
4. Discussion
4.1. Morphology
When the electrolyte without H2O2 is used in classical
electrodeposition, under direct current, the potential value
versus saturated calomel electrode may exceed − 1.5 V.
Therefore, reduction of water occurs, Eq. (2), as shown by
Kuo et al. [19] and H2 bubbles start to evolve from the cathode
surface leading to the formation of craters and holes at the
coating surface (Fig. 12a).
2H2 O + 2e− →H2 + 2OH− ð2Þ
The only way to avoid this problem is to apply weak current
densities (jmax = 10 mA/cm2) resulting on a weak basic pH value
(pHmax = 8) [29].
In pulsed electrodeposition current associated with H2O2,
the craters and holes disappear and the needles are agglom-
erated (Fig. 12b) because of two main reasons. First, during the
break time (tb) the ions diffuse from the solution to the surface
of the Ti6Al4V cathode and are adequately deposited. Second,
H2O2 is a strong oxidative reagent. It is reduced before water
and only OH− ions are produced as follow:
H2 O2 + 2e− ↔2OH− ð3Þ
Consequently, H2 emission is strongly reduced.
When the H2O2 amount exceeds 9% in volume the rate of
OH− generation is faster than the rate of OH− consumption by
hydrolysis reactions at the electrode. The OH− ions move away
from the electrode surface towards the electrolyte, resulting in
lower adhesion of the deposits [31].
4.2. Composition
In pulsed electrodeposition, the high current density used
(j = 15 mA/cm²) leads to a higher potential (−2 V vs. SCE). The
pH at the vicinity of the cathode is higher, therefore reaction (2)
is followed by acid–base reactions of phosphate ions such as:
H2 PO−4 + OH− →HPO2−
4 + H2 O ð4Þ
−
HPO2− 3−
4 + OH →PO4 + H2 O ð5Þ
792 MA TE RI A L S CH A R A CT ER IZ A TI O N 61 ( 20 1 0 ) 7 8 6–7 9 5

At these pH values (more than 12), the minority specie is When H2O2 is added into the electrolyte, reaction (3) takes
HPO2− 3−
4 and the predominant specie is PO4 as shown by Eliaz et place and the pH increases as a function of H2O2 amount,
al. [32]. Therefore, two phases are formed: leading to a decrease of HPO2−
4 specie. In that case the formation
of HAP phase following reaction (6) becomes predominant.
▪ Hydroxyapatite Finally, one can claim that pulsed electrodeposition
associated with H2O2 and appropriate thermal treatment
10Ca2 + + 6PO3− − leads to either monophasic (HAP) or biphasic (HAP, β-TCP)
4 + 2OH →Ca10 ðPO4Þ6 ðOHÞ2 ð6Þ
coatings.
▪ Apatitic tricalcium phosphate It is well known that calcium phosphate phases (as HAP
and β-TCP) exhibit different biological behaviors after immer-
9Ca2 +
+ 5PO3− − sion in physiological liquid or in contact with cells, such as
4 + HPO4 + OH →Ca9 ðHPO4 ÞðPO4 Þ5 ðOHÞ
2−
ð7Þ
resorbability, bioactivity, and dissolution. The association of
After heat treatment, all the apatitic tricalcium phosphate different calcium phosphate phases allows the modulating of
is converted into β-tricalcium phosphate (β-TCP) such as [33]: these properties [34,35].
heat treatment
In a previous study concerning biocompatibility of Ca-def
Ca9 ðHPO4 ÞðPO4 Þ5 ðOHÞ → 3Ca3 ðPO4Þ2 + H2 O ð8Þ HAP coatings obtained by classical electrodeposition [36],

Fig. 9 – Characterization of the obtained coating in pulsed electrodeposition current with 6% H2O2 into electrolyte: (a) SEM
micrograph (magnification ×5000), (b) STEM micrograph of agglomerated needles (magnification ×20000), (c) EDXS spectrum,
(d) SEM cross-section, (e) XRD pattern before heat treatment, (f) XRD pattern after heat treatment (1000 °C, 15 h).
 M A TE RI A L S CH A RACT ER IZ A TI O N 61 ( 20 1 0 ) 7 8 6 –7 9 5 793

Fig. 9 (continued).

we showed that these coatings promote human osteoblastic

differentiation and favour the extracellular matrix production.
It can be point out that when they are immersed into
Dulbecco's modified eagle's medium (DMEM), one observes
a rapid dissolution [37]. We believe that the newly devel-
oped protocol (pulsed electrodeposition current associated
with H2O2) will lead to biocompatible calcium phosphates
coatings with controlled dissolution kinetic. These studies
are in progress and the results will be reported in future
publications.

Fig. 11 – Characterization of the obtained coating in pulsed

electrodeposition current with 9% H2O2 into electrolyte :
(a) SEM micrograph (magnification ×5000), (b) EDXS spectrum,
(c) XRD pattern after heat treatment (1000 °C, 15 h).

5. Conclusion

In this study, calcium phosphate coatings were prepared by

pulsed electrodeposition current methods associated with
H2O2 into electrolyte. The physico-chemical and the structural
Fig. 10 – Chrono-potentiometric curve obtained in pulsed analysis were performed respectively by complementary
electrodeposition current with 9% H2O2 into electrolyte. SEM–STEM and XRD. The results showed that the obtained
794 MA TE RI A L S CH A R A CT ER IZ A TI O N 61 ( 20 1 0 ) 7 8 6–7 9 5
Fig. 12 – SEM micrographs (magnification ×200) of the
obtained coatings : (a) by direct electrodeposition current at
j = 5 mA/cm2, (b) by pulsed electrodeposition current.
coatings were better adhered and more uniform compared to
those made by classical electrodeposition. Moreover, the
addition of H2O2 made possible obtaining different calcium
phosphate phases.
Acknowledgments
The authors would like to sincerely thank Professor Jean
Ebothe (LMEN, Universite de Reims France) for his help and
CRITT-MDTS (Charleville-Mézières, France) for performing
adhesion measurements.
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