Materials Chemistry and Physics xxx (2014) 1e9

Contents lists available at ScienceDirect

Materials Chemistry and Physics

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

Effects of pulse electrodeposition parameters and alkali treatment

on the properties of nano hydroxyapatite coating on porous
MgeZn scaffold for bone tissue engineering application
Z.S. Seyedraoufi*, S. Mirdamadi
School of Metallurgy and Materials Engineering, Iran University of Science and Technology, 16846-13114 Tehran, Iran

h i g h l i g h t s g r a p h i c a l a b s t r a c t

Study on effects of pulse elc-

trodeposition parameters on HA
coating on MgeZn scaffold.

Synthesis of needle-like nano HA
coating developed perpendicularly to
the scaffold.

Converting as-deposited DCPD and
OCP into HA after alkali treatment.

Improving corrosion resistance of Mg
eZn scaffold with electrodeposition
of HA coating.

a r t i c l e i n f o a b s t r a c t

Article history: MgeZn scaffolds are potential biodegradable materials due to their attractive biological properties and
Received 14 August 2013 applications in bone tissue engineering. The aim of this study is to investigate the effects of pulse
Received in revised form electrodeposition parameters such as temperature, peak current density and duty cycle and alkali
7 June 2014
treatment on surface characteristics and corrosion properties of nano hydroxyapatite (Ca10(PO4)6(OH)2)
Accepted 29 June 2014
coating on the porous Mge2wt.% Zn scaffold. The results showed that the optimum conditions to create
Available online xxx
uniform nano hydroxyapatite coating on the MgeZn scaffold are at 40 mA cm2 peak current density, 0.1
duty cycle, 1 h time and 85  C temperature and the as-deposited coating consists of Ca10(PO4)6(OH)2 and
Keywords:
Biomaterials
CaHPO4$2H2O and Ca8H2(PO4)6$5H2O with needle-like and plate-like structures under optimum con-
Microporous materials ditions. The post-treated coating was composed of needle-like hydroxyapatite of less than 100 nm in
Coatings diameter developed almost perpendicularly to the substrate, which exhibits a similar composition of
Nanostructures natural bone. Electrochemical tests showed the corrosion potential of scaffold shifted from 1.47
Corrosion to 1.15 V and the corrosion current density reduced from 8  103 to 1.5  104 A cm2 after surface
modified by HA coatings.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction
Recently porous scaffold substitutes have attracted great inter-
est in bone tissue engineering applications [1]. In fact, porous
* Corresponding author. Tel.: þ98 21 77459151; fax: þ98 21 77240480.
E-mail address: zahraseyedraoufi@iust.ac.ir (Z.S. Seyedraoufi).
scaffold provides the needful support for proliferating cells and
maintaining their function. The ideal bone substitute material
should be biodegradable, osteoconductive and strong enough to
perform the required load-bearing functions [1,2]. Recently because
Mg has excellent mechanical properties, low densities and high
strength-to-weight ratios and is biodegradable, it has been recog-
nised as a very promising biomaterial for bone implants in load-
bearing applications [1e12]. Some studies have shown Mg ions

http://dx.doi.org/10.1016/j.matchemphys.2014.06.067
0254-0584/© 2014 Elsevier B.V. All rights reserved.

Please cite this article in press as: Z.S. Seyedraoufi, S. Mirdamadi, Effects of pulse electrodeposition parameters and alkali treatment on the
properties of nano hydroxyapatite coating on porous MgeZn scaffold for bone tissue engineering application, Materials Chemistry and
Physics (2014), http://dx.doi.org/10.1016/j.matchemphys.2014.06.067
2 Z.S. Seyedraoufi, S. Mirdamadi / Materials Chemistry and Physics xxx (2014) 1e9
may raise bone cell attachment and tissue growth on the scaffold
[8], but the high corrosion rate of Mg alloys leads to high concen-
trations of Mg ion and hydrogen gas release. It is essential to control
corrosion rate of Mg and Mg alloys. Zn element is recognised as an
essential element for humans, improves the corrosion resistance
and increases the mechanical properties of Mg alloys [13e16]. In
order to improve the corrosion resistance of magnesium alloys, an
effective approach might be the application of a surface modified
with HA. HA is currently used as a biomedical material due to its
excellent biocompatibility and bioactivity, attributed to its chemical
and structural similarities to bone and tooth minerals. On account
of its low strength and high brittleness, an important use of HA is as
a bioactive coating on metallic substrates [17]. The morphology and
crystal structure of HA is important for its biocompatibility and
osteoconductivity; moreover in recent years, there are growing
approaches toward nano particles and nano coatings which can
provide improved properties on their applications. Nano hydroxy-
apatite coating can have structure that is more matched to the bone
structure in which the implants should function and have lower
sintering temperature [18]. Many methods have already been
developed to prepare HA coatings on metallic substrates, such as
solegel process, electrophoretic deposition, sputtering process and
biomimetic methods; however, these cannot be used to deposit HA
coating on Mg alloy because of its low melting point and poor heat
resistance [12,17]. Electrochemical deposition has unique advan-
tages due to its capability of forming a uniform coating on a porous
substrate or one with a complex shape, its controllability with re-
gard to the thickness and chemical composition of the coating and
its low deposition temperature [12,17e19]. In addition, the
morphology of coating can be controlled easily by varying the
electrochemical potential and electrolyte concentration [12,18,19].
It is thus recognized as one of the most promising techniques to
produce degradable Mg alloy. Nevertheless, in a traditional
cathodic electrodeposition process, when a static potential is
applied, loose, porous and low adhesive coatings can easily
develop. The main reasons are: first, a concentrations polarization
is formed, since the speed of ion diffusion from the main body of
the solution to the surface of the metallic substrate is too slow; and
secondly, H2 is produced in the cathode due to the reduction of H2O.
In order to solve this problem, it is suggested that pulsed power can
be used for deposition of an adherent coating [17e22].
Wen et al. [2], Zhuang et al. [1] and Seyedraoufi et al. [23]
produced porous Mg and MgeZn scaffolds and investigated the
mechanical properties of the samples. However, compared with
the porous bioactive ceramic and polymeric scaffold, the porous
Mg and MgeZn specimens have proper mechanical properties
which are closer to those of natural bone. Furthermore, the porous
magnesium specimens have changeable in vitro degradable rates,
which are enhanced by increasing the porosity [1]. Therefore, it is
suggested that corrosion resistance of Mg scaffolds is improved.
Until now, there has not been study on coating of the porous
MgeZn scaffolds to improve of corrosion resistance and effects of
pulse electrodeposition parameters to coating of nano hydroxy-
apatite (HA) on the MgeZn scaffold. Because anti-corrosion
property of MgeZn alloy can be effectively improved by Zn
element when the content is less than 3% [15], we decided to
synthesize Mge2Zn (wt.%) scaffold as substrate. In the present
work, porous Mge2Zn (wt.%) specimens have been fabricated
using a powder metallurgy process. Nano HA coating was directly
deposited on the porous Mge2Zn (wt.%) scaffold using pulse
electrodeposition method under optimum conditions after inves-
tigation of effects of temperature, peak current density and duty
cycle parameters, then post-treated in alkali solutions. The
microstructural and compositional changes of HA coating, as well
as the degradation behaviour of as-synthesized, as-deposited and
Please cite this article in press as: Z.S. Seyedraoufi, S. Mirdamadi, Effects of pulse electrodeposition parameters and alkali treatment on the
properties of nano hydroxyapatite coating on porous MgeZn scaffold for bone tissue engineering application, Materials Chemistry and
Physics (2014), http://dx.doi.org/10.1016/j.matchemphys.2014.06.067
post-treated porous Mge2Zn (wt.%) scaffolds in simulated body
fluid (SBF) were investigated.
2. Experimental
2.1. Synthesise of scaffold
Pure magnesium (purity 99%, particle size 100 mm) and pure
zinc (purity 99.8%, particle size 45 mm) powder purchased from
Merck were utilised as starting materials. Carbamide (CO(NH2)2)
particles purchased from Merck were employed as the space-
holder agent. The particle size of the spacer agent material was in
the range of 200e400 mm with a purity of 99.9%. After mixing the
starting materials with the space-holder particles, porous Mge2Zn
(wt.%) specimens were prepared through a powder metallurgy
process. The mixtures of magnesium and zinc powder were pre-
pared based on 2 weight percent zinc amount, while the carbamide
particles were thoroughly added to the above specimens with
volume content of 15%.
The mixed powder was uniaxially pressed at a pressure of
200 MPa into green compacts with dimensions of 10 mm in
diameter and 10 mm in length. The green compacts were subse-
quently heat treated to burn out the spacer particles and to sinter
the porous MgeZn specimens separately in a tube furnace under an
argon atmosphere. The heat treatment process consisted of two
steps: first heating up to 250  C at a rate of 3.75 per minute and
staying at that temperature for 4 h, and then heating up to 550  C at
a rate of 8 per minute and staying at the final temperature for 2 h.
After the sintering stage, the specimens were furnace cooled down
to room temperature.
2.2. Coating process
The synthesized Mge2Zn (wt.%) scaffold was considered as the
substrate material. During the electrodeposition, a Mge2Zn (wt.%)
alloy sample was used as the working electrode and a cylindrical
graphite served as the counter electrode. Before deposition, in or-
der to obtain a clean and fresh working surface, the samples were,
sequentially, polished with silicon carbide papers of
400e1000 grits, cleaned ultrasonically in acetone, activated with
10% HNO3 for 10 s, and dried using a drying apparatus. The elec-
trolyte used for deposition of calcium phosphate was prepared by
mixing a solution of 0.042 mol L1 Ca(NO3)2, 0.025 mol L1
NH4H2PO4 and 0.1 mol L1 NaNO3. The pH value of the electrolyte
was adjusted to 5.0 by dilute HNO3 and (CH2OH)3CNH2. These re-
agents were all analytical grade. Deposition was performed with
fixed frequency (100 Hz) by different pulse peak current densities
of 20 and 40 mA cm2 for 1 h, positive pulse duty cycles of 0.1 and
0.2 for 1 h and temperatures of room temperature, 55, 70, 85 and
100  C for 1 h. The example of pulse electrodeposition parameters
are shown in Fig. 1, i.e. the pulse-peak current density is
40 mA cm2, 0.1 pulse duty cycle and the plating time of 10 ms.
When the specimens were coated with calcium phosphate, they
were removed from the electrolytic solution, rinsed in distilled
water and dried for about 4 h in air. Then the as-deposited samples
under optimum conditions of coating were immersed in
0.25 mol L1 NaOH solution at 80  C for 4 h, rinsed in distilled water
and dried at 80  C for 4 h.
2.3. Characterization
Chemical composition of the scaffold and coatings was per-
formed by X-ray diffractometer (Philips 1800PW) with Cu Ka ra-
diation. The structural analysis of obtained coatings was
determined by Fourier transform infrared spectroscopy (Nicolet
 Z.S. Seyedraoufi, S. Mirdamadi / Materials Chemistry and Physics xxx (2014) 1e9 3

Fig. 1. Example of schematic diagram of pulse-current waveform used in the pulse

electrodeposition process.

IR100). The surface morphology and element composition of scaf-

fold and coatings were identified by scanning electron microscopy
(TscaneVega) equipped with energy dispersion spectroscopy (EDS)
facility.

2.4. Electrochemical measurement

In order to understand the in vitro degradation behaviour of
MgeZn scaffold, potentiodynamic polarization experiments were
carried out in SBF at a temperature of 36.5 ± 0.5  C. A three-
electrode cell with the samples as the working electrodes was
used for the electrochemical measurements. The counter electrode
was made of platinum and the reference electrode was an AgeAgCl
electrode. The real area of the working electrode exposed to the
solution was 0.85 cm2. The potentiodynamic polarization curves
were obtained using a potentiostat (Autolab/PGSTAT302N) at a
constant voltage scan rate of 5 mV sel. Before the beginning of the
polarization tests, the samples were kept in the solution for 1 h to
establish the open circuit potential. The composition and prepa-
ration procedure of SBF were as reported in Ref. [24]. The solution
was buffered at pH 7.4 using trisehydroxymethyl aminomethane
((HOCH2)3CNH2) and hydrochloric acid (HCl) at 37  C. The con-
centration of each ion in the SBF was listed in Table 1.
3. Results and discussion
3.1. Microstructure and composition of scaffold
Fig. 2 shows the optical micrograph of porous Mge2Zn (wt.%)
scaffold, sintered at 550  C. It is clear that the pore sizes are
200e400 mm. The black phases correspond to porosity, while white
phases belong to Mg matrix. Using Ref. [1], the porosity volume
fraction of the scaffold is z20 vol.%. Visual characterisation of the
pores revealed that two types of pores, open interconnected mac-
ropores and small isolated micropores, were distinguishable within
the microstructure of the porous scaffold. Some of the micropores
are formed as a result of volume shrinkage of the magnesium and
zinc powders during the sintering process.
X-ray diffraction pattern of scaffold sintered at 550  C temper-
atures is shown in Fig. 3. As observed in the pattern, Mg peaks were
detected in the sample, and MgO was detected as the minor phase
in the pattern. In fact, the presence of the magnesium oxide peaks
Fig. 2. Optical micrograph of the Mge2Zn (wt.%) scaffold sintered at 550  C.
indicates that MgO was most likely formed during the preparation
and/or sintering process; however, MgO is a non-toxic oxide bio-
logically [25]. However, X-ray diffractometer (XRD) result could not
reveal the presence of any other possible phases. EDS elemental
mappings of the Mge2Zn (wt.%) scaffold sintered at 550  C is
shown in Fig. 4 and it can be inferred that the Zn is uniformly
distributed in the Mg matrix.
3.2. Effects of pulse electrodeposition parameters
3.2.1. Effect of temperature
Fig. 5 presents the Scanning electron microscopy (SEM) micro-
graph of the obtained coating at room temperature. It is shown that
the coating structure have a micro size flake type morphology.
Therefore, pulse electrodeposition process performed at higher
temperature to achieve nano size calcium phosphate coating. Fig. 6
shows SEM micrographs of the calcium phosphate coatings ob-
tained at temperatures of 100, 85, 70 and 55  C for 1 h at 0.1 duty
cycle and peak current density of 40 mA cm2. It is shown that with
increasing of the temperature not only will decrease size of
deposited particles but also the morphology of the coating will be
changed from plate-like structure approximately 250 nm in thick-
ness to needle-like structure less than 100 nm in diameter and
about 2e3 mm length. An increase in the temperature results

Table 1
Ion concentration in SBF [24].

Ions Naþ Kþ Mg2þ Ca2þ Cl- HCO

3 HPO2
4 SO2
4

Concentration 142.0 5.0 1.5 2.5 147.8 4.2 1.0 0.5

(mmol L1)
Fig. 3. XRD pattern of the Mge2Zn (wt.%) scaffold sintered at 550  C.

Please cite this article in press as: Z.S. Seyedraoufi, S. Mirdamadi, Effects of pulse electrodeposition parameters and alkali treatment on the
properties of nano hydroxyapatite coating on porous MgeZn scaffold for bone tissue engineering application, Materials Chemistry and
Physics (2014), http://dx.doi.org/10.1016/j.matchemphys.2014.06.067
4 Z.S. Seyedraoufi, S. Mirdamadi / Materials Chemistry and Physics xxx (2014) 1e9

Fig. 4. (a) SEM micrograph of the Mge2Zn (wt.%) scaffold sintered at 550  C, (b) and (c) elemental mapping images of (a).

increase in the number of particles and since the growth process is
diffusion controlled finer particles are obtained. Compared to plate-
like surface, the needle-like one might provide more area for the
deposition of Ca and P in SBF. It may be beneficial to have a needle-
like structure for bone growth, since the inorganic apatite in bone
has a needle-shaped morphology 2e3 nm in thickness and tens of
nanometres in length and width [17]. Therefore, according to SEM
results in different temperatures it can imply that 85  C tempera-
ture is the optimum temperature to coat calcium phosphate on the
porous MgeZn scaffold in the electrodeposition process.

3.2.2. Effect of duty cycle

SEM micrograph of the deposited calcium phosphate coating
obtained at duty cycles of 0.2 for 1 h at peak current density of
40 mA cm2 and 85  C temperature were shown in Fig. 7. It is found
that compared to Fig. 6c, the increasing of the duty cycle leads to
the changes in crystal structure of the deposited coating and
smaller particles are obtained at higher duty cycles. The duty cycle
is the time that potential is applied on the electrode and electro-
nation takes place. In fact, in PC method, the duty cycle (g) corre-
sponds to the percentage of total time of a cycle and is given by
[26]:

duty cycleðgÞ ¼ TON =TON þ TOFF (1)

Fig. 5. SEM micrograph of coating obtained at room temperature.
During TON base generation occurs and in high pH values
deposition starts and as a result the concentration of active species
around the electrode is reduced. At TOFF, deposition is almost
stopped and the electrolyte has time to diffuse toward the surface
and recover electrolyte concentration [18]. Cathodic reactions
result in a significant increase in pH value near the cathode. The
rate of OH formation is crucially important for the deposition
process. When there is an unbalance between OH generation and
consumption, the high pH boundary moves away from the

Please cite this article in press as: Z.S. Seyedraoufi, S. Mirdamadi, Effects of pulse electrodeposition parameters and alkali treatment on the
properties of nano hydroxyapatite coating on porous MgeZn scaffold for bone tissue engineering application, Materials Chemistry and
Physics (2014), http://dx.doi.org/10.1016/j.matchemphys.2014.06.067
 Z.S. Seyedraoufi, S. Mirdamadi / Materials Chemistry and Physics xxx (2014) 1e9 5

Fig. 6. SEM micrographs of the obtained coatings at temperatures of (a) 55, (b) 70, (c) 85 and (d) 100  C.

electrode resulting in lower coagulation of deposits. This is due to
pulsating diffusion layer and pulse limiting current density, at
which concentration at the electrode surface of reacting species
reaches to zero, therefore, it can be said that by increasing the duty
cycle mass transformation is limited and there is less opportunity
for concentration recovery and as a result new nuclei don't find
enough particles to grow; while by decreasing the duty cycle,
enough opportunity for preferential growth of particles and for-
mation of needle-like phase. Therefore, according to SEM results in
two duty cycles it can say that 0.1 duty cycle is the optimum duty
cycle to coat calcium phosphate on the porous MgeZn scaffold in
the electrodeposition process.

3.2.3. Effect of peak current density

Fig. 8 shows SEM micrographs of deposited coatings at peak
current densities of 20 and 40 mA cm2 at 0.1 duty cycle and 85  C
temperature for 1 h. It can be seen that with increasing of the peak
current density the morphology of the coating change from plate-
like to needle-like structure. As the peak current density in-
creases electronation and the overpotential increases, which in
turn increases the nucleation rate resulting in finer crystal and
preferential growth in the longitudinal direction.
Taking into consideration all the above-mentioned data, it is
found that nano structured calcium phosphate coating with
needle-like morphology can be obtained under optimum condi-
tions of 0.1 duty cycle, peak current density of 40 mA cm2, 85  C
temperature and time of 1 h.

3.3. Microstructure and composition of coating

XRD patterns of the as-deposited coating under optimum con-

Fig. 7. SEM micrograph of the obtained coating in 0.2 duty cycle. ditions and post-treated coating (Fig. 9) indicated that during

Please cite this article in press as: Z.S. Seyedraoufi, S. Mirdamadi, Effects of pulse electrodeposition parameters and alkali treatment on the
properties of nano hydroxyapatite coating on porous MgeZn scaffold for bone tissue engineering application, Materials Chemistry and
Physics (2014), http://dx.doi.org/10.1016/j.matchemphys.2014.06.067
6 Z.S. Seyedraoufi, S. Mirdamadi / Materials Chemistry and Physics xxx (2014) 1e9

Fig. 8. SEM micrographs of the obtained coatings in peak current densities of (a) 40 and (b) 60 mA cm2.


electrodeposition process a mixture of Ca10(PO4)6(OH)2 (HA) and Stage II: Reaction of Ca2þ with PO3 2
4 , OH and HPO4 to form HA,
CaHPO4$2H2O (DCPD) and Ca8H2(PO4)6$5H2O (OCP) was formed DCPD and OCP.
(as-deposited coating). In electrodeposition process, with applying
a high cathode current, the cathodic polarization of the Mg alloy 
leads to an increase in the pH at the interface between the alloy and 10Ca2þ þ 6 PO3
4 þ 2OH /Ca10 ðPO4 Þ6 ðOHÞ2 (4)
the electrolyte due to the formation of OH ions. Not only does this
sudden increase in pH trigger crystal nucleation of the desired Ca2þ þ HPO2
4 þ 2H2 O/CaHPO4 $2H2 O (5)
CaeP phase directly on the substrate surface but also that initiates
the CaeP crystal growth. Numerous studies have been performed þ
8Ca2þ þ 6 PO3
4 þ 2H þ 5H2 O/Ca8 H2 ðPO4 Þ6 $5H2 O (6)
on the precipitation of calcium phosphates from solutions con-
taining Ca2þ and PO34 . There are four kinds of calcium phosphates, DCPD and OCP formed on the as-deposited coating is converted
which are, in order of increasing solubility: HA, TCP into HA after post-treated with NaOH solution. The following re-
(Ca2(PO4)3_nH2O), OCP and DCPD. HA is the most stable calcium actions showed the transforming process:
phosphate ceramic under local strongly basic conditions. The
electrodeposition reactions on the surface of substrate are sug- 10CaHPO4 $2H2 O ¼ Ca10 ðPO4 Þ6 ðOHÞ2 þ 4H3 PO4 þ 18H2 O (7)
gested as follows:
10Ca8 H2 ðPO4 Þ6 $5H2 O ¼ 8Ca10 ðPO4 Þ6 ðOHÞ2 þ 12H3 PO4
Stage I: Reduction reaction of H2PO 2
4 and HPO4 .
þ 34H2 O (8)

2H2 PO  2
4 þ 2e /2HPO4 þ H2 [ (2) As HA is the most stable calcium phosphate ceramic in alkaline
solution [19], during the alkali treatment, the DCPD and OCP

coating is dissolved releasing Ca2þ and PO3 4 ions locally. The
2HPO2 3
4 þ 2e /2PO4 þ H2 [ (3) nucleation and growth of HA rely on the increased supersaturation
[27]. In fact, NaOH solution is used to increase the pH. In the
alkaline solution such as NaOH, the conversion of DCPD and OCP to
HAP is promoted due to the favourable thermodynamics and suf-
ficient OH [28,29]. In this system, the transformation will occur
without the introduction of the additional calcium and phosphate
ions, so that it is much easier to trace the conversion processes
during the transformation. By the abundant OH in the alkaline
solution, favourable nucleation sites are provided for the formation
of HAP. After nucleation, the HAP crystals grew outward by
consuming the Ca2þ and PO3 4 inside the DCPD and OCP. The
detailed process of HAP crystal growth may involve the dissolution
of the DCPD and OCP, outward diffusion of Ca2þ and PO3 4 ions and

combination of Ca2þ and PO3 4 ions with OH ion on the HAP crystal
surface to form HAP nano-needles. The crystallization of HAP nano-
needles completed via rearranging the orientation [28].
Fourier transform infrared spectroscopy (FTIR) spectra of the as-
deposited under optimum conditions and post-treated coatings
obtained on the MgeZn scaffold are shown in Fig. 10. These FTIR
spectra reveal the presence of characteristic peaks of absorbed
water, phosphate and carbonate species in the both of the coating,
Fig. 9. XRD pattern of coatings: (a) as-deposited under optimum conditions and (b) DCPD and OCP in the as-deposited and hydroxyl in the post-treated
post-treated by NaOH. coating. The broad peak around 3350e3550 cm1 in both of the

Please cite this article in press as: Z.S. Seyedraoufi, S. Mirdamadi, Effects of pulse electrodeposition parameters and alkali treatment on the
properties of nano hydroxyapatite coating on porous MgeZn scaffold for bone tissue engineering application, Materials Chemistry and
Physics (2014), http://dx.doi.org/10.1016/j.matchemphys.2014.06.067
 Z.S. Seyedraoufi, S. Mirdamadi / Materials Chemistry and Physics xxx (2014) 1e9
Fig. 10. FTIR spectrum of coatings: (a) as-deposited under optimum conditions and (b)
post-treated by NaOH.
spectra and the band at 1635 cm1 in Fig. 10b corresponds to the
adsorbed water [12,27]. The bands of 3165 cm1 in Fig. 10a and
2965 cm1 in Fig. 10a and b can be assigned to the OeH stretching
of water. In the spectrum of as-deposited coating H2O bending is
observed at 1574 and 1643 cm1 and in the one of the post-treated
coating the band at 3697 cm1 corresponds to OHe group [27]. The
band located around 1000 cm1 is originated by phosphate modes
and the split band at about 1030 cm1 is attributed to the formation
of a well-crystallized HA in both of the spectra. The absorption
bands at 1030, 600 and 565 cm1 detected in two spectra can be
confirmed as being the typical peak of PO3 4 ion [27,30]. In both of
the spectra the absorption bands between 1400 and 1500 cm1 are
attributed to the CO2
3 ion, because CO2 in the air dissolved in the
electrodeposition process [12] and CO2
3 ions are substituting A and
Fig. 11. (a) SEM micrograph and (b) EDS analysis pattern of as-deposited coating under optimum conditions.
Please cite this article in press as: Z.S. Seyedraoufi, S. Mirdamadi, Effects of pulse electrodeposition parameters and alkali treatment on the
properties of nano hydroxyapatite coating on porous MgeZn scaffold for bone tissue engineering application, Materials Chemistry and
Physics (2014), http://dx.doi.org/10.1016/j.matchemphys.2014.06.067
7
B sites of the apatite structure (corresponding to the phosphate and
hydroxyl ion, respectively) [27,30]. The bands between 2160 and
2400 cm1 detected in the spectrum of the as-deposited coating
can be attributed to DCPD and OCP [12]. In fact, the results of FTIR
spectra confirm that DCPD and OCP formed on the as-deposited
coating are changed into HA after post-treated with NaOH solution.
SEM micrographs of the as-deposited under optimum condi-
tions and post-treated coatings were shown in Fig. 11a (as-depos-
ited), Fig. 12a, b and c (post-treated). Both of the as-deposited and
post-treated coatings exhibit needle-like structure less than
100 nm in diameter. However, the as-deposited coating shows
some plate-like structures less than 100 nm in thickness. A small
amount of DCPD and OCP contained in the as-deposited coating is
the possible reason for this morphology difference. Compared to
plate-like surface, the needle-like one might provide more area for
the deposition of Ca and P in SBF. In addition, in the post-treated
coating, these needles are developed almost perpendicularly to
the substrate, with adjacent curled needles fusing together at joint
to construct the macroporous structure. It may be beneficial to have
a needle-like structure for bone growth, since the inorganic apatite
in bone has a needle-shaped morphology 2e3 nm in thickness and
tens of nanometres in length and width [17]. It is known that the
bioactivity of apatite highly depends on its composition. EDS
analysis in Figs. 11b and 12d shows the coatings contain Ca, P, O, Mg
and Na elements. The Mg2þ and Naþ ions may substitute the Ca2þ
position, which is similar to the composition of biological apatite
from natural bone mineral [12]. The Ca/P atomic ratios of the as-
deposited and post-treated coatings are nonstoichiometric, it is
found that Ca/P atomic ratio is always improved to a certain extent
after post-treating by NaOH due to DCPD and OCP have changed to
HA. The average Ca/P atomic ratios of the as-deposited and post-
treated are calculated about 1.42 and 1.55, respectively. Those are
both lower than the theoretical value 1.67 of HA, therefore, the
prepared coating is Ca-deficient HA (CDHA, CaeP with an atomic
ratio ranging from 1.33 to 1.65). This just meets the requirements
for biodegradable implants, because many studies have indicated
that the dissolution of HA in the human body after implantation is
too slow to achieve optimal results, while Ca-def HA seems to be
more soluble and may induce precipitation of a new bonelike
apatite after implantation [17].
3.4. Electrochemical behaviour of samples
Representative electrochemical polarization curves for different
samples in SBF are presented in Fig. 13. Generally, the cathodic
polarization curves are assumed to represent the cathodic
hydrogen evolution through water reduction, while the anodic
ones represent the dissolution of magnesium. The cathodic parts of
the curves in Fig. 13 indicate that the cathodic polarization current
8 Z.S. Seyedraoufi, S. Mirdamadi / Materials Chemistry and Physics xxx (2014) 1e9

Fig. 12. (a), (b) and (c) SEM micrographs in the different magnifications and (d) EDS analysis pattern of post-treated coating by NaOH.

of the hydrogen evolution reaction on the as-deposited under op-
timum conditions and post-treated MgeZn scaffolds is higher than
that on the uncoated MgeZn substrate. This means that the over-
potential of the cathodic hydrogen evolution reaction is lower on
the as-deposited under optimum conditions and post-treated
MgeZn scaffolds than on the uncoated MgeZn substrate. Further-
more, it proves that the cathodic reaction occurs kinetically easier
on the as-deposited and post-treated MgeZn specimens than on
the bare one, which may be due to the existence of the Ca-def HA
coating. As can be seen from the results, the anodic sites have been
covered with the as-deposited and post-treated coatings. On the
other hand, according to the morphology of the coatings and their
needle-like structures, macropores between needles could affect
the performance of the hydrogen current concentration and,
therefore, the cathodic current of the coated specimens can be
more than that of the bare one. But, as the coatings covered the
anodic sites, a decrease in the anodic current density is more sen-
sible than an increase in the cathodic current density and, there-
fore, the corrosion potentials were shifted in the positive direction.
Values of corrosion potential (Ecorr) and corrosion current density
(icorr) were extracted from the electrochemical polarization curves
and are listed in Table 2.
The Ecorr of substrate shifted from 1.47 to 1.15 V after surface
modifying by HA. According to the data, icorr of MgeZn substrate

Please cite this article in press as: Z.S. Seyedraoufi, S. Mirdamadi, Effects of pulse electrodeposition parameters and alkali treatment on the
properties of nano hydroxyapatite coating on porous MgeZn scaffold for bone tissue engineering application, Materials Chemistry and
Physics (2014), http://dx.doi.org/10.1016/j.matchemphys.2014.06.067
 Z.S. Seyedraoufi, S. Mirdamadi / Materials Chemistry and Physics xxx (2014) 1e9
Fig. 13. Polarization curves of MgeZn scaffold, as-deposited under optimum condi-
tions and post-treated HA-coated scaffolds in SBF.
Table 2
Electrochemical parameters of the scaffolds obtained from the polarization curves.
Specimen Ecorr (V) icorr (A cm2)
MgeZn scaffold 1.47 8  103
As-deposited HA-coated 1.3 1.4  103
Post-treated HA-coated 1.15 1.5  104
reduced from 8  103 to 1.5  104 A cm2 which means HA
coating has improved the corrosion resistance of the substrate in
the SBF. In fact, the phosphorus in HA forms a gel-like layer and
completely covers the surface, thereby protecting the underlying
coating from environmental attacks [31]. An increase in resistance
will reduce the initial corrosion rate of implants and, therefore, it is
important for maintaining the implant's mechanical strength in the
initial bony reunion period. It could be seen that Ecorr and icorr
changed, respectively, from 1.3 to 1.15 V and from 1.4  103 to
1.5  104 A cm2 after alkali treatment. Thus, it is concluded that
the alkali treatment can improve the substrate corrosion resistance.
These phenomena indicate that the alkali treatment causes the HA
coating to have a better stability. Therefore, not only does the
protection capacity of the substrate depend on the chemical
composition of the coating, but also it depends on the coating's
stability.
4. Conclusions
In this study, bone needle-like nano hydroxyapatite coating was
obtained by pulse electrodeposition process to improve the
biodegradation behaviour of porous MgeZn scaffold. Calcium
phosphate coatings on the porous MgeZn scaffolds were prepared
by pulse electrodeposition at different temperatures, duty cycles
and peak current densities. Results showed that pulse electrode-
position parameters effects on the morphology and crystal size of
the coatings. The most optimum coating with less than 100 nm in
Please cite this article in press as: Z.S. Seyedraoufi, S. Mirdamadi, Effects of pulse electrodeposition parameters and alkali treatment on the
properties of nano hydroxyapatite coating on porous MgeZn scaffold for bone tissue engineering application, Materials Chemistry and
Physics (2014), http://dx.doi.org/10.1016/j.matchemphys.2014.06.067
9
diameter and about 2e3 mm length was obtained at conditions of
0.1 duty cycle, peak current density of 40 mA cm2, 85  C tem-
perature and time of 1 h. The as-deposited HA coating under op-
timum conditions containing other calcium phosphates such as
DCPD and OCP exhibited mainly needle-like and partially plate-like
structures. After alkali treatment in NaOH solution, the post-treated
coating presented needle-like HA particles of 2e3 mm in length and
less than 100 nm in diameter developed almost perpendicularly to
the substrate. The mechanism of formation of HA coating by elec-
trodeposition involves reduction of H2PO 2
4 and HPO4 , reaction of
3  2 2þ
PO4 , OH and HPO4 ions with Ca ions resulting in formation of
HA, DCPD and OCP, and conversion of DCPD and OCP to HA. The
Ecorr value of the MgeZn scaffold shifted from 1.47 to 1.15 V and
icorr reduced from 8  103 to 1.5  104 A cm2 after surface
modified by HA coatings. The Ca-def HA coating can therefore delay
the corrosion of the Mg substrate in SBF. This study revealed that
electrodeposition of HA coating is a useful approach to improve the
corrosion resistance of porous MgeZn scaffold in SBF and to
develop Mg-based degradable implants.
References
[1] H. Zhuang, Y. Han, A. Feng, Mater. Sci. Eng. C 28 (2008) 1462e1466.
[2] C.E. Wen, M. Mabuchi, Y. Yamada, K. Shimojima, Y. Chiho, T. Asahina, Scr.
Mater. 45 (2001) 1147e1153.
[3] A.K. Khanra, H.C. Jung, S.H. Yu, K.S. Hong, K.S. Shin, Mater. Sci. 33 (2010)
43e47.
[4] N.T. Kirkland, N. Birbilis, M.P. Staiger, Acta Biomater. 8 (2012) 925e936.
[5] Z. Li, X. Gu, S. Lou, Y. Zheng, Biomaterials 29 (2008) 1329e1344.
[6] W.D. Müller, M.L. Nascimento, M. Zeddies, M. Co  rsico, J. Mater. Res. 10 (2007)
5e10.
[7] C.E. Wen, Y. Yamada, K. Shimojima, Y. Chino, H. Hosokawa, M. Mabuchi,
Mater. Lett. 58 (2004) 357e360.
[8] Y. Xin, K. Huo, H. Tao, G. Tang, P.K. Chu, Acta Biomater. 4 (2008) 2008e2015.
[9] Y. Xin, T. Hu, P.K. Chu, Corros. Sci. 53 (2011) 1522e1528.
[10] H. Krawiec, S. Stanek, V. Vignal, J. Lelito, J.S. Suchy, Corros. Sci. 53 (2011)
3108e3113.
[11] A. Atrens, M. Liu, N.I.Z. Abidin, Mater. Sci. Eng. B 176 (2011) 1e28.
[12] C. Wen, S. Guan, L. Peng, C.H. Ren, X. Wang, Z. Hu, Appl. Surf. Sci. 255 (2009)
6433e6438.
[13] X. Gu, Y. Zheng, S. Zhong, T. Xi, Biomaterials 31 (2010) 1093e1103.
[14] A. Kaya, D. Eliezer, G. Ben-Hamu, O. Golan, Y.G. Na, K.S. Shin, Met. Sci. Heat
Treat. 48 (2006) 50e54.
[15] D. Yin, E. Zhang, S. Zeng, T. Nonferr, Metal. Soc. 18 (2008) 763e768.
[16] E. Zhang, D. Yin, L. Xu, L. Yang, K. Yang, Mater. Sci. Eng. C 29 (2009) 987e993.
[17] H.X. Wang, S.K. Guan, X. Wang, C.X. Ren, L.G. Wang, Acta Biomater. 6 (2010)
1743e1748.
[18] M. Saremi, B. Mottaghi Golshan, Iran. J. Mater. Sci. Eng. 3 (2006) 1e5.
[19] Y.W. Song, D.Y. Shan, E.H. Han, Mater. Lett. 62 (2008) 3276e3279.
[20] W. Lia, S.H. Guana, J. Chenb, J. Hua, S.H. Chena, L. Wanga, S.H. Zhu, Mater.
Charact. 62 (2011) 1158e1165.
[21] Z. Chun-Yan, Z. Rong-Chang, L. Cheng-Long, G. Jia-Cheng, Surf. Coat. Technol.
204 (2010) 3636e3640.
[22] E.C. Meng, S.K. Guan, H.X. Wang, L.G. Wang, S.J. Zhu, Appl. Surf. Sci. 257 (2011)
4811e4816.
[23] Z.S. Seyedraoufi, Sh. Mirdamadi, J. Mech. Behav. Biomed. 21 (2013) 1e8.
[24] T. Kokubo, H. Takadama, Biomaterials 27 (2006) 2907e2915.
[25] M.B. Kannan, R.K.S. Raman, Biomaterials 29 (2008) 2306e2314.
[26] S.A. Lajevardi, T. Shahrabi, Appl. Surf. Sci. 256 (2010) 6775e6781.
[27] M. Jamesh, S. Kumar, T.S.N. Sankara-Narayanan, J. Coat. Technol. Res. 9 (2012)
495e502.
[28] X.J. Zhang, D.Y. Lin, X.H. Yan, X.X. Wang, J. Cryst. Growth 336 (2011) 60e66.
[29] X.B. Chen, N. Birbilis, T.B. Abbott, Corros. Sci. 53 (2011) 2263e2268.
[30] M. Manso, C. Jimenez, C. Morant, P. Herrero, J.M. Martinez-Duart, Biomaterials
21 (2000) 1755e1761.
[31] K.C. Elzbieta, Corros. Sci. 46 (2004) 2487e2502.