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Composites: Part A 38 (2007) 535–539

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Formation of bone-like apatite on titanium filaments incubated in


a simulated body fluid by using an electrochemical method
Jia-Horng Lin a, Chia-Hao Chang a,*
, Yueh-Sheng Chen b,c
, Gau-Tyan Lin d

a
Graduate Institute of Textile Engineering, Feng Chia University, Taiwan, ROC
b
Institute of Chinese Medical Science, China Medical University, Taiwan, ROC
c
Department of Medical Radiology Technology, China Medical University, Taiwan, ROC
d
Department of Orthopedic Surgery, Kaohsiung Medical University, Taiwan, ROC

Received 11 July 2005; received in revised form 6 February 2006; accepted 19 February 2006

Abstract

Apatite (HA) layer can be formed on the surface of titanium using the electrochemical deposit method. In the present study, we found
the current and loading time strongly affected the granule size and quantity of HA. When a low current was applied, needle-like HA was
formed and irregular granules were seen at a higher current. We also found the main components of both the HA structures were Ca and
P, and the percentage Ca/P was 1.69, which is similar to that of a natural bone.
 2006 Elsevier Ltd. All rights reserved.

Keywords: B. Strength; E. Heat treatment

1. Introduction transformed to tricalcium phosphate (TCP) and tetracal-


cium phosphate (TTCP). Unfortunately, both the TCP
Different materials for the orthopedic or dental purposes and the TTCP have a larger degradation rate than the HA,
have been used, such as titanium, titanium alloy [1], titanium resulting in shortening their utilization period [10,11]. There-
filaments [2], and stainless steel [3]. Titanium, titanium alloy fore, how to keep the coated HA on the material is impor-
(Ti6Al4V) and 316L stainless steel possess several proper- tant, especially if it will be used clinically. Kokubo et al.
ties, including high tenacity and thermal stability, resistance found by soaking the substrates in a simulated body fluid
to corrosion, and superior mechanical strength, which have (SBF) with ion concentrations equal to those of the human
been used to make artificial skeletons. However, all these blood plasma could resolve the melting problem [12]. In
skeleton substitutes do not have a good biological capability the present study, we therefore also incubated titanium fila-
as integrating with the bone tissue [4]. To increase their bio- ments in a simulated body fluid. To accelerate the HA for-
compatibility, investigators have used the plasma-spreading mation on the surface of the filaments, we anodized the
method to coat the hydroxyapatite (HA) on the materials’ body fluid with different electric currents, electrolyte temper-
surface [5–8]. HA is commonly seen in the hard tissue, which atures and action periods [13,14]. Morphology and crystal-
is a bioactive material with a high biocompatibility [9]. After linity of the deposited HA were observed and examined.
iron-exchanging with its surrounding tissue, HAs bonding
strength and osteoconductivity can be increased. However, 2. Materials and methods
the plasma-spreading method is usually operated at a high
temperature that could melt the coated HA which will be 2.1. Titanium filament and surface treatment preparation

*
Corresponding author. The cathode was a commercially pure titanium filament,
E-mail address: P9010598@fcu.edu.tw (C.-H. Chang). 1 mm in diameter (President Co., Ltd. Taiwan), and the

1359-835X/$ - see front matter  2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesa.2006.02.013
536 J.-H. Lin et al. / Composites: Part A 38 (2007) 535–539

Table 1
Ion concentrations (mM) of SBF and human blood plasma
Na+ K+ Mg2+ Ca2+ Cl HCO
3 HPO2
4 SO2
4

Blood plasma 142.0 5.0 1.5 2.5 103.0 27.0 1.0 0.5
SBF 142.0 5.0 1.5 2.5 147.8 4.2 1.0 0.5
Modified SBF 142.0 5.0 1.5 3.75 147.8 4.2 1.0 0.5

anode was a platinum filament, 1 mm in diameter. Both the nH2 O incorporates the sodium ions in it. Thereafter, the
electrodes were washed by acetone and distilled water treated titanium or titanium alloy are heated, the sodium
sequentially, dried in an oven at 80 C, and then immersed titanate hydrogel layer will be dehydrated and stabilized
in a SBF solution. The electrolyte currents were set at 100, as an amorphous sodium titanate layer. Finally, the
200, 300, 500 and 1000 mA with a fixed distance of 8 cm. sodium ion in the surface layer will replace the H3O+ ion
The current loading periods were controlled for 1, 3, 5, in SBF, producing Ti–OH groups on the surface of the tita-
10, and 20 min, respectively. After the electrochemical pro- nium to induce the apatite nucleation.
cess, bone-like HA was deposited on the titanium filament, These negatively charged species are combined with
which was then consolidated at 400 C for 1 h. alkali ions in the aqueous solution, resulting in the forma-
tion of an alkali titanate hydrogel layer. During the heat
2.2. SBF incubation treatment, the hydrogel layer is dehydrated and densified
to form a stable amorphous or crystalline alkali titanate
A modified SBF with a high concentration of Ca2+ was layer. When exposed to SBF, the alkali titanate layer is
prepared by mixing reagent-grade chemicals of NaCl, again hydrated to transform into TiO2 hydrogel via release
NaHCO3, KCl, K2HPO4 Æ 3H2O, MgCl2 Æ 6H2O, CaCl2, of alkali ions from the alkali titanate layer into SBF. This
and Na2SO4 one by one in the distilled water sequentially. kind of alkali release is essentially accompanied by ion
The solution was buffered to a pH value of 7.4 with 50 mM exchange with H3O+ ions in SBF, resulting in a pH
trishydroxyaminomethane [(CH2OH)3CNH2] and an ade- increase in the surrounding fluid. The pH increase gives rise
quate amount of hydrochloric acid at 37 C. The concen- to an increase in the ionic activity product of apatite
trations of ions in the modified SBF are shown in Table 1. according to the equilibrium in SBF [15].
Using the electrochemical method, the nucleation of
2.3. Surface observation and analysis bone-like HA also can be formed by the alkaline and the
heat treatment. However, the incubation period can be
A variable vacuum scanning electron microscopy was reduced. The apatite deposition formed by the electro-
used to observe the surface structures (HITACHI chemical method begins due to heterogeneous nucleation.
S3000N, Japan). Energy dispersive spectrometer (HOR- The crystallinity of apatite depends upon some thermody-
IBA, UK) was used for element analysis. The XRD attach- namic factors including activation energy barrier. Since
ment (MAC SCIENCE, Japan) and Cu Ka radiation with electrostatic current loading can reduce the energy barrier
a wavelength k of 0.154 nm were used. The operating con- [16] that it can provide more effective templates for deposi-
ditions were 40 kV and 30 mA. The scan rate was set at 2/ tion of relative ions.
min in a 2h range of 20–60. Fig. 1 shows the bone-like apatite deposition at different
loading periods. As incubated in the SBF for 1 min at a low
3. Results and discussion current of 100 mA, the titanium filament was etched, form-
ing a rough surface with few tinny granules. Following form
In the SBF, the metal substrates need alkaline and heat the description of Faraday’s laws it should be clear that, if a
treatment to produce an amorphous hydrogel titanate for current of I amperes flows for t seconds in an electrolytic cell
inducing nucleation of HA. The reaction is illustrated as resulting in W gram of a substance of atomic weight A and
follow [12]: valence z being deposited, or dissolved, then: [17]
TiO2 þ OH ! HTiO
3 ItA
W ¼
Ti þ 3OH ! 
Ti(OH)þ
3 þ 4e  zF
1 With the incubation periods extended, more bone-like
Ti(OH)þ 
3 þ e ! TiO2  H2 O þ H2 " apatite was formed completely covering the filament. The
2
þ 
Ti(OH)3 þ OH $ Ti(OH)4 bone-like apatite is a bioactive material containing calcium
and phosphorous, which is biocompatible for cells to
TiO2  nH2 O þ OH $ HTiO
3  nH2 O attach on and proliferate.
When a titanium metal is treated with NaOH aqueous Fig. 2 shows the apatite formed at different electric cur-
solution, a sodium titanate hydrogel layer will be formed rents. Needle-like apatites were seen at 100 mA. As increas-
on its surface and then the negatively charged HTiO 3þ
ing the current loading to 1000 mA, the apatite structure
J.-H. Lin et al. / Composites: Part A 38 (2007) 535–539 537

Fig. 1. Bone-like apatite deposition at 100 mA at different loading periods: (a) 1 min, (b) 5 min, (c) 10 min and (d) 20 min.

Fig. 2. SEM micrographs of the apatite formed at different electric currents for 10 min: (a) 100 mA, (b) 300 mA, (c) 500 mA and (d) 1000 mA.

   
became more irregular and granulated. The size of the apa- U  K g
G ¼ G0 exp exp
tite was increased with the current loading and the electrol- RðT c  T 1 Þ T c ðDT Þf
ysis time. It is well known that Hoffman et al. defined and
reported the crystallization kinetics that explain the relations where G is the overall growth rate or the crystallization
of crystallization rate and the temperature [18]. Whereby rate, G0 is the pre-exponential factor, U* is the activation
538 J.-H. Lin et al. / Composites: Part A 38 (2007) 535–539

energy, R is the universal gas constant, f is the correction (OCP) to carbonate-containing apatite and then releasing
factor and Kg is the nucleation constant. the H2O molecules.
Although it seems that the current density is not related When the OCP was transformed to the apatite, its b and
to the crystallization according to the equation, some c axes directions were shared with each other [21]. The
researchers claimed that the crystallization of calcium car- OCP may collapse in a manner somehow reflects its crystal
bonate would be inhibited under magnetic field treatment structure. The direction of the slit formation seems to relate
for scaling water prevention [19,20]. In the typical magnetic to the distribution of H2O molecules in its crystal structure.
field, the energy dE/dV of the electromagnetic field per unit The EDS spectrum shows that the major elements of the
volume is given by the formula: incubated titanium filament were carbon, oxygen, phos-
dE 1 2 phorus, calcium and titanium (Fig. 4). When the filament
¼ B þ 2e0 E2 was immersed under a small electric current loading, e.g.,
dV 2l0
100 mA used in this study, the coated HA layer was so thin
where B is the magnetic induction and E the intensity of the that the scanning beam could easily pass through it and
electric field, l0 and e0 are the permitivity and permeability detect the titanium. However, as the current loading was
of the free space, respectively. In the same way, enhanced increased to 300 mA, the titanium filament was completely
current loading that generates higher magnetic field inten- covered by the bone-like apatite and the calcium/phos-
sity restricted the crystallization of apatites. phate ratio was 1.69, which is similar to that of a natural
Without the electrochemical treatment, a smooth sur- bone (1.67) [22].
face conglomerated by granules forming an apatite layer Fig. 5 shows XRD patterns of the electrodes at different
and crystallized structure on the filaments was seen loading periods under 100–1000 mA in the SBF electrolyte.
(Fig. 3) [2]. We know that the crystal phase of the HA
deposits is determined by the reaction time, the reaction
temperature, and the composition of the SBF solution
[14]. Thus, the bone-like HA deposited on the titanium fil-
aments would consolidate at 400 C for 1 h in the electro-
chemical process, converting the octacalcium phosphate

Fig. 4. The EDS spectrum of the incubated titanium filament under


different electric current loadings for 10 min: (a) 100 mA, (b) 300 mA,
(c) 500 mA and (d) 1000 mA.

Fig. 5. XRD patterns of the electrodes under different current loadings


Fig. 3. Surface of the titanium filaments soaked in SBF for 15 days and periods: (a) 100 mA for 10 min; (b) 200 mA for 10 min; (c) 300 mA for
(a) 120· and (b) 20,000·. 10 min; (d) 300 mA, 20 min.
J.-H. Lin et al. / Composites: Part A 38 (2007) 535–539 539

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