Available online at SciVerse ScienceDirect

J. Mater. Sci. Technol., 2013, 29(4), 330e338

Fabrication and Characterization of Porous Sintered TieAg Compacts

for Biomedical Application Purpose
Legan Hou1), Li Li1), Yufeng Zheng1,2)*
1) Center for Biomedical Materials and Engineering, Harbin Engineering University, Harbin 150001, China
2) Department of Materials Science and Engineering, College of Engineering, Peking University, Beijing 100871, China
[Manuscript received September 20, 2012, in revised form January 15, 2013, Available online 15 February 2013]

Porous sintered TieAg compacts with different Ag content were fabricated by powder metallurgy. The associated
hydrothermal treatment and the effect on the apatite formation were studied. The results suggested that TiO was
generated under the condition of low vacuum (1
102 Pa) during the process of burning out the spacer-holding
particles. After hydrothermal treatment, a sub-microscale porous layer was formed at the pore wall surface of the
samples. The apatite-inducing ability of hydrothermal treated porous sintered TieAg compacts with different Ag
content was evaluated in modified simulated body fluid (SBF). And the results proved that there is a clear
correlation between the apatite-inducing ability and Ag content. The higher Ag content in porous leads to the
decrease of Naþ ions and basic hydroxyl (OH)b amount, resulting in the decline of apatite-inducing ability in
the first stage. However, their apatite-inducing ability was not significantly different from that of Ti after two
weeks SBF immersing. Hence, the ionic activity should restore with the processing of SBF soaking, as the
saturation of Ag effect.

KEY WORDS: Porous sintered TieAg compacts; Ag content; Hydrothermal treatment; Apatite-inducing ability

1. Introduction In recent years, the titanium alloys with introduction of Ag

Titanium and some of its alloys have been extensively used as
orthopedic implant materials because of their excellent me-
chanical properties and biocompatibility[1e3]. Hence, stable
osteointegration and the mismatch of Young’s modulus between
Ti (90e105 GPa) and bones (0.3e30 GPa) are still two impor-
tant factors limiting their application[4e7]. To meet the demand of
stable osteointegration, TieAg alloys have been widely stud-
ied[8e18]. Meanwhile, a number of approaches have been
investigated to solve mismatch problem, such as alloying with
low modulus[19,20], composite materials[21,22], porous mate-
rials[23,24] and so on. Among them, porous titanium by intro-
ducing a porous structure to reduce the Young’s modulus of Ti-
based biomaterials has been considered as the best way. This
method can help to minimize the stress-shielding of the tissues
around implant materials and even to prolong the implant life-
time[25e27]. Thus, porous alloys may offer a very good combi-
nation of stable osteointergration and matching with bone.
* Corresponding author. Prof., Ph.D.; Tel./Fax: þ86 10 62767411;
E-mail address: yfzheng@pku.edu.cn (Y. Zheng).
1005-0302/$ e see front matter Copyright Ó 2013, The editorial office of
Journal of Materials Science & Technology. Published by Elsevier
Limited. All rights reserved.
http://dx.doi.org/10.1016/j.jmst.2013.02.013
have been extensively investigated[28]. However, the report about
the formation and characterization of porous sintered TieAg
compacts is still very little. In order to provide a better retrieval
condition for coordination between implant materials and bony
site, porous sintered TieAg compacts with a low Young’s
modulus were fabricated, by using a special powder metallurgy
method[2931]. In this work, our aim is to understand the role of
Ag content in formation of porous sintered TieAg compacts and
their hydrothermal treatment, as well as its impact on the apatite-
inducing ability in a modified simulated body fluid (SBF)[32e34].
2. Materials and Methods
2.1. Materials preparation
Four kinds of porous sintered TieAg compacts with Ag
content of 0%, 1%, 3% and 5% were fabricated by metallurgy
process. Ti powder (purity, 99.4%) and Ag powder (purity,
99.9%) were the raw materials for preparing TieAg compacts.
First, raw powders and stainless steel balls (6 mm in diameter) in
a weight ratio of 1:10 were put into stainless steel containers with
the protection of Ar atmosphere. And then the containers were
milled in a planetary mill (QM-1SP04, China) with a rotation
rate of 600 r/min at room temperature. Urea particles sieved to
300e600 mm were used as space-holding material. After
 L. Hou et al.: J. Mater. Sci. Technol., 2013, 29(4), 330e338 331

Table 1 Concentrations of reagent-grade chemicals for preparing SBF

Chemicals Concentration (g/L) Purity

NaCl 8.036 >99.5%

NaHCO3 0.352 >99.5%
KCl 0.225 >99.5%
K2HPO4$3H2O 0.230 >99.0%
MgCl2$6H2O 0.311 >98.0%
CaCl2 0.293 >96.0%
Na2SO4 0.072 >99.0%

metallurgy process, they were mixed with ball-milled powders in

a weight ratio of 1:1. The mixture was then cold compressed in a
stainless steel mold at 100 MPa for 5 min into green compact Fig. 2 Particle size distribution graph of the powders with different Ag
with a diameter of 20 mm. The resultant green compacts were contents after 5 h ball milling.
heated to 250  C for 1 h to burn out the spacer-holding particles
with a vacuum furnace (1
102 Pa). Then, the porous green
14 days, respectively. And the SBF was refreshed every other
compacts were directly sintered at 1350  C for 2 h in Ar
day. For preparation of SBF, chemicals NaCl, NaHCO3, KCl,
atmosphere.
K2HPO4$3H2O, MgCl2$6H2O, CaCl2, and Na2SO4 were added
into distilled water and buffered with Tris and 1.0 mol/L HCl at
2.2. Hydrothermal treatment
pH 7.40.

For the hydrothermal treatment, the sintered TieAg compacts

samples (10 mm
10 mm
1 mm) were soaked in aqueous
5.0 mol/L NaOH solution at 60  C for 24 h. After the treatment,
the samples were cleaned with fresh distilled water and dried at
40  C. In the following, HT-TieAg compact represents the hy-
drothermally treated TieAg compact.
2.3. Simulated body fluid immersion
The apatite-inducing ability was evaluated by immersing the
porous HT-TieAg samples in SBF (Table 1) at 37  C for 7 and
2.4. Structure characterization
For structure characterization, X-ray diffraction (XRD),
scanning electron microscopy (SEM), energy dispersive X-ray
spectrometer (EDS), X-ray photoelectron spectroscopy (XPS)
and Fourier transform infrared absorption (FT-IR) spectroscopy
were used to investigate the characteristics of the samples.
2.4.1. XRD. The surface phases of the porous sintered TieAg
compacts before and after hydrothermal treatment and after be-
ing incubated in SBF were analyzed by X-ray diffraction (XRD,

Fig. 1 SEM morphology of the powders with different Ag contents after 5 h ball milling: (a) 0%, (b) 1%, (c) 3%, (d) 5%.
332 L. Hou et al.: J. Mater. Sci. Technol., 2013, 29(4), 330e338
Fig. 3 XRD patterns of the powders with different Ag contents after 5 h
ball milling: (a) 0%, (b) 1%, (c) 3%, (d) 5%.
Fig. 4 XRD patterns of the porous sintered TieAg compacts with
different Ag contents: (a) 0%, (b) 1%, (c) 3%, (d) 5%.
Fig. 5 SEM morphology of the porous sintered TieAg compacts with different Ag contents: (a) 0%, (b) 1%, (c) 3%, (d) 5%.
D/max-gB, Japan) using CuKa radiation with continuous scan-
ning mode at a rate of 4  /min under a current of 50 mA and
accelerating voltage of 40 kV.
2.4.2. SEM and EDS. To observe the morphologies and detect
elemental concentrations of the sample surfaces, a scanning
electron microscope (Quanta 200, FEICo., American) equipped
with an energy dispersive X-ray spectrometer (EDS, EDAX,
American) was used.
2.4.3. XPS. An X-ray photoelectron spectroscopy (XPS, K-
Alpha, Thermofisher Scienticfic Co., American) with AlK
(1486.6 eV) X-ray source was used to detect the chemical
compositions of the sample surfaces under vacuum of
1.0
106 Pa (1.0
108 mbar) and beam current of 6 mA.
And the resolution for energy was 0.5 eV with a scanning step of
0.1 eV.
2.4.4. FT-IR. Fourier transform infrared absorption spectroscopy
(FT-IR, a Bruker the Vector 22, German) with a scanning area
from 4000 to 400 cm1 and resolution of 4 cm1 was used to
analysis the structure of the functional groups on the HT-TieAg
compacts surface before and after SBF immersion. The surface
coatings were scraped off from the sample, then mixed with KBr
powder and pressed into transparent disks with a diameter of
13 mm for FT-IR works.
2.4.5. Degree of porosity. The porosity of each porous sample
was calculated by measuring their weight and dimensions.
Accordingly, six samples from each group were weighed by a
precision digital balance. Meanwhile, their dimensions were
measured using a digital caliper. The height and diameter of
cylindrical samples were measured at three different positions in
order to minimize the measurement error.
 L. Hou et al.: J. Mater. Sci. Technol., 2013, 29(4), 330e338 333

Table 2 Degree of porosity for the porous sintered TieAg compacts

Samples Degree of porous (%)

Ti 65.7  1.1
Tie1% Ag 63.9  1.3
Tie3% Ag 62.6  1.6
Tie5% Ag 59.1  2.3

3. Results

3.1. Characterization of porous sintered TieAg compacts

The morphologies of milled powders with different Ag con-
tents are shown in Fig. 1. It was noticeable that no significant
difference was found among the samples under the same process.
Particle size distribution graphs of those powders are presented
in Fig. 2. The particle size mainly gathered at 30 and 2 mm.
Figs. 3 and 4 show the XRD patterns of the milled powders
and porous sintered TieAg compacts, respectively. No reaction
happens during the 5-h ball milling (Fig. 3). But after sintering,
instead of Ag, the peaks corresponding to TiO are shown in
Fig. 4. This was caused by the low vacuum condition
(1
102 Pa) during the process of burning out the spacer-
holding particles. The small amount of oxygen has plenty time
to react with sufficient Ti at certain temperature. Thus, TiO was
generated during that process.
SEM micrographs of the porous sintered TieAg compacts
with different Ag content are shown in Fig. 5. The pores with
size in the range of 200e500 mm were open and interconnected
throughout all the samples. The degree of porosity in the porous
sintered TieAg compact samples with different Ag contents is
shown in Table 2. The weight ratio of the metal powders to the
Fig. 7 XRD patterns of hydrothermally treated porous TieAg compacts
with different Ag contents: (a) 0%, (b) 1%, (c) 3%, (d) 5%.
amount of space-holding material was 1:1, which means the
porosity would be around 70%. However, as the introduction of
Ag, the real degree of porosity showed a decline trend with
increasing Ag content, varying from 65.7% to 59.1% (lower than
the calculated value). This suggests that Ag may play a pro-
moting role in densification of the porous sintered TieAg
compacts, which corresponds to the results in Fig. 5.
As shown in Fig. 6, through EDS surface scanning analysis, it is
confirmed that Ti, O and Ag exist in the porous sintered TieAg
compacts and distribute evenly.
3.2. Characterization of hydrothermally treated porous sintered
TieAg compacts
Fig. 7 shows the XRD patterns of the porous HT-TieAg
compacts. No changes can be observed between the XRD results

Fig. 6 Elemental distribution of the surface for porous sintered TieAg compacts with 3% Ag content: (a) as-sintered porous TieAg compacts, (b) Ti,
(c) O, (d) Ag.
334 L. Hou et al.: J. Mater. Sci. Technol., 2013, 29(4), 330e338

Fig. 8 SEM morphology of hydrothermally treated porous TieAg compacts with different Ag contents: (a) 0%, (b) 1%, (c) 3%, (d) 5%.

before and after hydrothermal treatment, because only a sub-
microscale porous layer was formed at the pore wall surface of
the samples, as shown in Fig. 8. By comparing the element
concentrations of the samples surface before and after hydro-
thermal treatment (Table 3), it was found that the concentration
of O element increased dramatically after hydrothermal treat-
ment. Meanwhile, Na was introduced into the sample surfaces,
and its concentration decreased with increasing Ag content.
XPS spectra indicated the chemical difference between the
surface and the hydrothermally treated sample. Similar to the
EDS results in Table 3, the elements Ag, Ti, O, Na can be
detected from the surface (Fig. 9). Devolution of the Ti2p peak
reveals that the titanium existed as TiO2 in the surface, but
another peak corresponding to TiO3  appeared after etching
(Fig. 10). Meanwhile, the devolution of the O1s shows that the
oxygen existed as TiO2 and basic hydroxyl (OH)b in the surface,
and after etching the amount of basic hydroxyl (OH)b decreased
(Fig. 11). Furthermore, the devolution of Ag3d indicates that the
silver existed as AgO and Ag2O in the surface and samples
(Fig. 12).
Comparing the FT-IR spectra of the sub-microscale porous
layer on the porous HT-TieAg compacts with 0% and 3% Ag, it
was found that the sample without Ag has more TiO3  and basic
hydroxyl (OH)b (Fig. 13).
3.3. Apatite-inducing ability of the porous HT-TieAg compacts
Figs. 14 and 15 show the XRD patterns of the porous HT-Tie
Ag compact with different Ag contents after soaking in the SBF
for 7 and 14 days, respectively. After 7-day immersion, no sig-
nificant difference can be observed from the diffraction peaks.
Namely, just Ti and TiO but nothing else can be observed in
Fig. 14. Hence, changes happened after another week. Compared
to the patterns of the porous HT-TieAg compacts in Fig. 14,
those of samples in Fig. 15 displayed a number of relatively
weak and broad peaks, which can be marked as HA (hydroxy-
apatite). The broad peak at 32.6 corresponded to the over-
lapping of (211), (112), (300) and (202) diffraction peaks, and
the peak at 25.9 points to the (002) plane of HA. The diffraction
peaks of apatite indicate that the porous HT-TieAg compacts
possess apatite-inducing ability. It was clear from the intensity of
apatite diffraction peaks that porous HT-TieAg compact with
different Ag contents have distinct apatite-inducing abilities
during the same time. The amount of deposited apatite on the

Table 3 Element concentrations of the surface of porous sintered TieAg compacts before and after hydrothermal treatment

Element Before hydrothermal treatment (wt%) After hydrothermal treatment (wt%)

0% Ag 1% Ag 3% Ag 5% Ag 0% Ag 1% Ag 3% Ag 5% Ag

Ti 73.5 70.82 67.92 65.58 58.9 55.7 54.2 55.85

O 26.5 28.32 30.13 31.58 38.46 41.16 42.45 40.21
Ag e 0.86 1.95 2.84 e 0.83 1.71 2.66
Na e e e e 2.64 2.31 1.64 1.28
 L. Hou et al.: J. Mater. Sci. Technol., 2013, 29(4), 330e338 335

Fig. 11 XPS high-resolution spectra of O1s of the hydrothermally

Fig. 9 XPS survey of the hydrothermally treated porous TieAg com- treated porous TieAg compacts with different Ag contents
pacts with different Ag contents before and after etching: (a) before and after etching: (a) before etching and (b) after
before etching and (b) after etching. etching.

Fig. 10 XPS high-resolution spectra of Ti2p of the hydrothermally Fig. 12 XPS high-resolution spectra of Ag3d of the hydrothermally
treated porous TieAg compacts with different Ag contents treated porous TieAg compacts with different Ag contents
before and after etching: (a) before etching and (b) after before and after etching: (a) before etching and (b) after
etching. etching.
336 L. Hou et al.: J. Mater. Sci. Technol., 2013, 29(4), 330e338
Fig. 13 FT-IR spectra of the hydrothermally treated porous TieAg
compacts with different Ag contents.
porous HT-TieAg compact with 3% Ag is more than the other
three samples.
Figs. 16 and 17 show the SEM pictures of the porous HT-Tie
Ag compacts after soaking in SBF for 7 and 14 days, respec-
tively. The SEM results indicate that the Ag content has a sig-
nificant impact on the apatite-inducing ability. Apatite nucleation
first appears in the porous HT-TieAg compact with low Ag
content (Fig. 16 (a) and (b)), but there is no apatite formation on
the porous compact with higher Ag content during the same
time. Proceeding with the SBF soaking, apatite formed on every
sample. And no clear difference can be observed in the quantities
of apatite formed among the Fig. 17 (a)e(d) after 14-day SBF
immersing.
The FT-IR spectra of apatite coating formed on porous HT-
TieAg compacts after SBF incubation for 14 days are shown in
Fig. 18. Absorption peaks of PO4 bands were observed including
the triply degenerated asymmetric stretching mode of n3PO4
band at 1033 cm1, triply degenerated bending mode of n3PO4
band at 602 and 566 cm1 and double degenerated bending
mode of n2PO4 band at 471 cm1[32]. Meanwhile, the broad
absorption band at 3441 cm1 indicates the presence of (OH)b in
the apatite coating. The FT-IR result confirms that the apatite
formed on the porous HT-TieAg compacts is HA.
4. Discussion
In this paper, porous sintered TieAg compacts with different
Ag contents were prepared by sintering milled powders in Ar
atmosphere. Hydrothermal treatment was conducted on them.
The structure and properties of the porous HT-TieAg compacts
Fig. 14 XRD patterns of hydrothermally treated porous TieAg com-
pacts with different Ag contents after SBF immersion for
7 days: (a) 0%, (b) 1%, (c) 3%, (d) 5%.
Fig. 15 XRD patterns of hydrothermally treated porous TieAg com-
pacts with different Ag contents after SBF immersion for 14
days: (a) 0%, (b) 1%, (c) 3%, (d) 5%.
have been investigated. According to current results, it can be
found that the effect of Ag element on the phase composition,
element concentrations and apatite-inducing ability of porous
HT-TieAg compact is significant.
4.1. Effect of Ag on surface phase composition after
hydrothermal treatment
In the present study, it is assumed that hydrothermal treatment
offers plenty of OH and energy, leading to reaction between
OH and surface alloy elements and their oxide, as listed in Eqs.
(1)e(5)[35].
TiO2 þ OH /HTiO3  (1)
Ti þ 3OH /TiðOHÞ3 þ þ 4e (2)
TiðOHÞ3 þ þ e /TiO2 ,H2 O þ 0:5H2 [ (3)
TiðOHÞ3 þ þ OH 4TiðOHÞ4 (4)
TiO2 ,nH2 O þ OH 4HTiO3  ,nH2 O (5)
Besides the reactions between Ti and OH, it can also react
with Ag, as listed below
Ag þ OH /AgOH þ e (6)
2AgOH 4Ag2 O þ H2 O (7)
The XPS results of Ag provide strong evidence to support this
view. Devolution of the Ag3d peak reveals that the Ag existed as
AgO and Ag2O in the surfaces (Fig. 12). Due to the reactions with
silver, a lot of e is generated, but the OH is consumed. This
greatly limits the reaction listed in Eq. (4), but plays a promoting
role in the formation of TiO2 and TiO3  (Eq. (3)). This assumption
is consistent with the XPS results of Ti2p as shown in Fig. 10.
Namely, the devolution of the Ti2p peak shows that besides TiO2,
Ti existed as TiO3  in the porous HT-TieAg samples after
 L. Hou et al.: J. Mater. Sci. Technol., 2013, 29(4), 330e338 337

Fig. 16 SEM morphology of hydrothermally treated porous TieAg compacts with different Ag contents after SBF immersion for 7 days: (a) 0%,
(b) 1%, (c) 3%, (d) 5%.

etching. And its amount increases with the higher Ag content in the
porous HT-TieAg compact. Meanwhile, Agþ ions also limits the
number of Naþ ions as their competition to catch negative func-
tional groups, correlating with the data in Table 3.
4.2. Effect of Ag on apatite-inducing ability
Considering the nucleation of HA, the process can be
described as below. On the soaked sample surface, the TiO3 
negative functional group is formed by releasing Naþ ions. The
negative charges caused by TiO3  on the porous HT-TieAg
compact sample surface might catch Ca2þ ions by Coulomb’s
force. Meanwhile, HPO4 2 group and OH ions may also be
attracted by the Ca2þ ions around the surface. As the enrichment
of Ca2þ, HPO4 2 and OH ions, HA (Ca10(PO4)6(OH)2) can be
produced according to the following equilibrium in SBF[35]:
10Ca þ 6HPO4 2 þ 8OH /Ca10 ðPO4 Þ6 ðOHÞ2 þ 6H2 O (8)
Thus, the decrease of Naþ ions amount caused by increasing Ag
content leads to the decline of apatite nucleation ability. Further-
more, basic hydroxyl (OH)b plays an important role in apatite-
inducing ability[35]. Hence, the Agþ ions have a strong oxidizing
ability, as their high reduction potential. Thus, the Agþ ions
consume and control a large quantity of (OH)b, limiting the apatite-
inducing ability.

Fig. 17 SEM morphology of hydrothermally treated porous TieAg compacts with different Ag contents after SBF immersion for 14 days: (a) 0%,
(b) 1%, (c) 3%, (d) 5%.
338 L. Hou et al.: J. Mater. Sci. Technol., 2013, 29(4), 330e338
Fig. 18 FT-IR spectra of the hydrothermally treated porous TieAg com-
pacts with different Ag contents after SBF immersion for 14 days.
Considering the two parameters caused by Ag content, Naþ
ions and basic hydroxyl (OH)b, the ionic activity should restore
with the processing of SBF soaking, as the saturation of Ag
effect. And then apatite can deposit on the porous HT-TieAg
compact surfaces as shown in Fig. 17.
5. Conclusion
Porous sintered TieAg compacts with a series of Ag content (0%,
1%, 3% and 5%) can be fabricated by powder metallurgy sintered at
1350  C for 2 h in Ar atmosphere. TiO was generated under the
condition of low vacuum (1
102 Pa) during the process of burning
out the spacer-holding particles. After hydrothermal treatment, a sub-
microscale porous layer was formed at the pore wall surface of the
samples. It consists of TiO2, TiO3  , AgO, Ag2O and basic hydroxyl
(OH)b. Moreover, it was found that the sample without Ag appears
with more TiO3  and basic hydroxyl (OH)b. Meanwhile, Na was
introduced into the sample surfaces, and its concentration decreases
with increasing Ag content. Naþ ions and basic hydroxyl (OH)b are
the two mainly factors, which affected the apatite-inducing ability,
directly determined by Ag content. The higher Ag content in porous
leads to the decrease of Naþ ions and basic hydroxyl (OH)b amount.
However, their apatite-inducing ability was not significantly
different from that of Ti after 14 day SBF immersing.
Acknowledgments
This work was supported by the National Basic Research
Program of China (“973 Program”, Nos. 2012CB619102 and
2012CB619100), National Science Fund for Distinguished
Young Scholars (Grant No. 51225101), the Fundamental
Research Funds for the Central Universities (Nos. HEUCFZ1017
and HEUCFR1020), and the Natural Science Foundation of
Heilongjiang Province, China (No. ZD201012).
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