Material processing of hydroxyapatite and titanium alloy (HA/Ti)

composite as implant materials using powder metallurgy: A review

Amir Arin
a,b
, Abu Bakar Sulong
a,
, Norhamidi Muhamad
a
, Junaidi Syarif
a
, Mohd Ikram Ramli
a
a
Department of Mechanical and Material Engineering, Universiti Kebangsaan Malaysia, 43600 Bangi, Selangor, Malaysia
b
Department of Mechanical Engineering, Sriwijaya University, 30662 Indralaya, Sumatera Selatan, Indonesia
a r t i c l e i n f o
Article history:
Received 24 July 2013
Accepted 17 September 2013
Available online 25 September 2013
Keywords:
Ceramicmetal composite
Powder metallurgy
Material processing
Biocompatibility
Mechanical properties
a b s t r a c t
The bio-active and biodegradable properties of hydroxyapatite (HA) make this material a preferred can-
didate for implants such as bone replacement in replacing natural tissues damaged by diseases and acci-
dents. However, the low mechanical strength of HA hinders its application. Combining HA with a
biocompatible material with a higher mechanical strength, such as a titanium (Ti) alloy, to form a com-
posite has been of interest to researchers. A HA/Ti composite would possess characteristics essential to
modern implant materials, such as bio-inertness, a low Youngs modulus, and high biocompatibility.
However, there are issues in the material processing, such as the rheological behavior, stress-shielding,
diffusion mechanism and compatibility between the two phases. This paper reviews the HA and Ti alloy
interactions under various conditions, in vitro and in vivo tests for HA/Ti composites, and common pow-
der metallurgy processes for HA/Ti composites (e.g., pressing and sintering, isostatic pressing, plasma
spraying, and metal injection molding).
2013 Elsevier Ltd. All rights reserved.
1. Introduction
The rapid growth of the global population is leading to an in-
creased demand for implants for bone dysfunction caused by dis-
eases such as arthritis and cancer [1]. Such implants are
necessary to repair or alter natural body tissues [2]. However, gi-
ven the unique structures and mechanical properties of natural tis-
sues such as bone tissue, repairing or changing them is challenging.
Since the introduction of bioceramics as medical implants in the
1960s, metal implants such as titanium alloy, stainless steel, and
cobaltchromium alloys have been extensively used in medical
applications [3]. In the early period of medical implant develop-
ment, the only criteria for implant material suitability were appro-
priate physical properties and non-toxicity [4]. Today, the criteria
include the physical properties of the bone implant material and
its ability to promote the growth of body tissue [5]. Metal-based
implants have a higher Youngs modulus than bones, which leads
to stress shielding. Metal implants also have poor biocompatibility,
which is necessary to promote the growth of natural tissue. How-
ever, metal-based implants have the benecial mechanical proper-
ties of strength and corrosion resistance. Hydroxyapatite (HA) is a
bioceramic material with poor mechanical properties, especially
for load-bearing applications. However, HA has a similar structure
to bones and can promote the growth of natural tissues. Combining
a titanium alloy with HA creates a new biomaterial with excellent
mechanical and biological properties. Thus, research on this mate-
rial and its preparation process has been conducted [610]. This
paper aims to review the interaction between titanium alloys
and HA as a medical implant composite. Common methods of com-
bining HA and titanium are also discussed.
2. Criteria for biomaterials applications
In the early period of implant material development, a material
was considered suitable to replace natural tissue when it had min-
imal or zero toxicity [11]. Later on, the ability to promote natural
tissue growth was considered. Several studies have been con-
ducted to achieve this goal in terms of the processing route, design
and material modication [1218]. Biomaterials for implants
should not be cytotoxic. Cytotoxicity is caused by increased metal-
lic ion content in the blood. Thus, biocompatibility itself can be
translated simply as do no harm to the body and due to encour-
age healing [19]. The roughness of an implant surface is conducive
to the bonding between implant materials and tissues [20]. Porous
structures and rough surfaces are necessary for facilitating bone in-
growth and osteointegration [11,2123]. Rough surfaces and por-
ous structure able to control by its processing condition [2429].
Stress shielding is a common problem of biomaterials [30,31].
This phenomenon arises when the Youngs modulus of bones
(Fig. 1) and the implant material are different, which causes bone
resorption. Most biomaterials based on metals and ceramics have
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http://dx.doi.org/10.1016/j.matdes.2013.09.045

Corresponding author. Tel.: +60 3 89216678; fax: +60 3 89259659.

E-mail address: abubakar@eng.ukm.my (A.B. Sulong).
Materials and Design 55 (2014) 165175
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higher Youngs modulus than cortical and trabecular bones [32,33]
(Table 1). Material selection and manufacturing processes have
been performed to address this problem. Titanium alloys are po-
tential implant materials because their Youngs modulus are closer
to that of bone (1030 GPa) compared to other metal implants
[34]. Another approach involves controlling the Youngs modulus
of bone by modifying its porosity [35].
3. Titanium and titanium alloys
Since the mid-1940s, titanium and its alloys have been widely
used for medical applications, aerospace structures, and chemical
industries [37,38]. Many researchers continue to develop titanium
alloys for medical applications because of their unique properties,
such as high specic strength, lightweightness and bioinertness
[1,3941]. Titanium and its alloys are classied as light materials
with adequately high specic strength in engineering structures
(Fig. 2). Titanium has a density of 4.5 g/cm
3
and a melting point
of 1668 C. Titanium alloy has a tensile strength of approximately
1400 MPa at room temperature. At high temperatures, titanium
becomes reactive with other materials. Meanwhile, titanium alloys
have high corrosion resistance at room temperature because of the
good biocompatibility and stable passivity of their surface oxide
lms [6]. Titanium alloys can be divided into a-, (a + b)-, and
b-type alloys. b-type alloys have the lowest Youngs modulus
(Table 1), which is closest to the Youngs modulus of bone
(1030 GPa) [42].
4. Hydroxyapatite
Hydroxyapatite theoretically exists as the hydroxyl end-mem-
ber of apatite, which was suggested in 1912 [44]. Hydroxyapatite
is one of the apatite structures that were observed in rock, the apa-
tite structure has the basic formula Ca
10
(PO
4
)
6
X
2
. X in the formula
is the representation group member of apatite and refers to a hy-
droxyl (OH) group for hydroxyapatite, a uoride (F) group for u-
orapatite, and a chloride (Cl) group for chlorapatite [45].
Synthetic HA is widely applied as a substitute for the hard tissues
of the human body damaged by disease or accident. HA as an im-
plant can bond and promote natural tissue growth because of its
chemical similarity to bone mineral [4649]. At high temperatures,
HA undergoes decomposition, which starts with dehydroxylation
at approximately 900 C in air and at 850 C in a water-free atmo-
sphere. The next stage is decomposition, which produces tetra cal-
cium phosphate (TTCP) and tri calcium phosphate (TCP). TCP
consists of b-TCP at <1200 C and a-TCP at >1200 C. HA loses
many hydroxyl groups above 1300 C and thus loses signicant
weight [45]. Other studies have revealed that at >1350 C, the
strength of HA drastically decreases [46].
5. Porous structure
A porous structure in an implant material has the function not
only to decreasing the Youngs modulus of the material implant
[50] but also of facilitating osteointegration. Moreover, characteris-
tics of the porous structure play an essential role in the regenera-
tion of bone [5153]. Porous structures can be divided into open or
Fig. 1. Stress shielding mechanism [36].
Table 1
Comparison of the mechanical properties of implant materials [43].
E (GPa) YS (MPa) r
f
(MPa) %EL BF 10
3
FeCrNiMo (316L) 210 450 250 40 1.2
CoCr (as cast) 200 500 300 8 1.5
CoNiCr (as wrought) 220 850 500 20 2.3
TiAl6VA 105 900 550 13 5.2
TiAl5Fe2.5 105 900 550 15 5.2
cp-Ti 100 300 200 40 1.8
cp-Ta 200 300 200 40 1.3
cp-Nb 120 250 150 70 1.3
YS = yield strength, E = Youngs modulus, r
f
= fatigue strength, BF = biofunctional-
ity = r
f
/E, %EL = elongation.
Fig. 2. Density of selected materials [43].
166 A. Arin et al. / Materials and Design 55 (2014) 165175
closed cells. In an open cell condition, each cell in the structure has
a connection. In a closed cell, no connection exists between cells on
the structure [54]. The interconnection of each cell is critical for
allowing blood and nutrition into the structure to encourage bone
ingrowth and osteointegration. The pore size depends on the appli-
cation and thus has no standard size. For bone ingrowth, the min-
imum pore size is 50 lm. Large pores tend to be drained of blood
and nutrient more than small pores. Thus, the pore size must be
considered when examining the mechanical properties of an im-
plant [51,55]. Powder metallurgy (PM) processes can be used to
produce combined small and large pores by adjusting the powder
size, pressure, sintering temperature, and method of adding the
powder to the space holder [35,50,5658].
6. Interaction of titanium alloys and hydroxyapatite
The interaction between titanium alloys and hydroxyapatite
has been studied by several researchers [6,35,5965]. Thermal sta-
bility has been observed to affect the synthesis of HA [45], such
that in the thermal processing of a HA/Ti system, TCP and TTCP
are commonly produced after dehydroxylation and decomposition
[66].
6.1. Argon environment
As previously discussed, dehydroxylation begins at approxi-
mately 900 C in air and at 850 C in a water-free atmosphere. Pure
HA is stable up to 1200 C under an argon atmosphere. However, in
HA/Ti composites, Ti ions react with the dehydrated water of HA to
yield titanium oxide, thereby accelerating the dehydroxylation and
decomposition of HA at approximately 800 C. CaO and TTCP are
the main products of HA decomposition in a Ti/HA system with in-
creased sintering temperature. TTCP then decomposes to CaO at
>1200 C such that only two phases are formed, namely, CaO and
an amorphous phase [64]. Balbinotti et al. reported that at approx-
imately 1026 C under an argon atmosphere, calcium titanate,
Ti
x
P
y,
and TCP phases are the decomposition products, as observed
in the XRD result in Fig. 3 [65]. These phases are formed at the
boundary that covers the titanium particles.
6.2. Air environment
Egorov et al. investigated and characterized the interactions
within Ti/HA composites in air at 7001200 C and observed that
titanium is oxidized (Fig. 4) [59]. This result is supported by other
studies on extreme oxidation at 1100 C.
TiO
2
is produced at 800 C, and only two crystalline phases exist:
TiO
2
and calcium titanate (CaTiO
3
). CaTiO
3
is produced by the inter-
action between titanium and HA [59]. Berezhnaya et al. compared
annealing results in air and argon [62]. Specimens annealed in ar-
gon have a smooth surface, and those annealed in air have a sur-
face covered with titanium oxide. Moreover, Berezhnaya et al.
revealed that annealing in air reduces the biocompatibility because
the optimum Ca/P ratio is not reached [45,62]. The optimum bio-
compatibility of HA is achieved at approximately 1.51.7 Ca/P.
6.3. Vacuum environment
Yang et al. studied HA/Ti composites in a vacuum at 1100 C,
and observed the formation of TCP, TTCP, and calcium titanium
oxide (Ca
2
Ti
2
O
5
) [60]. Fractured surface analysis revealed three
types of surface morphologies of the HA/Ti composite, as shown
in Fig. 5. Granular aggregation (calcium phosphate and Ca
2
Ti
2
O
5
),
a porous structure, and a glassy phase are observed in HA, and
a-TCP and TTCP are present in the composite. This morphology is
caused by the unequal melting points of the two materials as well
as by the fusion between HA and molten Ti.
There is a possibility of reactions between hydroxyapatite and
Ti under vacuum condition [60].
In the rst stage, hydroxyapatite loses a hydroxyl chain in the
following reaction:
Ca
10
PO
4

6
OH
2
in vacuum; > 800

C
! Ca
10
PO
4

6
OH
22x
O
x
xH
2
O gas 1
H
2
O oxidized titanium became titanium oxide (TiO
2
)
Ti 2H
2
O gas ! TiO
2
2H
2
2
Fig. 3. XRD pattern of Ti/10% HA composite at 1200 C for 2 h under argon
condition [65].
Fig. 4. XRD pattern of HA composite under an air environment [59].
A. Arin et al. / Materials and Design 55 (2014) 165175 167
CaTi
2
O
5
was resulted from the reaction hydroxyapatite with
TiO
2
Ca
10
PO
4

6
OH
2
2TiO
2
! 3Ca
3
PO
4

2
CaTi
2
O
5
H
2
O 3
Under elevated temperature a-TCP and TTCP
Ca
10
PO
4

6
OH
2
in vacuum; > 800

C
! Ca
4
P
2
O
9
2Ca
3
PO
4

2
H
2
O 4
6.4. Nitrogen environment
The fabrication of a HA/Ti system in a nitrogen environment has
been reported by several researchers [67,68].
Fig. 6 shows that at 1000 C, only a small quantities of a-Ca
3
(PO
4
)
2
, (a-TCP), and Ca
4
O(PO
4
)
2
were detected. The decomposition
phase of Ti/HA composites increase with increased sintering tem-
perature, and no reaction occurs between HA and titanium [67].
TCP in HA/Ti composites degrades faster than HA, promoting
new natural tissues and leading to unstable mechanical properties
of the implant for natural tissue growth [8,67].
6.5. Diffusion mechanism between HA and Ti
At the HA/Ti interface, the Ti atoms at elevated temperature
tend to oxidize to become TiO
2
, and normally, the TiO
2
position
on top of the titanium surface; however, parameter processing
tends to alter the formation passivation of TiO
2
. In this situation,
Ti atoms from the metallic bulk move and inter-diffuse on the lm
while oxygen atoms migrate to the titanium bulk [69,70]. The re-
sult of this simultaneous process is titanium oxide in amorphous
or crystalline form. The oxidation kinetics of titanium is deter-
mined by the adsorption rate of oxygen, oxygen as an interstitial
atom diffuses to the Ti lattice until reaching a saturation level, fol-
lowed by oxidation of titanium. The diffusion rate of oxygen will
decelerate when TiO
2
occur [71]. Ye et al. and Chu et al. also re-
ported that dehydroxylation of hydroxyapatite would be acceler-
ated by the presence of Ti atoms, under this condition, oxygen
diffuses to the Ti metallic bulk to form titanium oxides [64,67].
Furthermore, calcium and phosphorous ions diffuse into the Ti
substrate to affect the Ca/P ratio of apatite. The phosphorous ion
has the ability to migrate rapidly into the Ti substrate due to its
smaller radii and lower activation energy. Other authors reported
that Ca, P and Ti have been detected on some regions but other
phase that are common results of the reaction between HA and
TiO
2
were not observed. The presence of Ca, P and Ti atoms dem-
onstrated that interdiffusion occurred in the HA/Ti composite
[62,70].
Balbinotti et al. performed EDS line scans on the polished part of
a HA/Ti composite; titanium and a small amount of calcium were
detected on the polished area [65]. It was believed that the tita-
nium formation phase titanium and calcium tend to be fragile
and are partially lost because of the polishing mechanism. At the
HA/Ti interface, titanium and phosphorous were detected, as ob-
served in Fig. 7. The vertical arrow indicates the area where phos-
phorus was detected; under this condition, Ti and P were detected
in the formation Ti
x
P
y
phase which demonstrates that the phos-
phorus ion has diffused to the titanium ion during sintering. Com-
monly, differences in the thermal expansion of ceramic will lead to
cracking due to nonuniform of residual stresses in the material
[72]. Cracks have also been observed in HA/Ti composites that will
degrade their mechanical properties. Shi et al. observed micro
cracks in the HA/Ti composites, which were thought to be due to
differences in the thermal expansion of Ti and HA [69]. Moreover,
in addition, micro cracks were also found in the results using MIM
products as reported by Thian et al. [63].
Fig. 5. Scanning electron micrograph of the fracture morphology of Ti/HA composite in a vacuum: (a) 80% HA (1500 original magnication) and (b) 90% HA (1200 original
magnication). (A) Granular aggregation, (B) porous area, and (C) glassy phase [60].
Fig. 6. XRD spectra of HA20 vol% Ti in a nitrogen environment for 60 min at (a)
1000 and (b) 1100 C [67].
168 A. Arin et al. / Materials and Design 55 (2014) 165175
7. Nanostructure of HA/Ti system
Nanomaterials are known as great potential candidates for im-
plant material application [73]; Webster et al. reported that nano-
structure materials (with grain sizes less than 100 nm) have the
ability to increase function osteoblast adhesion, which supports
the next stage of tissue growth [27,29,74], as shown on Fig. 8. Oth-
ers researchers also reported that nanoscale topography played a
critical role in increasing cell activity, which rapidly encouraged
tissue growth compared with conventional materials [7577].
The fabrication of HA/Ti composites on the nanoscale have the
advantage of increasing consolidation between Ti and HA such as
the hardness value, youngs modulus and corrosion resistance
[14,78]. The combination of mechanical alloying and the powder
metallurgical process has been proposed by Niespodziana et al.
in the fabrication of nanostructure HA/Ti [78]. A unique method
has been proposed by Farnoush et al., these researchers have com-
bined friction stir processing and electrophoretic deposition to fab-
ricate nanostructure HA/Ti [79].
8. In vitro and in vivo test
Tests of biological properties are important in the manufacture
of implant materials [8]. These tests determine the suitability of an
implant material. In vivo and in vitro tests are extensively used for
biological evaluation. In vivo or in the living organism tests are
performed inside the body of a living organism, and in vitro or
in glass tests are performed in inanimate laboratory equipment
[80]. The biocompatibility of a material is tested in vitro by
immersing a specimen for a few weeks in simulated body uid
(SBF) whose conditions are similar to those in human blood plasma
[81]. The ion concentrations in SBF and human blood plasma are
listed in Table 2. Thian et al. reported that HA/Ti composites are
tested through immersion in SBF solution to induce complete dis-
solution of the secondary phase after 2 weeks [8,81]. Complete dis-
solution of the calcium phosphate phase occurs during the initial
stage of immersion, which results in the deterioration of the
mechanical properties of the specimen. In the next stage, the
mechanical properties of the HA/Ti composites signicantly in-
creases because of the precipitation of the apatite layer [8]. The
combination of titanium and HA promotes apatite nucleation. In
the secondary phase, Ti
2
O helps generate apatite on the composite
surface [82,83]. In addition, the dissolution of CaO encourages a
constructive location for apatite nucleation and growth [82].
In vivo tests of a HA/Ti composite have been conducted by Chu
et al. [66,68]. using New Zealand white rabbits. These researchers
cut the implant model into rectangular shapes 3.3 mm wide,
3.3 mm thick, and 56 mm long rectangular shapes, as illustrated
in Fig. 9.
In vivo tests revealed that the HA/Ti composite has excellent
biocompatibility that enables it to integrate with bone, which in-
creases osteointegration and bonding strength with time after
the initial stage of implantation [66,68,84]. According to Ning
and Zhou, HA/Ti composites produce a bone-bonding interface
with bone through an apatite layer. The bioactivity value of HA/
Ti compositesis determined by increasing the titanium content in
a HA/Ti system [85]. These researchers also revealed that the
in vivo and in vitro tests have similar results as conrmed by
in vivo and in vitro investigations performed on other materials
[86].
9. Powder metallurgy
PM is a manufacturing method in which powder metals are
compressed with or without other materials, and then heated
without a melting stage for solidication and strengthening [87].
PM produces excellent microstructures and compositions for man-
ufacturing near-net-shaped products [88]. Several methods have
been proposed to produce HA/Ti composites, such as conventional
PM [61,65,89], non-conventional PM [90], and plasma spraying
[9193]. The conventional method or pressing and sintering pro-
cess usually consists of mixing the powder, compacting the pow-
der in a desired mold, and sintering [94]. Occasionally, during the
compaction step, the mold temperature is raised to high tempera-
tures and is classied as hot pressing [66,68]. Non-conventional
processes include powder injection molding (PIM) and isostatic
pressing, which can be further divided into hot and cold processes
[94].
9.1. Pressing and sintering
Mixing is commonly required in PM and involves mixing the
powder with other powders as well as with a binder. Failure in
mixing irreversibly affects the next step. The mixing stage involves
numerous parameters such as mixing time, mixing temperature,
powder size, and powder shape, composition of powder, and com-
position of the binder [95]. Thian et al. proposed the ceramic slurry
approach for applying PIM and hot/cold isostatic pressure. Ti6Al4V
Fig. 7. SEM image of the polished surface of a HA/Ti composite (a) polished area and (b) EDS line scan analysis [65].
A. Arin et al. / Materials and Design 55 (2014) 165175 169
and HA powder were mixed with polyvinyl alcohol (PVA) as a bin-
der for a certain time [96]. To remove the binder, the Ti6Al4V slur-
ry was heated at 450 C in air and the consolidation stage was
performed at higher temperatures (600700 C). Using this
method, HA can be coated around the titanium core as shown in
Fig. 10.
In conventional PM, uniaxial pressure is applied when the
pressing powder is contained in a die. Removal of powder from
the die can only be performed through the in-line movement of a
punch from a no-cross-equipment mechanism [94]. Therefore, a
complex geometry cannot be produced using this method.
Moreover, the density of green compacts through conventional
PM varies. However, despite these limitations, PM has numerous
advantages such as low manufacturing cost, high tolerance, and
minimal secondary machining process requirements.
Fig. 8. Nanophase materials promote greater amounts of protein adsorption and encourage additional new bone formation compared with conventional materials [73].
Table 2
Concentration of ion simulated body uid (SBF) and human blood plasma [81].
Species Ion concentration (mmol/l)
Blood plasma SBF
Ca
2+
2.5 2.2
HPO
2
4
1.0 0.8
Na
+
142.0 140.3
Cl

148.8 148.0
Mg
2+
1.5 1.3
K
+
5.0 5.3
SO
2
4
0.5 0.5
HCO

3
4.2 4.0
Fig. 9. Implant model of a HA/Ti composite: (a) rectangular specimen and (b) cross-sectional viewof specimen (DB = defective bone region; region for bone healing area) [66].
Fig. 10. Scanning electron micrograph of HA/Ti6Al4V composite powder using the
ceramic slurry approach [96].
170 A. Arin et al. / Materials and Design 55 (2014) 165175
9.2. Isostatic pressing
Isostatic pressing is one well-known near-net-shape methods to
produce parts with highly complex shapes [97]. Unlike conven-
tional PM which uses uniaxial pressure, isostatic pressing powder
makes use of a exible mold enveloped-contained powder with
applied pressure through hydraulic pressure from all directions
as shown in Fig. 11 [98]. Isostatic pressing can be divided into
hot and cold types, wherein cold isostatic pressing operates at
room temperature using water and oil as the uid pressure. In con-
trast, hot isostatic pressing operates at elevated temperature [94].
Isostatic pressing is performed to induce maximum density
[99]. In hot isostatic pressing, some parameters such as the sinter-
ing temperature and pressure can be controlled to produce inter-
connected porosity, good mechanical properties, and high
permeability [100]. The resulting complete diffusion bond is one
of the main advantages of this method. The complexity of the inner
and outer surfaces of the product must be overcome to avoid the
Fig. 11. Illustration of exible mold movement in the isostatic pressing process [98].
Fig. 12. Cross section of the double layered capsule hydrothermal hot-pressing method [102].
Fig. 13. Illustration of plasma spray process [103].
A. Arin et al. / Materials and Design 55 (2014) 165175 171
negative effects of the large product size [97]. Under correct design
and control, the mechanical properties of the product of hot iso-
static pressing, i.e., near-wrought materials, and signicantly im-
prove [97,101].
Hot isostatic pressing requires necessary precision control for
every stage to achieve optimum results. The range time per cycle
is counted in hours to produce a specic component. However,
producing many parts in one batch can decrease the running cycle.
Sometimes, a product requires a high cooling rate to change its
microstructure and mechanical properties. Thus, conventional
hot isostatic pressing is the common option [97]. At high temper-
atures, HA decomposes into a secondary phase [45], especially
when the plasma-spraying method is used. Onoki and Hashida pro-
posed a route to avoid this problem. These researchers used hot
isostatic pressing to coat HA on titanium bars at low temperatures
through the double-layered capsule hydrothermal hot-pressing
method under hydrothermal isostatic pressure (Fig. 12) [102]. They
successfully coated HA on titanium bars at 135 C.
9.3. Plasma spray
Surface modication through plasma spraying may improve the
biocompatibility and mechanical properties of metal implants [93].
Plasma spraying coats a material with other materials possessing
specic properties (Fig. 13). For example, HA is used as a coating
material and titanium alloy is used as a substrate. Metal implants
with low biocompatibility are usually coated with a material of
higher biocompatibility [91].
The structural integrity of bonds between a substrate and coat-
ing under fatigue is determined by the suitability of the chemical
and thermal properties. To avoid mismatches between a substrate
and coating, an intermediate layer is used between them
[104,105]. The mechanism of bonding between HA and titanium
through plasma spraying that utilizes CaTiO
3
as a bond layer is
stronger than the bonding mechanism through mechanical inter-
locking. HA reacts with TiO
2
at 8001000 C on the Ti surface,
where CaTiO
3
and TCP are present as secondary phases [91]. Form-
ing composite coatings with Ti increases the strength of the adhe-
sive bonding coating. Consequently, Ti and HA can uniformly
spread on the surface. A SBF testing also indicates no reduction
in the bioactivity of a material [106]. The plasma-spraying method
is known as an easy and safe method to coat HA onto Ti alloys.
However, in biomedical applications, problems involving residual
stress, a low level of crystallinity, a low level of porosity, and
non-uniform distribution porosity are encountered [107,108]
Microporosity includes sizes of approximately 10300 nm caused
by a signicant decrease in the mechanical properties of a material
[109]. Combining plasma spraying and isostatic pressing has been
proposed by certain researchers to address this problem. Satisfac-
tory results have been obtained in decreasing the microporosity
and improving the mechanical properties of a material [109,110].
9.4. Metal injection molding
MIM is commonly used after modication and innovation at
each stage of PIM [111], as shown in Fig. 14. PIM itself is a combi-
nation of two methods: plastic injection molding and PM [95]. In
MIM, the volume fraction of plastic for PIM is substituted by metal
powder, which is mixed with plastic into pasta (feedstock). The
feedstock is injected into the molding machine (green part), fol-
lowed by an extraction binder and nally by sintering [112] If a
material used is ceramic, it is called ceramic injection molding,
whereas MIM denotes covering materials and ceramics [95]. The
metal injection process offers reduced production costs, especially
in producing complex components in large quantities [113,114]. In
titanium processing using MIM, the small and complex products
are contaminated by carbon, oxygen, and nitrogen, which affects
the other processes [115]. Contamination occurs in oxide form at
the interface of a particle that initiates cracking. The contamination
level of a material contributes to the fatigue properties of a product
[116].
MIM is used to fabricate biomaterial components
[8,12,113,117]. Developing composite structures containing tita-
nium alloys and HA for medical applications using MIM has been
extensively studied by Thian et al. [8,63,90,118]. HA/Ti composite
powder is prepared through the ceramic slurry approach with
Fig. 14. Stages of the metal injection process [111].
172 A. Arin et al. / Materials and Design 55 (2014) 165175
PVA as a binder. PVA is removed from the homogenized composite
powder by heating. The powder is then crushed into small particles
using a mortar and pestle [119]. The composite powder is mixed
with commercial a multi-component binder system consisting of
natural wax, fatty acid wax, stearic acid, poly-oxi-alkylen-ether,
and olen-hydrocarbons. A sigma blade mixer is used to mix feed-
stock consisting of HA/Ti6Al4V composite powder and binder at a
mixing temperature of 90 C until homogeneity is achieved. The
mixing temperature is determined by differential scanning calo-
rimetry [118]. For 50 wt% Ti6Al4V and 50 wt% HA, Thian et al.
found that a powder loading of 60 vol% is the most suitable for
yielding homogeneous and moldable feedstock [90]. The effects
of the sintering temperature, heating rate, and cooling rate on
the density and porosity are determined. At a sintering tempera-
ture of 1100 C, the density, hardness, exural strength, and ex-
ural modulus increase at heating rate of 7.5 C/min and cooling
rate of 5 C/min with a high exural strength and modulus at
1150 C [63].
At high sintering temperatures, a HA/Ti system decomposes at
800 C [46,60]. Ye et al. [64] found that the presence of titanium
in HA accelerates the dehydroxylation and decomposition of HA.
The decomposition of HA increases with increased sintering tem-
perature, and signicant decomposition begins after the specimens
are sintered above 1100 C [63]. In vitro experiments on HA/Ti
specimens have revealed their chemical content and surface mor-
phology after immersion in SBF. After 2 weeks, the dissolution of
secondary phases such as TCP, TTCP, and CaO is complete. At 2
4 weeks, the mechanical properties of the specimens decrease be-
cause of the dissolution of calcium phosphate layers. Afterwards,
the mechanical properties are recovered by the precipitation of
the apatite layer [8]. Some methods of fabricating HA/Ti compos-
ites that approach the mechanical properties of bone and have
Youngs modules ranging from 10 GPa to 30 GPa have been pro-
posed, as shown in Table 3. However, the manufacturing cost, size,
and geometry of the products must still be considered.
In the early weeks of in vitro tests, the dissolution of HA/Ti com-
posites generally produce secondary phases such as TCP, TTCP, and
CaO. The mechanical properties of implants signicantly decrease
and the mechanical properties increase to achieve the near-initial
value after the next stage [8].
10. Conclusions
Issues concerning the material processing and metallurgy char-
acteristics have been reviewed and discussed to meet the require-
ments for medical implant applications using existing
manufacturing process. The composition of titanium and HA deter-
mines the effectiveness of the mechanical properties and biocom-
patibility of HA/Ti composites. Moreover, the sintering parameters
are critical factors in determining the phase of two materials
formed during the diffusion process. In particular, the sintering
temperature plays a dominant role in the fabrication of HA/Ti com-
posites because this parameter affects the thermal stability of HA.
Generally, HA/Ti composites produce TCP, TTCP, and CaO in air,
with the main phases being TiO
2
and calcium titanate. In vivo
and in vitro tests validate the ability of HA/Ti composites to form
bonds with natural tissues, especially at the early stages of implan-
tation. In conclusion, optimization of process parameters especially
during sintering parameters (temperature, heating rate, time, gas
condition) should be further investigated to determine a better
working processing window for the manufacturing of HA/Ti
composites.
Acknowledgments
This work was supported by Grant No. UKM-DLP-2012-027
from the Universiti Kebangsaan Malaysias Research University
Grant and FRGS/1/2011/TK/UKM/02/20 from the Malaysia Ministry
of Higher Education (MOHE).
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