journal of the mechanical behavior of biomedical materials 49 (2015) 129140

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Research Paper

Sintering and the mechanical properties

of the tricalcium phosphatetitania composites
Ibticem Ayadi, Foued Ben Ayedn
Laboratory of Industrial Chemistry, National School of Engineering, Sfax University, Box 1173, 3038 Sfax, Tunisia

art i cle i nfo

ab st rac t

Article history:

The sintering of the tricalcium phosphate with different percentages of titania was

Received 5 February 2015

investigated. The samples were characterized by differential thermal analysis, dilatometry

Received in revised form

analysis, X-Ray diffraction, infrared spectroscopy, magic angle scanning nuclear magnetic

28 April 2015

resonance and scanning electronic microscopy measurements. The samples were exam-

Accepted 5 May 2015

ined by using the mechanical properties such as rupture strength, Vickers hardness and

Available online 14 May 2015

elastic modulus. The sintering of the tricalcium phosphatetitania composites indicates

Keywords:

the evolution of the microstructure, the densication and the mechanical properties. The

Sintering

performances of the composites increase with both the sintering temperature and the

Composites

addition of the titania. The highest values of the composites of rupture strength (33 MPa),

Mechanical properties

Vickers hardness (270 Hv), Young's modulus (33.1 GPa) and shear modulus (15.7 GPa) were

Tricalcium phosphate
TiO2

obtained after the sintering process with 40 wt% titania at 1200 1C. The increase of these
performances is due to the formation of the liquid-phase which helps to ll the pores in
the microstructure. Above 40 wt% TiO2, the mechanical properties of the composites are
hindered by the exaggerated grain growth formation.
& 2015 Elsevier Ltd. All rights reserved.

1.

Introduction

their mechanical properties which make it brittle, with poor

fatigue resistance (Elliott, 1994; Hench, 1998). Moreover, the

Tricalcium phosphate (-Ca3(PO4)2, -TCP) based on biomater-

mechanical properties of tricalcium phosphate are generally

ial has attracted considerable interest for orthopedic and

inadequate for many load-carrying applications (Bouslama

dental applications (Ben Ayed et al., 2006; Ben Ayed, 2011;

et al., 2009; Elliott, 1994; Hench, 1998). Hence, inert oxides

Bouslama et al., 2009, 2013; Destainville et al., 2003; Elliott,

such as alumina (Al2O3) or zirconia (ZrO2) have been widely

1994; Gaasbeek et al., 2005; Hench, 1993, 1998; Jensen et al.,

studied due to their bio-inertness, excellent tribological

2006; Sakka et al., 2013, 2014; Sallemi et al., 2015). The

properties, fracture toughness and strength (Elliott, 1994;

tricalcium phosphate has been used clinically to repair bone

Hench, 1998; Sakka et al., 2013, 2014; Sallemi et al., 2013,

defects for many years (Elliott, 1994; Gaasbeek et al., 2005;

2015). Thus, the study conducted by Sakka et al. (2013) has

Hench, 1993, 1998; Jensen et al., 2006). However, the major

recently concerned with the tricalcium phosphate/alumina

limitation to the use of -TCP as load bearing biomaterial is

system. The researchers were interested in producing the

Corresponding author. Tel.: 216 98 252 033; fax: 216 74 275 595.
E-mail address: benayedfoued@yahoo.fr (F. Ben Ayed).

http://dx.doi.org/10.1016/j.jmbbm.2015.05.001
1751-6161/& 2015 Elsevier Ltd. All rights reserved.

130

journal of the mechanical behavior of biomedical materials 49 (2015) 129 140

Al2O3TCP composites with different percentages of -TCP

(10 wt%, 20 wt%, 40 wt% and 50 wt%). As a result of this study,
the best mechanical properties of the alumina10 wt% tricalcium phosphate composites reached 13.5 MPa after the sintering process at 1600 1C (Sakka et al., 2013). In the second half,
the next study carried out by Sakka et al. (2014) has showed that the alumina10 wt% tricalcium phosphate5 wt%
TiO2 composites displayed the highest mechanical properties
(74 MPa) at 1600 1C. But, the low percentage of the tricalcium
phosphate (10 wt%) in the Al2O3TCPTiO2 composites limits
the use in the biomedical applications. Besides, the high
sintering temperature (1600 1C) proves the exaggerated growth
of grains which hindered the performances of these composites (Sakka et al., 2014). Even so, alumina is typically inactive
and incapable of forming a direct bond with the host tissue
(Runyan and Bennison, 1991). Also, the study done by Sallemi
et al. (2013) was interested to elaborate and to characterize the
tricalcium phosphatezirconia composites with different percentages of zirconia (25 wt%, 50 wt% and 75 wt%). Thus, the
ultimate values of the performances of the tricalcium phosphate was obtained with 50 wt% zirconia (Sallemi et al., 2013).
But the experimental results in this study indicate the appearance of low mechanical properties of the tricalcium phosphatezirconia composites (Sallemi et al., 2013, 2015). Based on
the results, the inverse allotropic transformation of zirconia is
sufcient to cause the degradation of mechanical properties of
these composites (Sallemi et al., 2013, 2015). Thus, the expansion in volume of the zirconia samples is responsible for the
fragility of the tricalcium phosphatezirconia composites
(Sallemi et al., 2013, 2015). In conclusion, the addition of
alumina or zirconia to the TCP matrix does not give a good
result of the mechanical properties (Sakka et al., 2013, 2014;
Sallemi et al., 2013, 2015). For this reason, we tested another
inert oxide like titania (TiO2). Besides, titania has attracted
much attention due to its excellent ability to chemically bond
with living hard tissue (Jung and Kim, 2010; Kaneko et al.,
2002). This happens through the formation of a bone minerallike tricalcium phosphate phase on the material surface that
ultimately induces direct bonding with native bone tissue (Li
et al., 2007; Mazaheri et al., 2009; Shin and Paek, 2006). Thus,
titania has been attracting attention as an implantable material because it is harmless to a living body, and with good
mechanical properties. Moreover, titania is an attractive
material, applicable to various elds, such as biomedical
applications (Jung and Kim, 2010; Kaneko et al., 2002; Li
et al., 2007; Mazaheri et al., 2009; Shin and Paek, 2006).
Furthermore, the titania is considered as having excellent
biocompatibility, manifested in various biomedical applications (Jung and Kim, 2010; Kaneko et al., 2002; Li et al., 2007;
Mazaheri et al., 2009; Shin and Paek, 2006). In the light of this
consideration, we have chosen titania as the agent to be added
to the tricalcium phosphate. Thus, titania can be mixed with
TCP to make bioceramic composites, which would combine
the biocompatibility of the TCP and the high tribological
properties of titania. The calcium phosphate/inert oxide system which can be a good combination of TCP and titania is
considered as a promising approach to prepare more appropriate biomaterials in the physiological environment (Ning
and Zhou, 2002). This is the principal advantage of using the
TCPTiO2 composites compared with other tricalcium

phosphateinert oxides composites previously reported. Most

studies are devoted to the knowledge of the sintering and the
mechanical properties of the pure TCP or the pure TiO2. On the
contrary little work has been reported on the performances of
the TCPTiO2 composites (Caroff et al., 1998; Lee et al., 2006;
Sprio et al., 2013). These papers are interested in obtaining
TCPTiO2 composites starting hydroxyapatite and titania
(Caroff et al., 1998; Lee et al., 2006; Sprio et al., 2013). There is
a possibility to incorporate the titania with the tricalcium
phosphate to enhance the mechanical properties of tricalcium
phosphate, but not to degrade its biocompatibility. This work
intends to study the inuence of titania on the phase transformation, the densication, the mechanical properties and
the microstructures of the tricalcium phosphate. Moreover, we
are interested in examining the effect of introducing the TiO2
on the TCP matrix sintered at various temperatures (1000 1C,
1100 1C, 1200 1C and 1300 1C) with different percentages of TiO2
(2.5 wt%; 5 wt%; 7.5 wt%, 10 wt%, 20 wt%, 30 wt%, 40 wt% and
50 wt%). After the sintering process, the characteristics of the
samples are examined by X-ray diffraction, infrared spectroscopy, magic angle scanning nuclear magnetic resonance and
scanning electron microscopy.

2.

Materials and methods

The commercial titania (Fluka, purity498%) and synthesized

tricalcium phosphate were used in this study. The -TCP
powder was synthesized by solid-state reaction from calcium
carbonate (CaCO3: Fluka, purity Z98.5%) and calcium phosphate dibasic anhydrous (CaHPO4: Fluka, purityZ 99%) (Sakka
et al., 2013). Stoichiometric amounts of high purity powders,
CaHPO4 and CaCO3 were sintered at 1000 1C for 2 h to obtain
-TCP according to the following reaction:
2 CaHPO4s CaCO3s -Ca3 PO4 2s H2 Og CO2g

Titania was introduced in the -TCP matrix at different

contents (2.5 wt%; 5 wt%; 7.5 wt%, 10 wt%, 20 wt%, 30 wt%,
40 wt% and 50 wt%) followed by homogeneous mixing in a
mortar. Synthesized tricalcium phosphate and commercial
titania powders were mixed with absolute ethanol in an agate
mortar. After milling these powders, the mixture ( -TCP and
TiO2) was dried at 80 1C for 24 h. After the drying, the powder
mixtures were molded in a cylinder having a diameter of
20 mm and a thickness of 4 mm and pressed under 150 MPa.
The heat treatment of the compacted disks was carried out in
a vertical programmable mufe furnace (Pyrox 2408) at
various temperatures (1000 1C, 1100 1C, 1200 1C and 1300 1C)
for one hour. The specimens were heated and cooled at a rate
of 10 1C min  1 and 20 1C min  1, respectively.
X-ray diffraction (XRD) analysis was conducted in order to
analyze the phase transformation in the different structures
of the composites before and after the sintering process at
various temperatures. The components phases of the sintered samples were identied by X-ray diffraction (Seifert
XRD 3000 TT diffractometer) with CuK radiation ( 1.54056
). The identication phase was carried out by comparing the
experimental XRD patterns with the standards les compiled
by the International Center for Diffraction Data (ICDD). The
powder is also submitted to infrared spectrometric (IR)

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journal of the mechanical behavior of biomedical materials 49 (2015) 129 140

analysis (Perkin-Elmer 783). The 31P magic angle scanning

nuclear magnetic resonance (MAS-NMR) spectra were collected on a Brucker 300WB spectrometer. The 31P observational frequencies were 121.49 MHz and 78.2 MHz,
respectively. 31P shifts are given in parts per million (ppm),
referenced to 85 wt% H3PO4.
The microstructure of the sintered compacts was investigated on samples of the fractured surfaces with a scanning
electron microscope (SEM) (JSM-5400). These samples were
coated with a gold layer for more electronic conductivity.
The size of the particles of the powder was measured by
means of a Micromeritics Sedigraph 5000. The specic surface
area (SSA) was measured with the BET method using azotes
(N2) as an adsorption gas (ASAP 2010) (Brunauer et al., 1938).
The main particle size (DBET) was calculated by assuming that
the primary particles are spherical (Bernache-Assollant, 1993)
6
DBET
S

dilatometer). About 20 mg of powder was heated up to

1500 1C at a heating rate of 10 1C min  1 along with alumina
as the reference material and a low stream of argon gas.
Differential thermal analysis (DTA) was carried out using
about 30 mg of powder (DTA, Setaram TMA 92). The heating
and cooling rates were 10 1C min  1 and 20 1C min  1,
respectively.
The Brazilian test was used to measure the mechanical
properties of the samples (ASTM C496, 1984; ISRM, 1978). The
rupture strength (r) (or mechanical strength) was calculated
based on the maximum applied load recorded (P) and sample
dimension; (D being the diameter and t being the thickness)
using Eq. (4)
r

where is the theoretical density and S is the surface

specic area.
The densication of the sintered specimens was evaluated
from measurements of the dimensions of the specimen. The
relative error of the densication value was about 1%. The
theoretical density (d) was determined using the following
equation:
3

where H is Vickers hardness, P is the indentation load and d

is the indent diagonal length. Average hardness value was
taken from 10 indents made for each sample and the maximum error obtained was found to be less than 5%.
The testing instrument includes a high-frequency generator Model 5077PR (Olympus). The samples have been
characterized and evaluated using the ultrasound techniques
(Bouslama et al., 2013; Chevalier, 2003). Young's modulus and
the shear modulus were calculated from the point of the
longitudinal and the transversal ultrasonic velocities
(Bouslama et al., 2013; Chevalier, 2003).

where A and B are the weight ratios and 3.07, 3.89 are the
theoretical densities of -TCP and anatase-TiO2, respectively.
The calculated theoretical densities of each composite are
illustrated in Table 1.
Thermal expansionshrinkage of the compact powder was
measured with a dilatometer (Model Setaram TMA 92

Table 1 Theoretical densities and the weight rates of

each compound used in the TCPTiO2 composites.
Aa (wt%)

Ba (wt%)

db (g/cm3)

2.5
5.0
7.5
10.0
20.0
30.0
40.0
50.0

97.5
95.0
92.5
90.0
80.0
70.0
60.0
50.0

3.090
3.111
3.131
3.152
3.234
3.316
3.398
3.480

a
b

At least six specimens were tested under each test condition. Average values (r) were calculated. The resulting dispersal is of the order of 15%.
The mechanical properties of the samples were also
assessed by Vickers indentation using loading values of about
49 or 98 N applied for 15 s. The surface of the samples was
polished between 1 mm and 3 mm using diamond paste. Ten
indents were made for each measurement and hardness (H)
was calculated using Eq. (5) (ASTM C1327-96, 2003):


5
H 1:854 P=d2

d 3:07A 3:89B=100

2P
Dt

3.

Results

3.1.

Characterization of the starting powders

The SSA, the calculated average grain sizes DBET and the
particles size distribution data (measured by granulometric
repartition) for the TiO2 and the -TCP powders are shown in
Table 2. The average grain size of the samples obtained by the
SSA (DBET) does not correspond to those obtained from the
granulometric repartition (D50). The discrepancy may be due
to the presence of agglomerates in the initial powders.

A and B are the weight rates of TiO2 and -TCP, respectively.

Theoretical density.

Table 2 Characteristics of powders used in the study.

Compounds

SSA (m2/g)

DBET (m)

D50a (m)

db(g/cm3)

Anatase-TiO2
-TCP

12.00
0.80

0.11
2.80

0.20
6.00

3.89
3.07

a
b

Mean diameter.
Theoretical density.

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journal of the mechanical behavior of biomedical materials 49 (2015) 129 140

Intensity (arbitrary units)

hkl

The XRD spectra obtained from the tricalcium phosphate

and titania powders are reported in Fig. 1. The peaks observed
in the X-ray diffraction pattern of the tricalcium phosphate
powder reveal only the presence of the phase (ICDD data le
No. 70-2065) (Fig. 1a). Fig. 1b shows the presence of characteristics peaks of the anatase phase of TiO2 (ICCD data le
No. 89-4921).
The DTA curve of the -TCP shows two endothermic peaks
(Fig. 2a). The rst large band (between 1230 1C and 1270 1C)
characterizes the rst allotropic transformation of the tricalcium phosphate ( to ) while the second peak around 1470 1C
characterizes the second transformation ( to 0 ). The results
are similar to those previously reported by literature
(Bouslama et al., 2010; Sakka et al., 2014). The DTA curve of
the TiO2 shows that no evolution can be obtained with the
sintering temperature (Fig. 2b). The TCP10 wt% TiO2 composites presents 2 endothermic peaks in the DTA curve (Fig. 2c).

10

20

30

40

50

60

2 (degrees)

Fig. 1 XRD patterns of different powders: (a) -TCP and

(b) TiO2.

The peak at 1470 1C is relative to the second allotropic

transformation of the tricalcium phosphate ( to 0 ). Furthermore, the new peak appearing at 1440 1C is probably attributed to the formation of a liquid phase. The melting
temperatures of the pure TiO2 and the pure -TCP are
1855 1C and 1756 1C, respectively (Caroff et al., 1998). Thus,
the liquid phase is formed between TiO2 and -TCP, and it is
not relative to the melting point of the initial powders. The
results are similar to the one found in the previous studies
(Caroff et al., 1998; Sakka et al., 2014). They show that in the
TiO2/-TCP system, there is an eutectic with a composition of
63 wt% TCP37 wt% TiO2 at 1380 1C (Caroff et al., 1998). Fig. 3
conrms the presence of the liquid phase which is showed in
the binary diagram of the Ca3(PO4)2/TiO2 (Caroff et al., 1998).
Fig. 4 shows the dilatometric measurements of different
powders used in this study (-TCP, TiO2 and TCP10 wt% TiO2
composites). The sintering temperature of the initial powder
began at about 1000 1C and at about 900 1C for the -TCP and
the TiO2, respectively (Fig. 4a and b). The rst allotropic
transformation of the tricalcium phosphate appears at
1230 1C (Fig. 4a). The shrinkage curve of the pure titania could
be divided according to the phase transformation of anatase
into rutile which is started at about 1090 1C (Fig. 4b). This
result was already conrmed by literature (Gouma and Mills,
2001). In fact, they showed that the commercial anatasetitania powder has been transformed into the rutile structure
at about 1000 1C (Gouma and Mills, 2001), which conrms our
results. Fig. 4c presents the shrinkage curve of the TCP10 wt
% TiO2 composites. The curve of the composites does not
report any process relative to the allotropic transformation of
the -TCP (Fig. 4b). On the other hand, the addition of titania
in the tricalcium phosphate matrix stabilized their structure
and partially prevented the inverse allotropic transformation
of the tricalcium phosphate from the phase to the phase
(at 1100 1C). These results prove the stabilization of the
structure of the tricalcium phosphate with the addition of
titania. This result was explained by the exchange of Ca2
and Ti4 between the -TCP and TiO2.

(a)
Endo

-5

Heat flow (V)

(c)
-10

(b)

-15

-20

-25

-30
0

200

400

600

800

1000

1200

1400

1600

T (C)

Fig. 2 DTA curves of: (a) -TCP, (b) anatase-TiO2 and (c) TCP
10 wt% TiO2 composites.

Fig. 3 Phase equilibrium diagram of the TiO2 Ca3(PO4)2

system (Caroff et al., 1998).

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journal of the mechanical behavior of biomedical materials 49 (2015) 129 140

88
(h)
(g)
Density (%)

83
(f)
78

(e)
(d)

73

(b)

(c)
(a)

68
950 1000 1050 1100 1150 1200 1250 1300 1350
T (C)
Fig. 5 Relative density versus temperature of the -TCP
sintered for one hour with different percentages of TiO2:
(a) 2.5 wt%, (b) 5 wt%, (c) 7.5 wt%, (d) 10 wt%, (e) 20 wt%,
(f) 30 wt%, (g) 40 wt% and (h) 50 wt%.

35

Mechanical Strength (MPa)

30
25
20
15
(e)
10
5
0
950

Fig. 4 Linear shrinkage curves of: (a) -TCP, (b) TiO2 and
(c) TCP10 wt% TiO2 composites.

3.2.
Effect of the addition of titania on the densication
and the mechanical properties of the tricalcium phosphate
The effect of the sintering temperature and the addition of
titania on the relative density of the tricalcium phosphate
was studied between 1000 1C and 1300 1C. Fig. 5 shows the
typical relationship between temperature and density. The
density of the -TCP sintered with different percentages of
the TiO2 (2.5 wt%, 5 wt%, 7.5 wt%, 10 wt%, 20 wt%, 30 wt%,
40 wt% and 50 wt%) increases with the sintering temperature
(Fig. 5). At 1200 1C, the optimum value of the densication

(g)
(f)
(h)

(d)
(c)
(b)
(a)
1000 1050 1100 1150 1200 1250 1300 1350
T (C)

Fig. 6 Mechanical strength versus temperature of the -TCP

sintered for one hour with different percentages of TiO2:
(a) 2.5 wt%, (b) 5 wt%, (c) 7.5 wt%, (d) 10 wt%, (e) 20 wt%,
(f) 30 wt%, (g) 40 wt% and (h) 50 wt%.

(89%) was obtained with 40 wt% TiO2 (Fig. 5g). Above 1200 1C,
the performances of the composites decrease abruptly
(Fig. 5ag).
Fig. 6 shows the inuence of the titania additive (2.5 wt%,
5 wt%, 7.5 wt%, 10 wt%, 20 wt%, 30 wt%, 40 wt% and 50 wt%)
and the sintering temperature (1000 1C, 1100 1C, 1200 1C and
1300 1C) on the mechanical strength of tricalcium phosphate.
The rupture strength of the TCPTiO2 composites increases
with both the sintering temperature and the percentage of
titania (Fig. 6). At 1200 1C, the rupture strength of the TCP
40 wt% TiO2 composites reached its maximum value (33 MPa)
(Fig. 6g). Above 1200 1C, the rupture strength of the TCPTiO2

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journal of the mechanical behavior of biomedical materials 49 (2015) 129 140

35
30

E (GPa)

25
20

(c)
(b)
(a)
(d)

15
10
5
0

10

15

20

25

30

35

40

45

Characterization of the TCPTiO2 composites

16
14
12
10
8

(c)
(b)
(a)
(d)

After the sintering process, the samples have been characterized by different techniques such as: XRD, IR, 31P MAS-NMR
and SEM.
The XRD analysis of the TCPTiO2 composites sintered at
1000 1C with different percentages of titania (10 wt%, 20 wt%,
30 wt%, 40 wt% and 50 wt%) are reported in Fig. 10. The X-ray
spectra of the -TCPTiO2 composites sintered with different

55

Fig. 8 Young's modulus of the -TCP sintered for one hour

with different percentages of TiO2 at: (a) 1000 1C; (b) 1100 1C,
(c) 1200 1C and (d) 1300 1C.

3.3.

50

TiO2 (wt.%)

G (GPa)

composites was hindered abruptly (Fig. 6). The discrepancy of

results appears especially after the addition of 50 wt% TiO2 in
the tricalcium phosphate matrix (Fig. 6g). The signicant
improvement of the characteristic of the TCP40 wt% TiO2
composites can be explained by the formation of the liquid
phase between -TCP and TiO2 which contribute to the better
densication and the high rupture strength.
Fig. 7 shows the variation of Vickers hardness of the TCP
TiO2 composites sintered at various temperatures with different percentages of TiO2. Vickers hardness of the composites increases with the sintering temperature and the
percentage of TiO2 (Fig. 7). Thus, Vickers hardness reached
its maximum value (270 Hv) after the sintering process at
1200 1C with 40 wt% TiO2. Vickers hardness of the composites
decreases with the increase of the sintering temperature.
The evolution of Young's modulus and the shear modulus
of the -TCP sintered at various temperatures (1000 1C,
1100 1C, 1200 1C and 1300 1C) with different amounts of TiO2
(2.5 wt%, 5 wt%, 7.5 wt%, 10 wt%, 20 wt%, 30 wt%, 40 wt% and
50 wt%) are illustrated in Figs. 8 and 9, respectively. The
elastics modulus (E and G) of the -TCPTiO2 composites
increased with both the sintering temperature and the addition of TiO2. Young's modulus and the shear modulus
obtained their optimum values at 1200 1C with 40 wt% TiO2:
33.1 GPa and 15.7 GPa, respectively. Above 40 wt% TiO2, the
performances of the composites were hindered with the
increase of the sintering temperature (Figs. 8 and 9).

2
0

10

15

20

25 30 35
TiO2 (wt.%)

40

45

50

55

Fig. 9 Shear modulus of the -TCP sintered for one hour

with different percentages of TiO2 at: (a) 1000 1C, (b) 1100 1C,
(c) 1200 1C and (d) 1300 1C.

Vickers hardness (HV)

280

230
(c)
(d)
180
(b)
130
(a)

80
0

10

15

20 25 30 35
TiO2 (wt.%)

40

45

50

55

Fig. 7 Vickers hardness versus temperature of the -TCP

sintered for one hour with different percentages of TiO2 at:
(a) 1000 1C; (b) 1100 1C; (c) 1200 1C; and (d) 1300 1C.

Fig. 10 XRD patterns of the -TCP sintered at 1000 1C with

different percentages of TiO2: (a) 10 wt%, (b) 20 wt%, (c) 30 wt%,
(d) 40 wt% and (e) 50 wt%. (: -TCP, : CaTiO3, : anatase, n:
rutile).

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journal of the mechanical behavior of biomedical materials 49 (2015) 129 140

percentages of titania revealed the -TCP, anatase-TiO2 and a

new phase relative to the CaTiO3 traces which indicate the
interaction between -TCP and TiO2 (Fig. 10). The X-ray
spectra of the tricalcium phosphate sintered with 10 wt%,
20 wt% or 30 wt% titania revealed the initial phases, the
majority peaks are relative to the -TCP phase (Fig. 10ac).
When the percentage of titania (40 wt% or 50 wt%) increases
in the composites, the anatase phase became in majority
quantities with traces of the rutile phase of titania (Fig. 10d
and e).
The XRD spectra of the TCPTiO2 composites sintered at
1200 1C with different percentages of titania (10 wt%, 20 wt%,
30 wt%, 40 wt% and 50 wt%) are showed in Fig. 11. The XRD
spectra of samples show the presence of the -TCP phase
beside the initial phase (-TCP and anatase-TiO2) (Fig. 11). The
addition of the 10 wt% TiO2 promotes the formation of the
rutile phase of titania, the majority peaks are relative to the TCP phase (Fig. 11a). The effect of TiO2 during the sintering

Fig. 11 XRD patterns of the -TCP sintered at 1200 1C with

different percentages of TiO2: (a) 10 wt%, (b) 20 wt%, (c) 30 wt%,
(d) 40 wt% and (e) 50 wt%. (: -TCP, : -TCP, : CaTiO3,
: anatase, n: rutile).

process was remarked in XRD spectra (Fig. 11be). Above

10 wt% TiO2, the quantities of the rutile phase increase in the
XRD spectra of the TCPTiO2 composites. Thus, the majority
peaks are relative to the rutile phase of titania (Fig. 11d and e).
Thus, the intensities of the rutile phase increase by the
addition of TiO2 while those of -TCP and -TCP decrease
which conrm the interaction between tricalcium phosphate
and titania (Fig. 11e).
Fig. 12A illustrates the infrared spectra of the composites
sintered at 1200 1C without and with different percentages of
TiO2 (10 wt%, 40 wt% and 50 wt%). Most bands characterize
the phosphate group of -TCP, especially at 548 cm  1,
585 cm  1, 605 cm  1, 941 cm  1, 971 cm  1, 1036 cm  1 and
1117 cm  1 (Fig. 12A). The peaks at 548 cm  1, 585 cm  1 and
605 cm  1 are assigned to the asymmetric deformation of the
PO34  ions (1). Indeed, the peaks at 941 cm  1 and 971 cm  1
are relative to the symmetric stretching of the PO34  ions (2)
and the peaks at 1036 cm  1 and 1117 cm  1 are relative to the
asymmetric stretching of the PO34  ions (3) (Fig. 12A). The
band obtained between 680 cm  1 and 750 cm  1 is assigned to
the stretching vibration of TiO derived from titania (Fig. 12A
(bd)). The intensity of the bands characteristics of the
phosphate group decreased with 40 wt% TiO2 (Fig. 12A-d).
The infrared spectrum of the composites shows a new peak
(at 420 cm  1) which is probably relative to the CaOTi band
(Fig. 12A-d). This result conrms the interaction between
tricalcium phosphate and titania. Infrared spectra of the
TCP40 wt% TiO2 composites sintered at various temperatures (1000 1C, 1200 1C and 1300 1C) are practically similar to
those in Fig. 12A and B . When the sintering temperature
increases, the new band appears at about 420 cm  1 which is
probably relative to the CaOTi band (Fig. 12B(b and c)).
The 31P MAS-NMR spectra of the TCPTiO2 composites
sintered at 1200 1C with different amounts of TiO2 (2.5 wt%,
10 wt%, 20 wt%, 30 wt%, 40 wt% and 50 wt%) are presented in
Fig. 13A. All curves prove the presence of tetrahedral environments (Fig. 13A). Fig. 13B shows the 31P MAS-NMR spectra
of the TCP40 wt% TiO2 composites sintered at various
temperatures (1000 1C, 1100 1C, 1200 1C and 1300 1C). These
spectra reveal the same structure practically, which are so

(c)

Transmittance (arbitrary units)

Transmittance (arbitrary units)

(d)

(c)

(b)

(a)

4000

3600

3200

2800

2400

2000

1600

Wavenumber (cm-1 )

1200

800

400

(b)

(a)

4000

3600

3200

2800

2400

2000

1600

1200

800

400

Wavenumber (cm-1 )

Fig. 12 Infrared spectra of the -TCP sintered: (A) at 1200 1C for one hour without and with different percentages of TiO2:
(a) 0 wt%, (b) 10 wt%, (c) 40 wt% and (d) 50 wt%. (B) for one hour with 40 wt% TiO2 at: (a) 1000 1C, (b) 1200 1C and (c) 1300 1C.

136

journal of the mechanical behavior of biomedical materials 49 (2015) 129 140

close to those obtained in Fig. 13A. Accordingly, introducing

titania on the tricalcium phosphate matrix conserves the
tetrahedral environment of the pure -TCP.
The microstructure of the TCPTiO2 composites sintered at
1200 1C with different percentages of TiO2 (2.5 wt%, 10 wt%,
40 wt% and 50 wt%) are shown in Fig. 14. These micrographs
of the composites show the coalescence between the -TCP
grains produced with different percentages of the added
titania (Fig. 14ad). The samples sintered with 10 wt% TiO2
present a continuous phase relative to the -TCP and an
intragranular porosity which is tailed between 1 mm and 2 mm
(Fig. 14b). Furthermore, the continuous phases in addition to

the formed spherical pores prove that a liquid phase

appeared at 1200 1C which is formed between TiO2 and TCP
(Fig. 14b). Therefore, a rather poor densication characterizes
the samples (Fig. 14a and b). However, a high densication
was caused after the addition of 40 wt% TiO2 to the TCP
matrix (Fig. 14c). The microstructure of the TCP40 wt% TiO2
composites sintered at 1200 1C shows a continuous phase
relative to the -TCP phases and a small-sized grains relative
to titania (Fig. 14c). At 1200 1C, the formation of liquid phase
helps to ll the pores in the microstructure of the TCP40 wt%
TiO2 composites (Fig. 14c). The densication of samples is due
to the transfer of mass in the liquid-phase sintering which is

(g)
(d)

(f)
(e)

(c)

(d)
(c)

(b)

(b)
(a)

(a)
40

20

-20

-40

(ppm)

40

20

-20

-40

(ppm)

Fig. 13 31P MAS-NMR spectra of the -TCP sintered: (A) at 1200 1C for one hour without and with different percentages of TiO2:
(a) 0 wt%, (b) 2.5 wt%, (c) 10 wt%, (d) 20 wt%, (e) 30 wt%, (f) 40 wt% and (g) 50 wt%. (B) for one hour with 40 wt% TiO2 at:
(a) 1000 1C, (b) 1100 1C, (c) 1200 1C and (d) 1300 1C.

5 m

5 m

5 m

5 m

Fig. 14 SEM micrographs of the -TCP sintered at 1200 1C for one hour with different percentages of TiO2: (a) 2.5 wt%, (b) 10 wt%,
(c) 40 wt% and (d) 50 wt%.

journal of the mechanical behavior of biomedical materials 49 (2015) 129 140

responsible to the better values of mechanical properties

(Fig. 14c). Excessive grain growth was apparent in the micrograph of the TCP50 wt% TiO2 composites (Fig. 14d). Thus, the
fragility of the composites and the decrease in their mechanical performances originated from the small expansion and
the grain growth when the percentage of titania increases
(50 wt% TiO2) (Fig. 14d).
The SEM examination of the fractured surfaces of the TCP
40 wt% TiO2 composites sintered at various temperatures
(1000 1C, 1100 1C, 1200 1C and 1300 1C) is reported in Fig. 15.
At 1000 1C, the microstructure of the TCP40 wt% TiO2 composites presents an intergranular porosity (Fig. 15a). The
continuous phases present the -TCP phase and the smallsized grains relative to titania phase (Fig. 15a). The presence
of the grains of TiO2 is distinguished with their white color
(Fig. 15a). The effects of the sintering temperature on the
TCPTiO2 composites reveal a distinct deference in the
samples' microstructure (Fig. 15bd). The sample presents
an important intergranular porosity subsequently eliminated,
with the grain growth (Fig. 15bd). When the sintering
temperature increases, the grains' growth becomes slowly
exaggerated (Fig. 15d). The microstructure of the composites
exhibited considerable densication under effect of the
increase of the sintering temperature which improves also
the performances of the composites value especially at
1200 1C.

4.

Discussion

The -TCP is a resorbable material which can form a strong

bond with the bone (Elliott, 1994; Hench, 1993, 1998). However, the poor mechanical properties of the tricalcium

137

phosphate limit the use of the bulk material to the biomedical applications. For this reason, the improving of the sinterability of the -TCP and enhancing its mechanical
performances is the aim of this work. The addition of titania
in the -TCP matrix could favor reasonable combination
because it has excellent tribological properties, high strength
and is bio-inert with human tissue (Kaneko et al., 2002; Li
et al., 2007; Mazaheri et al., 2009; Sakka et al., 2013, 2014;
Sallemi et al., 2015; Shin and Paek, 2006). In order to improve
the biocompatibility of titania and the strength of tricalcium
phosphate effectively and to search for an approach to
produce high performances of the tricalcium phosphate
titania composites, titania is introduced with different percentages in the -TCP matrix. The main reason behind the
use of the calcium phosphate/inert oxide system as implant
or bone substitute is their combination of resorbability of TCP
and high tribological properties of titania. This use leads to an
ultimate physicochemical bond between the implants (based
on TCP and TiO2) and bone-termed osteointegration.
The mechanical properties of the TCPTiO2 composites
reached an optimum value with the increase of the sintering
temperature and the percentage of titania. Indeed, the optimum values ( 89%, r 33 MPa, E 33.1 GPa, G 15.7 GPa
and H 270 Hv) of the TCPTiO2 composites performances
are obtained at 1200 1C with 40 wt% TiO2. These values are
compared to those of the bone tissues (Elliott, 1994; Hench,
1993). The fragility of the -TCP sintered with 50 wt% TiO2 is
due to the grains' exaggerated growth. This result is conrmed by SEM analysis (Fig. 14d).
Table 3 depicts literature examples of the mechanical
strength of the bioceramics and bone tissues. In this study,
the rupture strength of the -TCP40 wt% TiO2 composites reaches 33 MPa. This obtained result is close to the

10 m

10 m

10 m

10 m

Fig. 15 SEM micrographs of the -TCP sintered for one hour with 40 wt% TiO2 at: (a) 1000 1C, (b) 1100 1C, (c) 1200 1C and
(d) 1300 1C.

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journal of the mechanical behavior of biomedical materials 49 (2015) 129 140

mechanical strength of the dentin (Table 3). Moreover, this

value (33 MPa) is higher than the mechanical strength of
some calcium phosphates (-TCP and TCP33.16 wt% FAp)
realized in the literature (Ben Ayed, 2011; Bouslama et al.,
2009). Also, the obtained result in this work is similar to the
performances of the TCPZrO2MgO composites (Table 3;
Sallemi et al., 2015). Thus, the study made by Sallemi et al.
(2015) has showed that the best performances of the TCP
45 wt% ZrO210 wt% MgO composites reached at 1400 1C
(Table 3). On the contrary, the study conducted by Sakka
et al., 2014 has showed higher mechanical properties of the
alumina10 wt% tricalcium phosphatetitania composites at
1600 1C (74 MPa). Thus, the performances of the alumina
10 wt% tricalcium phosphate5 wt% titania composites are
higher than our value of the TCP40 wt% TiO2 composites
(Table 3). But, the low quantity of TCP (10 wt%) in the
aluminatricalcium phosphatetitania composites limits
their use in the biomedical applications (Sakka et al., 2014).
Generally, the discrepancy of the mechanical strength of
the samples may be due to the different processing parameters and the different mechanical modes other than the
Brazilian test used in the literature. Also, the wide variation
of the mechanical properties of the samples mentioned in the
literature is due to the use of different methods of preparation of powders and their different grain size.
In summary, this work proposes to study the effect of the
addition of titania on the mechanical properties of the
tricalcium phosphate. The optimum values of the mechanical
properties of the TCPTiO2 composites are reached at 1200 1C
with 40 wt% TiO2. Several examples of the mechanical properties (Vickers hardness, Young's modulus and shear mod-

ulus) of the bone tissues are shown in Table 4. The maximum

value of Vickers hardness of the -TCP40 wt% TiO2 composites reached 270 Hv. We notice that this value is between the
values of the dentin and the enamel (Table 4). The values of
the elastic modulus (E and G) of this study are close to the
bone tissues (Table 4). In fact, Young's modulus of the
composites obtained in the present work (33.1 GPa) is near
those of the thigh bone and cortical bone (Table 4).
At 1000 1C, the XRD analysis of the TCPTiO2 composites
shows that when the percentage of titania increases, it
promotes the presence of the anatase phase as majority peak
(Fig. 10d and e). At 1000 1C, the majority peaks are relative to
the rutile phase (Fig. 11be). The XRD analysis of the -TCP
sintered at various temperatures (1000 1C and 1200 1C) with
different percentages of the TiO2 (10 wt%, 20 wt%, 30 wt%,
40 wt% and 50 wt%) shows the formation of the CaTiO3 phase
traces (Figs. 10 and 11). Thus, the new peaks indicate the
interaction between the -TCP and TiO2. The substitution of
Ti4 by Ca2 leads probably to the formation of the CaTiO3
according to the following reaction:
Ca3 PO4 2 TiO2 -CaTiO3 Ca2 P2 O7

This result was previously conrmed by literature (Caroff

et al., 1998; Lee et al., 2006; Sprio et al., 2013). Also, the results
of the IR analysis and DTA analysis of the TCPTiO2 composites conrm those obtained by X-Ray diffraction.
The microstructure of the TCPTiO2 composites exhibited
considerable densication by the effect of the increase of the
temperature up to 1200 1C which improve also the mechanical property values. This result is due to the formation of the
liquid phase between TCP and TiO2 which leads to the

Table 3 Literature examples of the mechanical strength of the bioceramics and the bone tissues.
Materials

ra(MPa)

References

TCP
TCP33.16 wt% FAp
Al2O310 wt% TCP
Al2O310 wt% TCP5 wt% TiO2
TCP50 wt% ZrO2
TCP45 wt% ZrO210 wt% MgO
Dentin
Enamel
-TCP40 wt% TiO2

46
13.7
13.5
74
5.2
25
4555
812
33

Bouslama et al., 2009; Sakka et al., 2013

Bouslama et al., 2010
Sakka et al., 2014
Sakka et al., 2014
Sallemi et al., 2013
Sallemi et al., 2015
Hench, 1993; Elliott, 1994
Hench, 1993; Elliott, 1994
Present work

Mechanical strength.

Table 4 Literature examples of the mechanical properties of the bone tissues.

Materials

Ha (Hv)

Eb (GPa)

Gc (GPa)

References

Dentin
Enamel
Thigh bone
Cortical bone
Cancellous bone
-TCP40 wt% TiO2

4075
340370

270

18
82
20
725
0.050.5
33.1

15.7

Hench, 1993; Elliott, 1994; Chun et al., 2014

Hench, 1993; Elliott, 1994; Chun et al., 2014
Elliott, 1994; Ravaglioli and Krajewski, 1992; Shi, 2004
Elliott, 1994; Ravaglioli and Krajewski, 1992; Shi, 2004
Elliott, 1994 ; Ravaglioli and Krajewski, 1992; Shi, 2004
Present work

a
b
c

Vickers hardness.
Young's modulus.
Shear modulus.

journal of the mechanical behavior of biomedical materials 49 (2015) 129 140

detection of new phases CaTiO3 conrmed by the XRD

analysis. This result was previously conrmed by literature
(Caroff et al., 1998). They investigate the phase diagram of the
system TCPTiO2 proving the possibility of the presence of
the CaTiO3.
The produced TCPTiO2 composites with different percentages of titania exhibit much better performances than
reported values of TCP without titania. The optimum value
of the mechanical properties of the TCP40 wt% TiO2 composites was obtained at 1200 1C. This result is conrmed by the
SEM analysis. Thus, the microstructure of the TCPTiO2
composites sintered at 1200 1C showed a liquid-phase which
is formed between TCP and TiO2 and can be useful to cause a
higher mechanical properties through the transition from
solid-state sintering to liquid-phase sintering (Fig. 14). The
densication of samples is due to the transfer of mass in the
liquid-phase sintering (Fig. 14). The small amount of liquid in
the microstructure of the TCP40 wt% TiO2 composites helps
to ll the pores and consequently increase the mechanical
properties (Fig. 14c). The result was previously proven by the
literature (Sakka et al., 2014; Sallemi et al., 2015). However,
the liquid-phase sintering is an important method for the
industrial fabrication of many bioceramics. Moreover, the
liquid phase can allow enhanced densication and the
performances of the TCP40 wt% TiO2 composites at 1200 1C.
Generally, the determined values for the mechanical properties of our composites are not identical to those in Tables 3
and 4 because other authors have used different mechanical
tests. In addition, many factors inuence the mechanical
properties of the samples such as: the use of particular initial
powders as well as the conditions of the treatment process. In
conclusion, an interfacial reaction between -TCP and titania
has been studied in the nanocomposites of the TCP/TiO2
system. It was found that titania did not completely react
with -TCP. The mechanical characteristics should be taken
into consideration in order to better assess the relationship
between the processing conditions, the microstructural design
as well as the mechanical response.

5.

Conclusion

This study aimed at examining the effect of the TiO2 additive

on the densication and the mechanical properties of the -TCP
during the sintering process. The Brazilian test was used to
measure the rupture strength. Vickers hardness was assessed
by Vickers indentation. The ultrasound technique was used to
measure Young's modulus and the shear modulus. The DTA
analysis of the TCPTiO2 composites shows a new peak at
1440 1C which is probably attributed to the liquid phase formed
from the eutectic between TiO2 and TCP. Thus, the addition of
titania in the tricalcium phosphate matrix partially prevents the
inverse allotropic transformation of the tricalcium phosphate at
1100 1C. The mechanical properties of the TCPTiO2 composites
increase with the amount of TiO2 and the sintering temperature. Thus, the optimum values of the performances of the
composites are reached with 40 wt% TiO2 at 1200 1C. This result
is due to the presence of the liquid-phase which helps to ll the
pores in the microstructure of the composites. Above 40 wt%

139

TiO2, the mechanical properties are hindered by the exaggerated grain growth.

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