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Keywords: Orthopaedic prostheses still suffer from limited lifetime which imposes revision surgery with the associated risks
Layered material structure involved. This, to some extent, is related to the vulnerability of the biomaterials used for their fabrication that
Spark plasma sintering are commonly single-constituent and uniform. Therefore, hybrid biomaterials such as composites and
Orthopaedic implants functionally graded materials (FGMs) are being developed to overcome the shortcomings of available
Sintering behaviour
biomaterials. The present paper focuses on the study of the structural, physical and mechanical properties of
Mechanical properties
a FGM made of alumina–titanium fabricated by spark plasma sintering (SPS). The corresponding composites of
the individual FGM layer were also fabricated. After sintering, the structural, mechanical and physical tests were
carried out. The microstructural analysis using X-ray diffraction revealed the presence of Ti3Al and TiAl in the
composites, particularly with the increase of titanium content. Scanning electron micrographs revealed good
adhesion and bonding between the two phases and between the FGM layers. The hardness and bending strength
of the composites and FGM samples were tested and it was found that the increase in amount of Ti volume
fraction decreases these properties monotonically. Furthermore, the sintering behaviour and fracture mechan-
isms of the FGM sample were studied and discussed.
⁎
Corresponding author.
E-mail address: m.bahraminasab@yahoo.com (M. Bahraminasab).
http://dx.doi.org/10.1016/j.jmbbm.2017.04.024
Received 10 February 2017; Received in revised form 22 April 2017; Accepted 25 April 2017
Available online 26 April 2017
1751-6161/ © 2017 Elsevier Ltd. All rights reserved.
M. Bahraminasab et al. Journal of the Mechanical Behavior of Biomedical Materials 72 (2017) 82–89
Samples
of alumina-titanium composites (Braichotte and Cizeron, 1989; Peytour Physical properties Mechanical properties
et al., 1990; Ji et al., 1995; Lu et al., 1995; Günther et al., 2001; Wang
et al., 2003; Zhi et al., 2005; Gutierrez-Gonzalez et al., 2014; Guzman Structural analyses Fracture mechanisms
et al., 2016; Hayun et al., 2015; Meir et al., 2015; Xu et al. 2016). In
Sintering behaviour
recent years, several studies have focused on development of Al2O3-Ti
composites with different volume fractions by Spark Plasma Sintering
(SPS) (Wang et al., 2003; Zhi et al., 2005; Gutierrez-Gonzalez et al., Fig. 3. General steps for development of FGM and composite samples.
2014; Guzman et al., 2016; Hayun et al., 2015; Meir et al., 2015). SPS
offers the advantages of higher heating rates, high relative densities
achievable in very short time, and sintering of nano-sized particles
without substantial grain growth. This technology also has been used to
build up functionally graded materials with compositional or structural
variation; some investigations are (Jajarmi et al., 2016; Park et al.,
2016; Fujii et al., 2017). FGMs are a class of advanced composites
developed in a way to have gradient changes in the properties e.g.
elastic modulus (Askari et al., 2012; Oshkour et al., 2015). This happens
by using two or more different constituents whose volume fraction
gradually changes along a gradient direction. FGMs due to the
heterogeneous structure can use the advantage of the pure form of
each constituent, thus the compromise between the properties, which
usually occurs in homogeneous composites, is eradicated. Some of the
orthopaedic FGMs fabricated by SPS include Hydroxyapatite-yttria
stabilized tetragonal zirconia (Guo et al., 2003), and Hydroxyapatite- Fig. 4. XRD patterns of starting powders and sintered composite pellets, peaks.
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M. Bahraminasab et al. Journal of the Mechanical Behavior of Biomedical Materials 72 (2017) 82–89
Table 1
Comparison of physical and mechanical properties obtained for Alumina and FGM.
Specimen Measured density (g/cc) Theoretical density (g/cc) Hardness (GPa) Bending strength (MPa)
Fig. 5. SEM images of (a) 75%Al2O3-25%Ti, (c) 50%Al2O3-50%Ti, and (d) 25%Al2O3-75%Ti.
Al2O3-yttria stabilized zirconia (Afzal et al., 2012) and micro-/nano- time (3, 5 and 15 min) were also tested particularly for FGM. These
grain functionally graded hydroxyapatite bioceramics (Zhou et al., processing conditions did not approach us to acceptable mechanical
2015). To the best of the authors’ knowledge, Al2O3-Ti functionally and physical properties. However, it was found that increase of pressure
graded materials have not been investigated in the literature. In this and maintaining time provide better properties. Therefore, the applied
context, the present paper aimed at developing this material by SPS condition, here, was chosen based on the properties obtained. Recently,
technology and evaluating the structural, physical and mechanical a similar approach was used to manufacture Ti- Al2O3 composite as well
properties, for possible application in orthopaedic implants. (Meir et al., 2015). Fig. 3 shows the general steps for manufacture of
FGM and composites.
2. Materials and methods
2.1. Phase and microstructural characterization
The raw powder of α-Al2O3 with a purity of 99.8% and particle size
distribution of 0.1–3 µm was used along with Titanium powder of >
X-ray diffraction (XRD) technique was used for the phase analysis
98% purity sieved to have particle size of < 45 µm (mesh: 325). The
using Cu Kα radiation (λ=1.5405980 Å) and scanning angle (2θ)
powders with various Al2O3 and Ti ratios (volume fraction percentages)
ranged between 5° and 85° (Philips PW 3710). XRD analysis was
were initially ball milled (PM400, Retsch, Germany) using zirconia jar
performed on the raw powders of Ti and Al2O3, and on the individual
and balls at a speed of 100 rpm for 1 h and with a ball to powder ratio
composite pellets after sintering. However, XRD was not feasible to be
of 5:1 to provide mixtures for the layers of functionally graded material
conducted on the individual layers of FGM sample. Microstructure
(see Fig. 1).
analysis was carried out on the surface of the composite samples, along
Al2O3-Ti FGM, composites of the three layers (L2, L3 and L4) and a
the height of the FGM to observe the layers, and along the cross sections
pure Al2O3 samples were fabricated by Spark Plasma Sintering (SPS-
of all fractured samples (after three-point bending test) by scanning
20T-10, Easy Fashion Metal Products Trade CO. Ltd. China). Fig. 2
electron microscopy (SEM). Several images were also taken from the
shows the schematic of SPS apparatus and the machine used in this
interface of the two phases in the composites and FGM to check the
study. To fabricate FGM sample, first, the powder mixtures of Al2O3-Ti
bonding and possible existence of micro-cracks. The Energy Dispersive
ratios were inserted into graphite die (diameter of 30 mm) one by one
Spectroscopy (EDS) was also employed to conduct the elemental
to provide the layers. The walls of the die were covered by graphite
analysis of the FGM sample using the same SEM machine (TESCAN
sheet to avoid adhere of sample to the die. For all sample, the pressure
MIRA3 LMU).
of 10 MPa was applied at the beginning of the process and maintained
for three minutes. Then, the applied pressure was increased to 20 MPa
and held for the next ten minutes. Finally, at the end of thirteen 2.2. Physical and mechanical characterization
minutes, the pressure was set to be 40 MPa until the end of the SPS
process. The powders were sintered at 1350 °C under a vacuum below The densities of the composites, FGM and Al2O3 samples were
20 Pa by heating rate of 50–100 °C/min. The holding time at 1350 °C measured by the Archimedes’ method in water as the immersion
was 3 min for the composites and it was 30 min for the FGM and pure medium. Furthermore, the theoretical density of composites and FGM
Al2O3 samples. These conditions were chosen based on Ti melting point were estimated by Eqs. (1) and (2) respectively, for comparison. Where
(1668 °C) and Al2O3 sintering temperature (1500 °C in vacuum induc- Vt is the total volume of the sample, and ρ1 to ρ5 and V1 to V5 are the
tion furnace) to facilitate the densification of both constituents in the density and volume of layers 1–5, respectively. ρ2 to ρ4 were also
powder mixture under vacuum environment. Furthermore, other con- obtained by the volume fraction and rule of mixtures for composite
ditions of different applied pressure (10 MPa, 20 MPa) and maintaining materials (Eq. (2)).
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M. Bahraminasab et al. Journal of the Mechanical Behavior of Biomedical Materials 72 (2017) 82–89
Fig. 6. SEM images of the fabricated FGM (a) layers, (b) interface of L1-L2, (c) interface of L2-L3, (d) interface of L3-L4, and (e) interface of L4-L5.
ρtheo, composite = υTi × ρTi + υAl 2O3 × ρAl 2O3 (1) Vickers hardness test was performed on the polished surfaces (down
to 1 μm) of the sintered specimens using a micro Vicker's hardness
1 tester (MVK-H11, AKASHI, Japan) in which the pyramid-shaped
ρtheo, FGM = ( ρ1 × V1 + ρ2 × V2+⋯+ ρ5 × V5)
Vt (2)
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M. Bahraminasab et al. Journal of the Mechanical Behavior of Biomedical Materials 72 (2017) 82–89
Fig. 7. Micrographs of SEM and EDS analysis for Al2O3-Ti FGM. (For interpretation of the references to color in this figure, the reader is referred to the web version of this article).
however they have low ductility and may degrade the composite
strength (see Table 1, bending strength).
Figs. 5 and 6 represent the SEM microstructures of the sintered
composite pellets and the FGM. In these figures the darker phase is
Al2O3 and the brighter phase is Ti. As it can be seen in these images, the
two constituents homogeneously dispersed throughout the composite
materials and the FGM layers. In the composite with 25% Ti and in the
Al2O3-rich region of FGM, there was a dispersive microstructure of Ti
particles in the Al2O3 matrix (Fig. 5a). However, when the Ti volume
fraction rose to 50% and 75%, the microstructure changed and a typical
network structure was observed (Figs. 5b and c). The images from
Al2O3-Ti interface also showed well bonding and no micro-cracks
between the two phases. The cross-sectional images of the FGM sample
Fig. 8. SEM images of the fracture surface for (a) 50%Ti-50%Al2O3, (b) 25%Ti-75%Al2O3
composites.
and its layers’ interfaces (Fig. 6), showed the adherence of the layers
and absence of micro-cracking at the layers’ interfaces. It seems the
diamond indenter was used at a constant load of 3 N for 15 s. Three layers are compatible with each other and resist the stresses that might
indentations were applied on the surface of composite and Al2O3 generate due the mismatch of the coefficient of thermal expansion.
samples and along the layers of FGM. For three-point bending test, Fig. 7 shows the SEM image of the Al2O3-Ti FGM sample along with
the samples were cut into plain rectangular cross-section beams to have the EDS spectra. In these images, the red, green and yellow colours
gauge length of 14 mm (two samples for each materials). Based on the represent the concentration of Ti, Al and O respectively. The graded
forces caused specimens fracture, the bending strength was estimated structure of different compositions can be seen, where the Ti content
by Eq. (3). gradually increases from left to right of the micrograph. As it can be
observed from the image, the Al2O3 powders very slightly diffused in
3PL the 100% Ti layer probably due to the long maintaining time at
σ=
2bd 2 (3) 1350 °C.
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Fig. 9. SEM images of the fracture of (a) Ti-Al2O3 FGM, (b) L5-L4, (c) L4-L3, (d) L3-L2, (e) L2-L1, (f) Ti-Al2O3 particles and (g) 100%Ti layer.
pressure applied. The bending strength values in Table 1 show the value yttria stabilized tetragonal zirconia FGM at different sintering tempera-
of 294.55 MPa for pure alumina sample which decreases with increase tures. Furthermore, Yang et al. (2014) reported a value in the range of
of Ti, such that it reaches around 150 MPa for 75%Ti content. In fact, 90–100 MPa bending strength for FeCrAl (f)-HA functionally graded
the increment of the second phase into the alumina causes 58.7%, materials. Therefore, the prepared Al2O3-Ti FGM might be suitable for
55.8% and 50.9% of bending strength of the pure alumina respectively bone substitute. Nonetheless, use of this material for actual components
for 25%, 50% and 75% Ti. Gutierrez-Gonzalez et al. (2014) also of load-bearing prostheses may require more research to be done on the
obtained the same reduction percentages in bending strength for strength. One way to achieve this maybe use of a Ti-based alloys instead
composite with 25% Ti, however the values are different. The bending of Ti such as Ti-6Al-4V with approximately two-fold ultimate tensile
strength of FGM sample was about 81.5 Mpa. Nevertheless, this value is strength. The other approach to gain stronger components is to apply
much lower than pure alumina, but still in the range of human bone higher pressure during manufacturing process as the previous studies
flexural strength that was reported to be from < 50 MPa (around applied more pressure and attained higher strength in Al2O3-Ti
25 MPa) to around 300 MPa depending on the porosity value or composites (Gutierrez-Gonzalez et al., 2014; Meir et al., 2015).
calcium content (Currey, 1999). The bending strength of most FGM
developed for orthopaedic applications lie in this range. For example, 3.3. Fracture mechanisms of FGM sample
Chu et al. (2001) could obtain bending strength of 158.9 MPa for HA-
Ti/Ti/Ti-HA symmetrical FGM. In another study, Guo et al. (2003) The fracture mechanisms of the composite and FGM samples were
gained the bending strength of 160–210 MPa for hydroxyapatite (HA)- analysed by SEM image on the fractured surface of the samples which
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4. Conclusion
Acknowledgment
3.4. Sintering behaviour of FGM sample
The authors would like to thank Iran National Science Foundation:
The consolidation of the FGM sample during the SPS process was INSF (NO. 94011309) for funding this work.
assessed considering the curves of punches displacement versus time
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