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Journal of the Mechanical Behavior of Biomedical Materials 72 (2017) 82–89

Contents lists available at ScienceDirect

Journal of the Mechanical Behavior of


Biomedical Materials
journal homepage: www.elsevier.com/locate/jmbbm

Al2O3-Ti functionally graded material prepared by spark plasma sintering MARK


for orthopaedic applications

Marjan Bahraminasaba, , S. Ghaffarib, Hossein Eslami-Shahedb
a
Department of Tissue Engineering and Applied Cell Sciences, School of Medicine, Semnan University of Medical Sciences, Semnan, Iran
b
Department of ceramics, Materials and Energy Research Center, P.O. Box 31787316, Karaj, Alborz, Iran

A R T I C L E I N F O A B S T R A C T

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.

1. Introduction health problems such as tissue blackening and metallosis


(Bahraminasab et al., 2010). The application of Ti-based alloys, there-
Fabrication of new biomaterials with improved physical, mechan- fore, has been avoided in the locations where the wear resistance is of
ical and biological properties is the main goal in biomaterials technol- vital importance such as femoral condyles and femoral head of total
ogy. Metallic biomaterials such as Ti-based alloys, stainless steel and knee and hip replacements, respectively.
Co-Cr-based alloys are extensively used in making orthopaedic pros- To overcome these weaknesses, one way is to combine dissimilar
theses for reconstructive surgery due to their superb mechanical materials to gain superior properties compared with the pure form of
properties. Ti-based materials have shown many advantages of low each material alone. This includes making ceramic–metal composites
density, high mechanical strength, moderate elastic modulus, adequate and functionally graded materials (FGMs). The most obvious advantage
corrosion resistance and good biocompatibility (Geetha et al., 2008). of these materials is that they can practically combine the different
Nevertheless, this material experiences excessive wear while it is characteristics of ceramic and metal constituents in a single material
rubbed against itself or other metals (Bahraminasab et al., 2012). Wear system. Ceramics such as alumina (Al2O3) provides negligible wear
and the successive osteolysis (loss of bone tissue) is one of the main debris and osteolysis which is attributable to the high hardness, low
leading causes of aseptic loosening in orthopaedic implants (Köse, friction coefficient and reduced wear rates (Chevalier and Gremillard,
2016) such as knee and hip replacements at medium or long term. In 2009). Furthermore, the corrosion resistance and stability in physiolo-
joint replacements where a metal or ceramic component articulates gical environments of this material can combine with high toughness
against a polymeric part (usually ultra-high molecular weight poly- and high strength of Ti to alleviate the existing concerns related to ion
ethylene or UHMWPE), osteolysis predominantly has been attributed to release from metallic parts of implants and the brittleness of bulk
the accumulation of UHMWPE debris and, to a smaller degree, metal or ceramic components (Bahraminasab et al., 2013). Alumina composites
ceramic wear particles (Chen and Thouas, 2015; Köse, 2016). However, with different reinforcing materials have been widely investigated in
the metallic wear particles released from Ti alloys leads to adverse the literature, among which some research dedicated on development


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

Titanium powder Alumina powder

Ball milling to provide different


mixture based on volume fraction of
layers

Filling the mould/Stacking different


mixtures in the mould sequentially

Spark plasma sintering

Samples

Fig. 1. Schematic of functionally graded specimen.


Evaluations

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.

Fig. 2. Spark plasma sintering machine.

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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)

Al2O3 3.96 3.98 19.76 294.55


75%Al2O3-25%Ti 3.94 4.11 11.47 172.97
50%Al2O3-50%Ti 4.25 4.24 10.38 164.28
25%Al2O3-75%Ti 4.48 4.37 10.12 149.98
Al2O3-Ti FGM 4.24 4.24 L1 L2 L3 L4 L5 81.5
8.73 10.52 10.75 10.99 12.20

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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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.

where σ is the bending strength, P represents the applied load and L, b,


and d stand for the gauge length, the width and the thickness of the test
3.2. Physical and mechanical characterization
specimen, correspondingly.
The densities of all sintered samples and the theoretical values are
3. Results and discussions demonstrated in Table 1. The results showed full dense components
ρ
except for 75%Al2O3-25%Ti whose relative density is 96% ( ρarch %)
theo
3.1. Phase and microstructural characterization which is still sufficiently high. The results indicated that increase of Ti
content causes increase in density of composite materials. This can be
The phases were studied using the XRD data obtained from starting confirmed by considering the higher density of Ti than Al2O3 and
powders and individual sintered composite pellets which were the increase of its volume fraction. The achieved densities of the composites
constituents of FGM layers. However, it was not viable to have XRD with 50% and 75% Ti were a little greater than the theoretical densities
analysis on the Al2O3-Ti FGM cross section. Fig. 4 shows the XRD obtained by Eq. (1). These differences can possibly be related to the
patterns of the raw powders and compares the X-ray reflections of formation of new phases during the SPS process.
sintered composite pellets. The XRD reflections of starting powders The hardness values of the fabricated composites and layers of FGM
match with those of Alumina and Ti. As it can be seen, in 75%Al2O3- decreased gradually with rise of Ti amount. Based on the rule of
25%Ti composite pellet, the intensity of Al2O3 peaks is prominent, mixture, Vikers hardness should decrease with increase of Ti volume
causing the Ti peaks to be of less intensity and in some angles become fraction. Similar trends for density and hardness was observed in
untraceable. However, by decreasing the Al2O3 content and increasing previous measurements (Gutierrez-Gonzalez et al., 2014; Hayun et al.,
the amount of Ti, the intensity of Al2O3 peaks reduce whereas the Ti 2015). However, the measured hardness here was lower than those
peaks become stronger. Furthermore, several additional peaks appear obtained in the earlier study, for example, the hardness of 75%Al2O3-
in the XRD patterns of the composite materials which are related to new 25%Ti composite was about 11.5 GPa which is lower than the hardness
phases of Ti3Al and TiAl. These peaks are more obvious in the value reported previously (about 15 GPa) for a composite of the same
composites with higher content of Ti. The new peaks (i.e. Ti3Al and composition (Gutierrez-Gonzalez et al., 2014). This difference is
TiAl) are corresponded to lightweight phases which resist to oxidation probably due to different powder particle size, temperature and

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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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(ΔL-t), its derivative ((ΔL/Δt)-t), temperature versus time (T-t), and


pressure versus time (P-t). These curves are shown in Fig. 10. The peak1
in Fig. 10c is known as apparent densification which is commonly
associated with compaction of the starting powder caused by applied
pressure. Here, the pressure was set to rise from 10 to 20 MPa after
3 min from the beginning of the SPS process, thus the first peak
appeared in 180 s and then gradually decreased, taking up to13min
(see Fig. 10c). The thermal induced densification of the FGM started
around 950 °C. The densification rate became supreme at about
1150 °C, the second peak in Fig. 10c. When holding at the sintering
temperature (1350 °C), the densification rate decreased, except for
when the pressure was increased to 40 MPa 13 min after starting the
process which is indicated by the red circle and arrow in Figs. 10c and
d. The densification rate reached zero after 5 min of soaking. However,
the full densification of the FGM sample was attained after extra 25 min
of soaking. Similar curves were observed in the previous studies for
composite materials (Meir et al., 2014; Meir et al., 2015), nevertheless
the shape of the peaks were different from each other and from those
obtained in the present study. The differences are likely due to the
different strategies in applying pressure, heating rate and the starting
raw powders. For example, in Meir et al. (2015) TiH2 was used to make
Al2O3-Ti composites, therefore release of hydrogen caused different
shape in peak one. We believe the layer nature of FGM sample also can
be influential.

4. Conclusion

Al2O3-Ti FGM and the corresponding composites of individual


layers were fabricated using spark plasma sintering at 1350 °C with
30 and 3 min of soaking time, respectively. Microstructural analysis
indicated that titanium and alumina particles were uniformly distrib-
Fig. 10. SPS parameters and densification of FGM sample as a function of process time (a) uted in the layers of FGM and the related composites. Meanwhile, good
temperature, (b) densification, (c) densification rate, and (d) applied pressure. (For adhesion of the FGM layers was observed. Hardness values and bending
interpretation of the references to color in this figure legend, the reader is referred to the
strength decreased monotonically with the amount of the titanium
web version of this article).
volume fraction. Separation of layers was not seen in the fracture
surface of FGM layers except very slightly for the layer containing
are depicted in Figs. 8 and 9. In all the composite pellets and layers, Ti
75%Ti and 100% Ti. The reason is possibly due to the formation of new
particles (brighter phase in SEM images) were mostly failed due to
brittle phases (Ti3Al and TiAl) in the layers with high titanium content.
cleavage (low-energy brittle fracture) provided river-like patterns in the
Furthermore, de-bonding of titanium and alumina phases in some
SEM micrographs (shown within rectangles in Figs. 9f and g). However,
regions might reflect the fact that the ceramic-metal interface may
some regions were possibly deformed plastically (indicated by black
require stronger anchorage. The bonding strength may be improved by
open-head arrows in Figs. 9f and g). In the composite materials and
preventing the massive formation of the brittle intermetallic com-
layers, the failure and separation of some metal-ceramic interfaces is
pounds at the interface, for example by use of additives or a titanium
visible which are identified by yellow filled-head arrows. Separations
compound instead of pure Ti as starting powder material.
are more obvious for composites with 50% and 75% ceramic content
This study is the initial investigation on Al2O3-Ti FGM which
(see Fig. 8). These findings are in agreement with Gutierrez-Gonzalez
provides a basis for more research to be done on enhancement of such
et al. (2014) who developed 25%Ti-75%Al2O3 composite and found
FGM properties. Our future work will concentrate on the optimal
that plastic deformation of Ti is difficult to take place, therefore the
composition of the layers with more focus on mechanical and biological
metallic particles act as elastic bridges which fail when the cracks
properties. It would be also interesting to study the sensitivity of the
propagate. However, the bonding strength between Ti and Al2O3 may
material properties to applied pressure and holding time near those of
be enhanced by preventing the large formation of the brittle inter-
this study.
metallic compounds at the interface, for example by use of additives or
The potential application of Al2O3-Ti composites and their func-
a titanium compound e.g. TiH2 instead of pure Ti as starting powder
tionally graded material can be as bone substitute materials and in the
material (Wu et al., 2014; Hayun et al., 2015; Meir et al., 2015). In the
components of prostheses of load-bearing such as knee and hip
FGM sample, however, the same mechanism of failure was seen
implants. However, to manufacture actual components of these load-
between the two phases, de-bonding and separation of successive layers
bearing prostheses, higher strength may require which might be
was not observed (see Fig. 9b-d) except for some small region of L2-L1
achieved either by applying higher pressure during manufacture
interface (see Fig. 9e). This also may be due to the formation of new
process or by using Ti-based alloys.
phases with low ductility (Ti3Al and TiAl) in the layers with high
titanium content as observed in XRD pattern.

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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