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Influence of Magnesium Doping in Hydroxyapatite Ceramics
C. Y. Tan1, K. L. Aw2, S. Ramesh2 and M. Hamdi1
Faculty of Engineering, University Malaya, 50603 Kuala Lumpur, Malaysia Ceramics Technology Laboratory, University Tenaga Nasional, Selangor, Malaysia
Abstract—The sinterability of magnesium oxide (MgO) doped hydroxyapatite (HA) ranging from 0.05 to 1 wt% was investigated. Green samples were prepared and sintered in air at temperatures ranging from 1000°C to 1400°C. Sintered bodies were characterized to determine the phase stability, bulk density, hardness, fracture toughness and Young’s modulus. XRD analysis revealed that the HA phase stability was not disrupted throughout the sintering regime employed. In general, samples containing 1 wt% MgO and when sintered at lower temperatures possessed better mechanical properties than the undoped HA. The study revealed that all HA samples achieved > 98% relative density when sintered between 1050ºC–1300ºC. The addition of 1 wt% MgO when sintered at 1150°C was found to be most beneficial throughout the studied range as the samples exhibited the highest Young’s modulus of 136.3 GPa, Vickers’s hardness of 7.66 GPa and fracture toughness of 1.48 MPam1/2 as compared to 113.57 GPa, 7.10 GPa and 1.08 MPam1/2 for the undoped HA. Keywords— hydroxyapatite, magnesium oxide, bioceramics, sinterability, mechanical properties
I. INTRODUCTION As reviewed by Suchanek et al. , hydroxyapatite ceramic, HA [(Ca10(PO4)6(OH)2] has been identified as one of the most suitable biomaterial for medical implants due to its close chemical resemblance with the mineral components and crystal structure to apatite in human skeletal system of natural bone and teeth. Moreover, its identical calcium to phosphorus ratio to natural bone promotes strong bonding between bony tissues and the implant surface . In addition to that, evidence of rapid bone formation in the HA implant and subsequent healing around the damaged sites in the body were also observed, thus demonstrating its potency as a viable biomaterial for clinical usage . The applicability of HA as a biomaterial in clinical orthopaedic and dental applications, nevertheless, is limited to only non-stressed loaded regions owning to the brittle nature and the low fracture toughness (0.8-1.2 MPam1/2) of the bioceramic . Thus, the development of bioactive HA that has enhanced mechanical properties coupled with excellent biocompatibility are desirable. As a result, various studies ranging from powder processing techniques, composition and experimental conditions are carried out with the aim of determining the most effective synthesis method and
conditions to produce improved mechanical properties of sintered HA accompanied with superior biocompatibility with hard tissues . Suchanek et al.  found that HA composites, particularly with HA/HA whiskers, could improve the reliability of HA ceramics. However, the authors had also revealed the difficulty in densifying the HA-based composites by pressureless sintering. This problem associated with powder consolidation could be overcome by using other techniques such as hot pressing  and hot isostatic pressing  at the expense of high set-up as well as running cost. An alternative economical technique to obtain highly dense HA body is by incorporating appropriate lowtemperature sintering additives . Various attempts have been carried out in hope to enhance the mechanical properties of HA and biocompatibility through the incorporation of sintering additives such as zirconia, ceria and iron [9-11]. Among these additives, the inclusion of magnesium oxide on HA ceramics has not been studied extensively. Therefore, the primary objective of the present work was to study the phase stability and sinterability of synthesized HA ceramics by wet precipitation method when doped with up to 1 wt% magnesium oxide (MgO). II. METHODS & MATERIALS The HA powder used in the present work was prepared according to a novel wet chemical method comprising precipitation from aqueous medium involving calcium hydroxide and orthophosphoric acid . In the current work, up to 1 wt% MgO was mixed into HA powder by wet milling. After the mixing, the wet slurry was dried, crushed and sieved to obtain fine powder. The green samples were uniaxial compacted at about 1.3 MPa to 2.5 MPa into rectangular bar (4 x 13 x 32 mm) and circular discs (20 mm diameter) samples. The green compacts were subsequently cold isostatically pressed at a pressure of 200 MPa (Riken Seiki, Japan). This was followed by consolidation of the particles by pressureless sintering performed in air using a rapid heating furnace (ModuTemp, Australia), over the temperature range of 1000ºC to 1400ºC, with ramp rate of 2oC/min. (heating and cooling) and soaking time of 2 hours for each firing. All sintered samples were then polished to a 1 µm finish prior to testing. The phases present in the powders and sintered samples were determined using X-Ray diffrac-
tion (XRD) (Geiger-Flex, Rigaku Japan). The bulk densities of the compacts were determined by the water immersion technique (Mettler Toledo, Switzerland). The Young’s modulus (E) by sonic resonance was determined for rectangular samples using a commercial testing instrument (GrindoSonic: MK5 “Industrial”, Belgium). The modulus of elasticity or Young’s modulus was calculated using the experimentally determined resonant frequency . The microhardness (Hv) and fracture toughness (KIc) of the samples were determined using the Vickers indentation method (Matsuzawa, Japan). The indentation load (< 200 g) was applied and held in place for 10 seconds. Five indentations were made for each sample and the average value was taken. The KIc value was calculated using the equation derived by Niihara . III. RESULTS & DISCUSSION The sinterability of the HA powder were compared in terms of HA phase stability, relative density, Vickers hardness, fracture toughness, grain size measurement and Young’s modulus. All the samples, regardless of sintering conditions, did not show any cracking or distortion after sintering. The XRD traces indicate that the sintering of MgO-doped and undoped HA samples did not result in the formation of secondary phases throughout the sintering regime employed as typically shown in Figure 1.
sintered at 1400ºC and thus contradicted the findings of Royer et al.  and Wang et al. . In general, sintering of HA can lead to the partial thermal decomposition of HA into tricalcium phosphate (TCP) and/or tetracalcium phosphate (TTCP) . The thermal decomposition is normally accompanied in two steps i.e. dehydroxylation and decomposition. Dehydroxylation to oxyhydroxyapatite proceeds at temperatures about 850ºC to 900ºC by the fully reversible reaction in accordance to equation 1 : Ca10(PO4)6(OH)2 → Ca10(PO4)6(OH)2-2xOx + xH2Ogas (1)
The decomposition to TCP and TTCP occurs at temperatures greater than 900ºC according to the reaction given in equation 2 : Ca10(PO4)6(OH)2 → 2Ca3(PO4)2 + Ca4P2O9 + H2Ogas (2)
According to these equations, both the dehydroxylation and decomposition reactions include water vapour as a product. The rates at which these reactions proceed depend on the partial pressure of H2O in the furnace atmosphere . Therefore, the secondary phase formation during sintering could be suppressed by controlling the moisture content in the sintering atmosphere. The high moisture content present in the sintering atmosphere has the tendency to slow down the decomposition rate by preventing the dehydration of the OH group from the HA matrix. The difference in result in the present work with Royer et al. and Wang et al. could in part be attributed to the difference in relatively humidity in the sintering atmosphere and also the nature of the starting synthesized powder. The densification curves as a function of sintering temperatures is shown in Figure 2.
increasing dopant f e d c b a
Bulk Density (Mgm-3) 3.120
0.05 wt% Mg 0.1 wt% Mg 0.3 wt% Mg
Fig. 1 XRD patterns of HA samples sintered at 1400ºC showing no signs of HA decomposition. (a) undoped HA and HA containing (b) 0.05 wt%, (c) 0.1 wt%, (d) 0.3 wt%, (e) 0.5 wt% and (f) 1 wt% MgO, respectively.
0.5 wt% Mg 1 wt% Mg
The XRD results indicated that the phase stability of HA was not disrupted by the sintering schedule and temperature, pressing conditions prior to sintering as well as the dopant addition. Sintering at high temperatures, above 1300ºC, has been reported in the literature to be detrimental as HA phase instability was observed. However, in the present work, decomposition of HA phase was not observed even when
Sintering Temperature (ºC)
Fig. 2 Bulk density variation as a function of sintering temperatures for
In general, the bulk density variation of all the composition studied exhibited a similar trend with increasing sin-
tering temperature. A general observation that can be made from Figure 2 is that the dopant incorporated has marginal effect on the measured bulk density of HA samples. All the samples attained above 98% of theoretical density when sintered above 1050ºC. The relationship between the Young’s modulus of the sintered body, sintering temperature and MgO additions are shown in Figure 3. In general, the inclusion of MgO in HA lattice, particularly for the higher dopant concentration, was found to be beneficial in enhancing the stiffness of the sintered HA body. As shown in Figure 3, the highest value of 136.3 GPa is recorded for HA samples containing 1wt% MgO and when sintered at 1150ºC.
140 135 130 Young's Modulus (GPa) a 125 120 115 110 105 100 95 90 1000 1050 1100 1150 1200 1250 1300 1350 1400 Sintering Temperature (ºC) 0 0.1 wt% Mg 0.5 wt% Mg 0.05 wt% Mg 0.3 wt% Mg 1 wt% Mg
The beneficial effect of MgO especially for the 1 wt% addition in enhancing the hardness and toughness of HA has been revealed. A general observation that can be made from Figure 4 is that the measured hardness of all the samples revealed a similar trend, i.e. the hardness increased rapidly to a maximum value and then decreased slowly with increasing sintering temperatures. For example, the hardness of the undoped HA ceramic peaked at 1050ºC (7.23GPa) and further increase in temperature > 1050oC resulted in a decrease in the hardness. The results also revealed that the addition of 1 wt% MgO was beneficial as samples exhibited higher hardness value in the sintering regime employed as compared to undoped HA. Throughout the studied range, the highest hardness value of 7.66GPa is obtained for HA doped with 1 wt% MgO and when sintered at 1150ºC.
1.8 5 1.7 5 1.6 5 1.5 5 1.4 5 1.3 5 1.2 5 1.15 1.0 5 0 .9 5 0 .8 5 0 .7 5 10 0 0 10 5 0 110 0 115 0 12 0 0 12 5 0 13 0 0 13 5 0 14 0 0 S in t e rin g T e m p e ra t u re ( º C )
0 0 .0 5 wt % M g 0 .1 wt % M g 0 .3 wt % M g 0 .5 wt % M g 1 wt % M g
Fig. 3 The effect of MgO and sintering temperatures on the Young’s
modulus of HA
Fig. 5 The effect of MgO addition on the fracture toughness of HA. Generally, the fracture toughness of all compositions exhibited very similar trend as the sintering temperature increased. Further analysis indicates that this trend is in good agreement with the variation in Vickers hardness as described earlier. The results also show that the addition of MgO was effective in enhancing the fracture toughness (KIc) of the synthesized HA, particularly when sintered at 1150ºC. The 1 wt% MgO-doped HA samples exhibited the highest fracture toughness of 1.48 ± 0.17 MPam1/2 as compared to 1.28 ± 0.05 MPam1/2 measured for the undoped HA. It should be highlighted here that the KIc value obtained for the MgO-doped HA is very encouraging, as most researchers had reported that the experimental KIc values for HA varied from 0.9 MPam1/2 to about 1.2 MPam1/2 [18, 19]. IV. CONCLUSIONS The present research demonstrated that the additions of small amount of magnesium oxide can be beneficial in
The variation of the average Vickers hardness and fracture toughness of samples sintered at various temperatures is shown in Figure 4 and Figure 5, respectively.
7 Vicker's Hardness (GPa) a
0 0.05 wt% Mg 0.1 wt% Mg 0.3 wt% Mg 0.5 wt% Mg 1 wt% Mg
1050 1100 1150 1200 1250 1300 1350 1400
2 1000 Sintering Temperature (ºC)
Fig. 4 Effect of sintering temperature and MgO addition on the Vickers
hardness of HA.
enhancing the mechanical properties without affecting the HA phase stability even when sintered at 1400ºC. MgO additions, however was found to have a marginal effect on the bulk density of sintered HA regardless of the sintering temperature employed. The addition of 1 wt% MgO and when sintered at 1150°C was found to be most beneficial as the HA samples exhibited the highest Young’s modulus of 136.3 GPa, hardness of 7.66 GPa and fracture toughness of 1.48 MPam1/2
The authors gratefully acknowledge the support provided by Universiti Malaya, UNITEN and SIRIM Berhad.
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