ICCBT2008

Consolidation of Nanocrystalline Hydroxyapatite Powder for Medical Applications

K. L. Aw, Universiti Tenaga Nasional, MALAYSIA W. H. Yeo, Universiti Tenaga Nasional, MALAYSIA C. Y. Tan, Universiti Tenaga Nasional, MALAYSIA S. Ramesh*, Universiti Tenaga Nasional, MALAYSIA I. Sopyan, International Islamic University Malaysia, MALAYSIA M. Hamdi, University of Malaya, MALAYSIA

ABSTRACT The sinterability of synthesized nanocrystalline hydroxyapatite (HA) due to the effect of sintering temperature was investigated. The starting powders synthesis method is a novel wet chemical route and HA green compacts prepared from this powder are sintered at various temperatures in atmospheric condition. It was found that at high sintering temperatures, decomposition of HA phase did not occur. The results shows that the relative density increases to above 98% while the Youngs modulus increases to above 110 GPa when sintered above temperature of 1050oC. However, the hardness and the fracture toughness shows decline when temperature was increased beyond 1000oC. This occurrence is associated with the thermal-activated grain growth process. Keywords: Hydroxyapatite, Sinterability, Mechanical Properties

*Correspondence Author: Assoc. Prof. Ir. Dr. Ramesh Singh, Universiti Tenaga Nasional, Malaysia. Tel: +60389287282, Fax: +60389212116, E-mail: ramesh@uniten.edu.my

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1.

INTRODUCTION

Hydroxyapatite (HA) with a chemical formula of Ca10(PO4)6(OH)2, has a composition close to humans natural bone and teeth [1,2]. HA is bioactive, biocompatible and also exhibits osteoconductive behavior while showing stability against bioabsorption [2-5]. Due to these properties, HA is considered as one of the important biomaterials and is widely used in medical and dental applications such as dental implants, alveolar bridge augmentation, orthopedics, maxillofacial surgery and drug delivery systems [1,5]. However, pure HA is known to have poor mechanical strength, fracture toughness and also brittle, which limits its application usage to non-loading applications [1,3,4]. Many researches have been done to synthesize HA using various methods such as the solgel, homogeneous precipitation, hydrothermal, mechno-chemical, RF plasma spray, spray dry, combustion synthesis, supersonic rectangular jet impingement and ultrasonic spray freezedrying [5]. Although numerous studies on HA synthesized via wet precipitation technique are carried out, nevertheless, reports on the sinterability of HA synthesized through this technique are rather scarce. Therefore, in this work, a novel wet chemical technique was employed to manufacture nanocrystalline HA powder using high purity Ca2+ precursor. The sinterability and properties of the sintered product derived from these powders were evaluated.

2.

METHODS AND MATERIALS

The HA powder used in the present work was synthesized using a novel wet chemical method [6]. The morphology of the synthesized HA particles were examined using Transmission Electron Microscope (TEM) at IMAGE, University of Southern Illinois USA. Prior to examination, the powder was suspended in 1-2 ml of spectroscopic grade acetone (or double distilled water), agitated by pipette and, after allowing the largest granules to settle, approximately 50 microliters of the smaller particles were transferred to a 200 mesh nickel grid coated with a silicon monoxide film. Microscopy was carried out in a Hitachi H7100FA TEM operating at accelerating voltages of 100-125 kV. A calibration sample (MAG*I*CAL, Norrox Scientific Ltd.) was used to produce the magnification scales in the micrographs. Images were captured directly in the TEM using a Gatan 789 camera system. The as-prepared, nanocrystalline HA powder was uniaxially compacted at about 1.3 MPa to 2.5 MPa into rectangular and circular discs samples. The green compacts were subsequently cold isostatically pressed at 200 MPa. Consolidation of the particles by pressureless sintering was performed in air using a rapid heating furnace (ModuTemp, Australia), at various temperatures ranging from 900C to 1300C, maintained at the soak temperature for 2 hours before cooling to room temperature. All the sintered samples were subsequently polished to a 1 m mirror finish prior to evaluation. The nature of the crystalline phases in the powder and sintered body were examined by X-ray diffraction (XRD; Rigaku Geiger-Flex Japan) under ambient conditions using Cu-K as the radiation source. The peaks obtained were compared to standard reference JCPDS files available in the software for HA (No. 09-0432), -TCP (No. 09-0348), -TCP (No. 09-0169) and TTCP (No. 25-1137).
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The bulk density of the sintered samples was measured by Archimedes method, with distilled water as the immersion media. The relative density was calculated by taking the theoretical density of HA as 3.156 gcm-3. The Youngs modulus (E) by sonic resonance was determined for rectangular samples using a commercial testing instrument (GrindoSonic: MK5 Industrial, Belgium). The instrument permits determination of the resonant frequency of a sample by monitoring and evaluating the vibrational harmonics of the sample by a transducer; the vibrations are physically induced in the sample by tapping. The modulus of elasticity or Youngs modulus was calculated using the experimentally determined resonant frequency [7]. The microstructural evolution of the HA under various sintering temperature was examined by using a Philips XL30 Scanning Electron Microscope (SEM) and the grain size was determined from SEM micrographs using the line intercept analysis [8]. The microhardness (Hv) and fracture toughness (KIc) of the polished samples were determined using the Vickers indentation method. Five indentations were made for each sample and the average value was taken. The indentation fracture toughness was determined from the equation derived by Niihara [9].

3.

RESULTS AND DISCUSSION

The XRD analysis of the synthesized powder in this study as shown in Fig. 1 exhibited peaks that corresponded to stoichiometric HA. Thus, it is evident that the filtered crystals were mainly single-phase HA and is believed to be very small. Estimates of crystal size from peak broadening using the Scherrers formula [19] for the synthesized powder gives about 11 nm from the (2 1 1) reflection and about 30 nm from the (0 0 2) reflection.

Figure 1. Room temperature XRD signatures of nanocrystalline HA powder. All peaks corresponded to stoichiometric HA phase. The nanocrystalline nature of the derived powder was also confirmed by TEM as shown in Fig. 2. This result correlates well with the XRD analysis, which revealed that the particles were very small i.e. in the nanometer size range. In addition to that, the XRD analysis of all the sintered samples, regardless of sintering temperature ranging from 900C to 1300C, produced only peaks that corresponded to stoichiometric HA as shown in Fig. 3. This result indicates that HA did not decompose to secondary phases upon sintering even when

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consolidated at high temperature above 1200C. A similar result was also obtained in previous work even for sintering at high temperature of 1400C [20].

Figure 2. TEM micrograph of nanocrystalline HA particles derived in the present work.

Figure 3. Typical XRD patterns of HA sintered at 900-1300C revealing the presence of HA phase. The traces are superimposed on each other. The fact that decomposition of HA phase was not observed in the present material even for the high temperature (i.e. 1200C) sintered samples is not in agreement with the findings of Royer et al. [21] and Wang et al. [22] who reported that decomposition of HA starts at about 1300C, accompanied by deterioration of mechanical properties of HA ceramics. In general, sintering of HA can lead to the partial thermal decomposition of HA into tricalcium phosphate (TCP) and/or tetracalcium phosphate (TTCP) [23]. The thermal decomposition is accompanied in two steps i.e. dehydroxylation and decomposition. Dehydroxylation to oxyhydroxyapatite proceeds at temperatures about 850C to 900C by the fully reversible reaction in accordance to equation 1 [23]: (1) Ca10(PO4)6(OH)2 Ca10(PO4)6(OH)2-2xOx + xH2Ogas The decomposition to TCP and TTCP occurs at temperatures greater than 900C according to the reaction given in equation 2 [23]: Ca10(PO4)6(OH)2 2Ca3(PO4)2 + Ca4P2O9 + H2Ogas (2)

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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 [23]. 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 effect of sintering temperature on the relative density of HA is shown in Fig. 4. The maximum relative density of 99% was attained for sample sintered at 1150C. In general, the relative density increases rapidly from 83% at 900C to 97% at 1000C and then increase monotonically to > 98% for sintering 1050C. Thereafter, the bulk density did not change very much with increasing temperature up to 1300C. This could be associated with the final stages of sintering where small levels of porosity are removed.
100 Relative Density (%) a 98 96 94 92 90 88 86 84 82 850 950 1050 1150 1250 1350

Sintering Tem perature (C)

Figure 4. Bulk density variation as a function of sintering temperature. The variation in Youngs modulus (E) for the HA with sintering temperature is in agreement with the bulk density trend. The HA attained E values 100 GPa when sintered at a temperature as low as 1000C as shown in Fig. 5. Attempts to correlate the Youngs modulus with bulk density revealed a definite relationship exist as shown in Fig. 6. It was found that Youngs modulus of the sintered HA increased linearly up to a maximum of > 100 GPa with increasing bulk density up to > 98% of theoretical value. This result is in agreement with the work of Liu who observed that the Youngs modulus of HA was controlled by the pore volume fraction in the sintered body [24].

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120 a ) 110 a P G ( s 100 u l u d o 90 M s ' g n 80 u o Y 70 850 950 1050 1150 1250 1350 Sintering Temperature (C)

Figure 5. The effect of sintering temperature on the Youngs modulus of synthesized HA.
Young's Modulus (GPa) a 120 110 100 90 80 70 82 84 86 88 90 92 94 96 98 100 Relative Density (%)

Figure 6. A linear relationship exists between the bulk density and Youngs modulus of synthesized HA. SEM investigation revealed that when HA sintered at low temperature below 1000C, a uniform microstructure and distribution of equiaxed fine grains were obtained. However, as the sintering temperature was increased > 1000C, this was accompanied by grain coalescence with occasionally exaggerated grain growth observed, particularly for HA sintered 1150C. The dramatic change in the average grain size with sintering temperature is depicted in Fig. 7. It was found that initially the grain size increased slowly from 0.12 m at 900C to about 0.88 m at 1150C and thereafter accelerated by a factor of more than seven to 7.13 m when sintered at 1300C (Fig. 7).

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8 Average Grain Size (m) a 7 6 5 4 3 2 1 0 850 950 1050 1150 Sintering Temperature (C) 1250 1350

Figure 7. The effect of sintering temperature on the average grain size of sintered HA. The effect of sintering temperature on the fracture toughness KIc of the synthesized HA is shown in Fig. 8. It has been found that the fracture toughness of the sintered body increased with sintering temperature up a maximum of 1.22 MPam1/2 at 1000C and thereafter deceased almost linearly with increasing sintering temperature up to 1300C. Further to that, it was found that the variation in Vickers hardness Hv with sintering temperature (Fig. 9) is in good agreement with the fracture toughness trend. The hardness of the sintered HA increases rapidly from 2.8 GPa at 900C and reached a maximum of 7.21 GPa at 1050C before decreasing almost linearly to about 5.7-5.8 GPa at 1300C.
) a Fracture Toughness (MPam
1/2

1.3 1.2 1.1 1.0 0.9 0.8 850

950

1050

1150

1250

1350

Sintering Tem perature (C)

Figure 8. Fracture toughness variations of HA sintered at various temperature. The change in Vickers hardness and fracture toughness with grain sizes for samples sintered at various temperatures are presented in Fig. 10 and Fig. 11, respectively. It was found that samples with an average grain size of 0.3-0.5 m (i.e. sintered at 1000-1050oC) exhibited the highest hardness and fracture toughness. The low fracture toughness and hardness obtained for HA sintered at 1000C and 1050C, respectively are in agreement with the low measured bulk density (Fig. 4).

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7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 850

Vickers Hardness (GPa)

950

1050

1150

1250

1350

Sintering Tem perature (C)

Figure 9. Variation in the Vickers hardness of HA with increasing temperature. In contrast, as the grain sizes increases beyond 0.5 m resulting from sintering above 1050oC, the ceramics exhibited a gradual decrease in both the KIc and Hv even though they possessed high relative densities above 98% as shown in Fig. 4. This decreased in both the KIc and Hv, respectively could not be due to bulk density effect but rather can be interpreted as due to a grain size effect as shown in Fig. 10 and Fig. 11. As can be noted from both figures, the KIc and Hv, increases with grain size and reached a maximum value at a certain grain size limit (dc) before decreasing further with increasing grain size resulting from sintering at higher temperatures.
7.5 7 6.5 6 5.5 5 4.5 4 3.5 3 2.5 2 0 0.8 1.6 2.4 3.2 4 4.8 Average Grain Size (m ) 5.6 6.4 7.2 8

Based on these results, it is hypothesis that below some critical grain size of dc, the KIc and Hv are governed by bulk density (or porosity). In contrast, above dc the bulk density is not the controlling parameter but rather grain growth. However, at this stage the underlying mechanism that governs the hardness/fracture toughness-grain size relationship in HA produced by both consolidation methods is unclear.

Hv (GPa) a

Figure 10. The effect of grain size effect on the Vickers hardness of sintered HA.

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1.25 1.2 1.15
KIc (MPam 1/2) a

1.1 1.05 1 0.95 0.9 0.85 0 0.8 1.6 2.4 3.2 4 4.8 Average Grain Size (m ) 5.6 6.4 7.2 8

Figure 11. The effect of grain size effect on the fracture toughness of sintered hydroxyapatite.

4.

CONCLUSIONS

The sinterability of synthesized nanocrystalline HA particles was investigated and it was found that the sintering temperature plays an important role in determining the densification of the HA body. Furthermore, the phase stability of the synthesized HA was not disrupted through the sintering regime employed even when sintered at 1300C. Moreover, the relative density of > 98% of theoretical value and a Youngs modulus of > 100 GPa were obtained for samples sintered above 1000C. In addition, the Youngs modulus of synthesized HA was found to vary linearly with the bulk density, indicating that the matrix stiffness is governed by the density of the sintered ceramic. However, the average HA grain size was found to increase by a factor of more than seven from 0.88 m at 1150C to 7.13 m at 1300C. The increased in grain size was found to have an adverse effect on the fracture toughness and Vickers hardness of the sintered material whereby the fracture toughness started to decrease for grain size above 0.3 m while the hardness started to decline for grain size above 0.5 m despite the samples exhibiting relative densities above 98% of theoretical value. This phenomenon is believed to be due to a thermal-activated grain growth process.

ACKNOWLEDGMENTS The authors would like to thank the Ministry of Science, Technology and Innovation of Malaysia (MOSTI) for providing the financial support under the Science Fund Project No. 0302-03-SF0073. In addition, the support provided by UNITEN and SIRIM Berhad in carrying out this research is gratefully acknowledged.

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