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Materials Chemistry and Physics 104 (2007) 249253

In situ synthesis of spherical BCP nanopowders by microwave assisted process


Byong-Taek Lee a, , Min-Ho Youn a , Rajat Kanti Paul a , Kap-Ho Lee b , Ho-Yeon Song c,
a

Department of Biomedical Engineering and Materials, School of Medicine, Soonchunhyang University, 366-1, Ssangyoung-dong, Cheonan, Chungnam, 330-090, Korea b School of Advanced Materials Engineering, Chungnam National University, 220 Gung-dong, Yuseong-gu, Daejon 305-764, South Korea c Department of Microbiology, School of Medicine, Soonchunhyang University, 366-1 Ssangyoung-dong, Cheonan City, Chungnam 330-090, South Korea Received 3 April 2006; received in revised form 6 January 2007; accepted 12 February 2007

Abstract Hydroxyapatite (HAp) and biphasic tricalcium phosphate (BCP) nanopowders were synthesized by the microwave assisted process and their microstructures and crystal structures were investigated depending on the pH of the starting solution. The synthesized powders were spherical in shape and the average size was in the range of 5090 nm in diameter. In the range of pH 612, HAp and -TCP phases coexisted. The yield of HAp increased remarkably as the pH of the solution increased while -TCP and -TCP yields decreased. At pH 12, monolithic HAp powder was synthesized with nanoparticles. From the SBF experiment, the maximum resorption of Ca2+ was detected in the powders synthesized at pH 6. However, at pH 12, the monolithic HAp powder showed high stability in the SBF. 2007 Elsevier B.V. All rights reserved.
Keywords: HAp; BCP; Nanopowders; Microwave assisted process

1. Introduction Calcium phosphates such as HAp (Ca10 (PO4 )6 (OH)2 ) and TCP ( -/ -TCP, Ca3 (PO4 )2 ) are well-known biomaterials which provide an interfacial bond between an implant and the surrounding tissues due to their similarity to the mineral constituents of human bones and teeth [13]. However, the major disadvantages are low strength and low fracture toughness which limit their applications for non-load bearing parts, such as coatings and implants in non-stressed areas of the human body [4]. Thus, for load-bearing orthopedic and dental applications, the dense HAp bodies are generally required. However, most of the commercial HAp powders are a micron or sub-micron sized needle type. Thus, the particle composition, size, shape and morphol-

Corresponding author. Tel.: +82 41 570 2427; fax: +82 41 577 2415. Corresponding author. Tel.: +82 41 570 2412; fax: +82 41 577 2415. E-mail addresses: lbt@sch.ac.kr (B.-T. Lee), songmic@sch.ac.kr (H.-Y. Song).

ogy should be considered to obtain dense HAp ceramics with desired mechanical properties [5,6]. On the other hand, -tricalcium phosphate ( -TCP) ceramics have been developed as a biodegradable bone replacement material due to its resorption and excellent osteoconductivity [7,8]. Furthermore, biphasic calcium phosphate (BCP) consisting of HAp and TCP, has been reported to control the rate of biodegradation in the human body [9,10]. It has also been reported that osteo-integration of calcium phosphate ceramics depends on the ratio of TCP and HAp phases [11]. Moreover, the biomaterials implanted into bone defects should be spontaneously bonded to the living bone without any formation of surrounding brous tissue [12]. Thus, to investigate the bonding property of a biomaterial implanted into the living bone, the formation of bonelike apatite on its surface can be measured in a simulated body uid (SBF) with ion concentrations close to those of human blood plasma [13]. There are many reports on HAp synthesis such as using solid state reaction [14], precipitation [15], hydrothermal [16,17] and solgel methods [18,19], but they have some disadvantages, such

0254-0584/$ see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.matchemphys.2007.02.009

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Fig. 1. SEM images of HAp and -TCP nanopowders depending on the pH of the starting solution: (a) pH 6, (b) pH 8, (c) pH 10 and (d) pH 12.

as being time-consuming, having low quality control, chemical contamination, and powder at the sub-micron level. However, the microwave-hydrothermal method was found to synthesize the ultrane high purity nanopowder with high yield using high energy transformation in a short time [2022]. In this work, HAp and BCP nanopowders were synthesized using the microwave assisted process to investigate the depen-

dence of the results on the pH of the starting solution. The crystal structure and morphology of the synthesized powders were characterized using XRD, FE-SEM and TEM techniques. Moreover, SBF analysis was performed for the prediction of in vivo bioactivity of the synthesized nanopowders depending on the pH of the starting solution.
2. Experimental procedure
Commercial-grade Ca(OH)2 (Aldrich Chemical, 99.995%) and reagentgrade H3 PO4 (8587.0% H3 PO4 , Dongwoo Fine Chemicals, electronic grade) were used as starting materials for the synthesis of HAp and BCP nanopowders. These starting powders were weighed to coincide the stoichiometric HAp with a molar ratio of Ca/P = 1.67. The powder was mixed homogeneously by stirring it in de-ionized distilled water for 2 h. The pH of the initial solution was about 3.8. The pH of the starting solution was adjusted to 612 using a pH meter (IST-DC-

Fig. 2. XRD patterns of HAp and -TCP nanopowders depending on the pH of the starting solution at 700 W microwave irradiations: (a) pH 6, (b) pH 8, (c) pH 10 and (d) pH 12.

Fig. 3. Yield of HAp and TCP nanopowders depending on the pH of the starting solution.

B.-T. Lee et al. / Materials Chemistry and Physics 104 (2007) 249253 010036, istek, Korea) by the addition of ammonia solution. Subsequently, the suspension with a controlled pH was kept in a microwave oven (LG Electronics Co., Korea) which was operated with 2.45 GHz frequency microwave radiation while the operating power was kept at 700 W for 25 min at 300 C. After cooling to room temperature, the precipitate was washed thoroughly with de-ionized water several times and dried in an oven at 90 C. Finally, the calcination was carried out at 750 C in air. For the preparation of simulated body uid (SBF), the solution reported by Kokubo and Takadama [23] was used. The samples for the SBF experiment were made with a disk shape about 15 mm in diameter and 3 mm in thickness. The phase analysis of HAp and BCP nanopowders depending on the pH was identied using an X-ray diffractometer (XRD, D/MAX250, Rigaku, Japan). From the XRD patterns, the yields of the synthesized powders depending on the pH of the solution were calculated from the relative intensity of constituent phases. The morphology and microstructure of the synthesized powders were investigated using SEM (JSM-635F, JEOL) and TEM (JEM-2010, JEOL) techniques. The Ca2+ ion concentrations in the SBF were determined using ICP/AES (IRIS DUO, Thermo elemental, USA) technique.

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3. Results and discussion Fig. 1 shows the SEM images of BCP nanopowders which were synthesized by the microwave assisted process at 700 W for 25 min depending on the pH of the starting solution. The synthesized HAp and BCP powders had a spherical shape due to the short reaction time of the microwave system, which inhibited the growth of powders. On the other hand, the fast increase of energy in the system could be a reason for the decrease of the surface energy of the synthesized particles. The average particle size of the synthesized powders decreased as the pH of the solution increased, thus, the values at pH 6 and 12 were about 8090 and 5070 nm in diameter, respectively. Fig. 2 shows the XRD patterns of the synthesized nanopowders depending on the pH of the starting solution. At pH 6, the

Fig. 4. (a) TEM image, (b and c) EDS proles and (d) HRTEM image of HAp and -TCP nanopowders with pH 6 of the starting solution.

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synthesized powder showed mixed phases with -TCP, -TCP and HAp although the intensity of the -TCP phase was stronger than those of the -TCP and HAp phases. It was reported that in the phase diagram of the Ca(OH)2 H3 PO4 H2 O system, the solubility of the HAp increased with the decrease of the pH of the solution [24]. However, at pH 6, the solubility of the -TCP and -TCP phases decreased rapidly to precipitate a mixture of the TCP and HAp phases. On the other hand, at pH 8 (b), the -TCP phase was going to decrease due to its high solubility compared to the -TCP and HAp phases. However, at pH 12 (d), only a HAp phase was detected because the solubility of -TCP and -TCP phases was so high. Fig. 3 shows the yield of HAp, -TCP and -TCP powders depending on the pH of the starting solution. At pH 6, the in situ mixture powders with 12 wt% HAp, 60 wt% -TCP and 28 wt% -TCP phases were obtained. However, at pH 10, the main phases including HAp (52 wt%) and -TCP (42 wt%) and only a small amount of -TCP (6 wt%) were contained in the in situ mixture powders. Increasing the pH value caused the yield of -TCP and -TCP powders to gradually decrease. Thus, at

pH 12, monolithic HAp (100 wt%) powder was obtained without any other phases. Fig. 4 shows (a) the low magnication TEM image, (b and c) EDS proles and (d) HRTEM image of the nanopowders synthesized at pH 6. In the bright eld (a) TEM image, the dark and faint contrasts are comprised with HAp and -TCP phases, respectively. The contrasts were varied due to the Ca/P ratio of the HAP and -TCP phases as well as the thickness of the powders. The average particle size of the synthesized powders was about 8090 nm in diameter. The EDS proles (b) and (c) were taken from the P (dark contrast) and Q (comparatively faint contrast) regions in (a). From the EDS proles, it was conrmed that the HAp (Ca/P = 1.67) and TCP (Ca/P = 1.5) particles appeared with dark and faint contrasts, respectively. The HRTEM image (d) shows a typical lattice image of -TCP which was taken from [1 1 0] zone axis at region Q in Fig. 4(a). At the dotted circles in Fig. 4(d), a few edge dislocations were observed as well as strain eld contrast. These internal defects which can produce the lattice distortion are basically due to the local variation of Ca/P ratio.

Fig. 5. (a) TEM image, (b) EDS prole and (c) HRTEM image of HAp nanopowder with pH 12 of the starting solution.

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90 nm in diameter due to the rapid, high energy transformation. The phase composition of the synthesized powders was easily controlled depending on the pH of the starting solution. At pH 6, the synthesized powder was composed of -TCP (60 wt%), TCP (28 wt%) and HAp (12 wt%) phases while at pH 10, mostly HAp (52 wt%) and -TCP (42 wt%) phases were obtained. However, at pH 12, monolithic HAp powder was obtained with a particle size of 5070 nm. In SBF, the BCP ceramics showed maximum Ca2+ concentration due to their high resorption. Acknowledgements This work supported by NRL research program of the Korea Ministry of Science and Technology. The authors would like to acknowledge the kind assistance of Dr. J.K. Han. References
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Fig. 6. Simulated body uid (SBF) proles of synthesized powders depending on the pH of the starting solution.

Fig. 5 shows (a), a low magnication TEM image, (b) an EDS prole and (c) an HRTEM image of HAp powder synthesized at pH 12. Most of the synthesized powder was spherical, and 5070 nm in diameter, but a small amount was needle-shaped, with about 50 nm in diameter and 100150 nm in length. From the EDS prole which was taken from the P region in Fig. 5(a), it was conrmed that the Ca/P ratio was 1.67 of HAp powder. However, the HRTEM image (c) taken from the [1 1 0] zone axis at the P region in Fig. 5(a), shows a clear lattice image without strain eld contrast. This result was remarkably compared with that of -TCP as shown in Fig. 4(d). Fig. 6 shows the SBF proles of the microwave assisted synthesized powders depending on the pH of the starting solution. In the case of pH 6, the samples show the maximum Ca2+ ions concentration in the SBF for 1 week. This result indicated the high resorption of the BCP in the sample due to the high content of -TCP phase [23]. However, as the pH of the starting solution increased, Ca2+ ion concentrations in SBF decreased, and monolithic HAp powder at pH 12, shows the minimum Ca2+ ion concentrations due to its high stability in the SBF solution as well as less resorption than that of BCP ceramics. 4. Conclusion Using an aqueous solution containing Ca(OH)2 and H3 PO4 , BCP and monolithic HAp nanopowders were synthesized by a microwave assisted method at 700 W for 25 min and their morphologies were characterized. The synthesized nanopowders were spherical, having a particle size ranging from 50 to

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