Materials Chemistry and Physics 104 (2007) 249–253

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 50–90 nm in diameter. In the range of pH 6–12, 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 [1–3]. 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 fibrous 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 fluid (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 sol–gel methods [18,19], but they have some disadvantages, such

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the microwave-hydrothermal method was found to synthesize the ultrafine high purity nanopowder with high yield using high energy transformation in a short time [20–22]. The pH of the initial solution was about 3. electronic grade) were used as starting materials for the synthesis of HAp and BCP nanopowders. 99.67. and powder at the sub-micron level. as being time-consuming. 3. The powder was mixed homogeneously by stirring it in de-ionized distilled water for 2 h.8. SEM images of HAp and -TCP nanopowders depending on the pH of the starting solution: (a) pH 6.995%) and reagentgrade H3 PO4 (85–87. However.-T. 2. . Dongwoo Fine Chemicals. Lee et al. FE-SEM and TEM techniques. 2. SBF analysis was performed for the prediction of in vivo bioactivity of the synthesized nanopowders depending on the pH of the starting solution. (c) pH 10 and (d) pH 12. having low quality control. (c) pH 10 and (d) pH 12. The crystal structure and morphology of the synthesized powders were characterized using XRD. In this work. (b) pH 8. Fig. chemical contamination.0% H3 PO4 . XRD patterns of HAp and -TCP nanopowders depending on the pH of the starting solution at 700 W microwave irradiations: (a) pH 6. Moreover. (b) pH 8. Yield of HAp and TCP nanopowders depending on the pH of the starting solution. The pH of the starting solution was adjusted to 6–12 using a pH meter (IST-DC- Fig. These starting powders were weighed to coincide the stoichiometric HAp with a molar ratio of Ca/P = 1. Experimental procedure Commercial-grade Ca(OH)2 (Aldrich Chemical. 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.250 B. 1. / Materials Chemistry and Physics 104 (2007) 249–253 Fig.

Finally. istek. USA) technique. 251 3. 2 shows the XRD patterns of the synthesized nanopowders depending on the pH of the starting solution. The phase analysis of HAp and BCP nanopowders depending on the pH was identified using an X-ray diffractometer (XRD. the calcination was carried out at 750 ◦ C in air.. the yields of the synthesized powders depending on the pH of the solution were calculated from the relative intensity of constituent phases. Results and discussion Fig. At pH 6. thus. For the preparation of simulated body fluid (SBF). which inhibited the growth of powders. the precipitate was washed thoroughly with de-ionized water several times and dried in an oven at 90 ◦ C. JEOL) and TEM (JEM-2010. The Ca2+ ion concentrations in the SBF were determined using ICP/AES (IRIS DUO. The synthesized HAp and BCP powders had a spherical shape due to the short reaction time of the microwave system. the solution reported by Kokubo and Takadama [23] was used. Lee et al. From the XRD patterns. On the other hand. The morphology and microstructure of the synthesized powders were investigated using SEM (JSM-635F. Korea) by the addition of ammonia solution. the values at pH 6 and 12 were about 80–90 and 50–70 nm in diameter. Japan). Fig. D/MAX250. The samples for the SBF experiment were made with a disk shape about 15 mm in diameter and 3 mm in thickness.-T. the fast increase of energy in the system could be a reason for the decrease of the surface energy of the synthesized particles. JEOL) techniques. Thermo elemental. the suspension with a controlled pH was kept in a microwave oven (LG Electronics Co. / Materials Chemistry and Physics 104 (2007) 249–253 010036.45 GHz frequency microwave radiation while the operating power was kept at 700 W for 25 min at 300 ◦ C.B. After cooling to room temperature. (b and c) EDS profiles and (d) HRTEM image of HAp and -TCP nanopowders with pH 6 of the starting solution. 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. Rigaku. Korea) which was operated with 2. . The average particle size of the synthesized powders decreased as the pH of the solution increased. Subsequently. respectively. (a) TEM image. the Fig. 4.

the solubility of the -TCP and -TCP phases decreased rapidly to precipitate a mixture of the TCP and HAp phases. 3 shows the yield of HAp. (b) EDS profile and (c) HRTEM image of HAp nanopowder with pH 12 of the starting solution. (b and c) EDS profiles and (d) HRTEM image of the nanopowders synthesized at pH 6. On the other hand. Fig. the solubility of the HAp increased with the decrease of the pH of the solution [24]. Fig.67) and TCP (Ca/P = 1. at pH 8 (b). the -TCP phase was going to decrease due to its high solubility compared to the -TCP and HAp phases. Fig. at pH 12.252 B. It was reported that in the phase diagram of the Ca(OH)2 –H3 PO4 –H2 O system. (a) TEM image. The average particle size of the synthesized powders was about 80–90 nm in diameter. At pH 6. respectively. 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. At the dotted circles in Fig. -TCP and HAp although the intensity of the -TCP phase was stronger than those of the -TCP and HAp phases. monolithic HAp (100 wt%) powder was obtained without any other phases. 4(d). These internal defects which can produce the lattice distortion are basically due to the local variation of Ca/P ratio. Lee et al. However. However.-T. The EDS profiles (b) and (c) were taken from the P (dark contrast) and Q (comparatively faint contrast) regions in (a). -TCP and -TCP powders depending on the pH of the starting solution. at pH 12 (d). 4 shows (a) the low magnification TEM image. Increasing the pH value caused the yield of -TCP and -TCP powders to gradually decrease. 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 HRTEM image (d) shows a typical lattice image of -TCP which was taken from [−1 1 0] zone axis at region Q in Fig. In the bright field (a) TEM image. it was confirmed that the HAp (Ca/P = 1. respectively. the dark and faint contrasts are comprised with HAp and -TCP phases.5) particles appeared with dark and faint contrasts. However. / Materials Chemistry and Physics 104 (2007) 249–253 synthesized powder showed mixed phases with -TCP. Thus. the in situ mixture powders with 12 wt% HAp. 4(a). 60 wt% -TCP and 28 wt% -TCP phases were obtained. a few edge dislocations were observed as well as strain field contrast. From the EDS profiles. at pH 6. . 5. at pH 10. only a HAp phase was detected because the solubility of -TCP and -TCP phases was so high.

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