Materials Letters 63 (2009) 12071209

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Materials Letters
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a t l e t

Synthesis of nanoporous calcium phosphate spheres using poly(acrylic acid) as a structuring unit
Peng Wang a, Se-Won Yook a, Shin-Hee Jun a, Yuan-Long Li a, Miyoung Kim a, Hyoun-Ee Kim a,, Young-Hag Koh b
a b

Department of Materials Science and Engineering, Seoul National University, Seoul, 151-744, Republic of Korea Department of Dental Laboratory Science and Engineering, Korea University, Seoul, 136-703, Republic of Korea

a r t i c l e

i n f o

a b s t r a c t
Calcium phosphate (CaP) spheres with nanopores were synthesized using poly(acrylic acid) (PAA) as the structuring unit. In this method, colloidal droplets of the PAA/Ca2+ complex were prepared by adding a Ca(NO3)2 solution to a PAA aqueous solution and then mixed with an (NH4)2HPO4 solution, which allowed the nucleation and growth of CaP nanocrystals in the PAA matrix. Thereafter, the as-synthesized PAA/CaP spheres were heattreated at 550 C for 3 h to remove the PAA phase, followed by treatment in ammonium nitrate solution to remove the CaO phase formed as an impurity. The prepared CaP spheres showed a narrow size distribution with an average diameter of 146 43 nm and nanopores formed via the removal of the CaO phase. 2009 Elsevier B.V. All rights reserved.

Article history: Received 15 December 2008 Accepted 18 February 2009 Available online 23 February 2009 Keywords: Ceramics Powder technology Calcium phosphate spheres Poly(acrylic acid)

1. Introduction Calcium phosphate (CaP) ceramics have been widely utilized in the eld of bone tissue engineering, owing to their excellent biocompatibility, bioactivity and osteoconductivity [1]. The biological properties of these materials, particularly in the form of particles, would be expected to be strongly inuenced by both their intrinsic (e.g. chemical compositions and crystalline structures) and extrinsic properties (particle size and morphology). Therefore, a great deal of attention has been focused on the synthesis of CaP particles with a controlled morphology. So far, a variety of CaP particles in the forms of needle-like nanocrystals [2], nanorods [3], whiskers [4], microtubes [5], and so forth, have been synthesized via different processing routes. However, only a few attempts have been made to prepare spherical CaP particles [6], although these materials, particularly with micro- or nanopores, can nd very useful applications in diverse elds, such as ion exchangers, adsorbents, and catalysts as well as bone scaffolds [7,8]. Therefore, in this study, we demonstrate a novel and simple method for the synthesis of nanoporous CaP spheres with a narrow size distribution in a cost-effective way. To accomplish this, we employed poly(acrylic acid) (PAA) as the structuring unit, since it would be expected to form colloidal droplets of the PAACa2+ complex in an aqueous solution containing calcium ions [911]. These complex colloids would then react with the PO3 ions, consequently, allowing the 4 nucleation and growth of CaP nanocrystals in a PAA matrix. The assynthesized CaP spheres were heat-treated at 550 C for 3 h in air to

remove the PAA phase, followed by treatment in an ammonium nitrate (NH4NO3) solution to remove any possible secondary phases (e.g. CaO). The prepared spheres, i.e., the as-synthesized PAACaP spheres and CaP spheres before and after treatment in NH4NO3 solution were examined by considering their morphologies, compositions, chemical structures, crystalline phases, and surface areas.

2. Experimental procedure All of the chemicals used in this study were commercially obtained from Sigma-Aldrich (Sigma-Aldrich, St. Louis, MO, USA), unless otherwise specied. Low-molecular-weight poly(acrylic acid) (PAA, Mw = 5000) was used as the structuring unit. Calcium nitrate tetrahydrate [Ca(NO3)2U4H2O] and diammonium hydrogen phosphate [(NH4)2HPO4] were used as the precursors for the synthesis of the CaP nanocrystals. PAA/CaP spheres were synthesized using colloidal droplets of the PAACa2+ complex as the structuring unit, prepared according to a similar method to that reported in the literature [11]. Firstly, a PAA stock solution containing 10 mM of repeating units was prepared in distilled water with a pH of 11.5 adjusted by the addition of NH4OH. Thereafter, 5.5 mL of a 0.1 M Ca(NO3)2 solution was added dropwise to 60 mL of the PAA solution at room temperature and stirred for 30 min, inducing the complexation of PAA with the calcium ions and water molecules. Following this, a predetermined amount (Ca/P = 1.67) of 0.1 M (NH4)2HPO4 aqueous solution with a pH of 10.5 prepared in a separate process was added dropwise to the PAA/Ca(NO3)2 solution and aged at room temperature for 12 h with magnetic stirring to induce the nucleation and growth of CaP nanocrystals in the PAA

Corresponding author. Tel.: +82 2 880 7161. E-mail address: kimhe@snu.ac.kr (H.-E. Kim). 0167-577X/$ see front matter 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.matlet.2009.02.033

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P. Wang et al. / Materials Letters 63 (2009) 12071209

Fig. 1. SEM micrographs of (A) the as-synthesized PAA/CaP spheres and (B) the CaP spheres after heat-treatment at 500 C for 3 h.

matrix. The resultant PAA/CaP spheres were then washed with distilled water several times and freeze dried, followed by heattreatment at 550 C for 3 h in air to remove the PAA phase. Thereafter, any possible secondary phases (e.g. CaO) were removed by washing the CaP spheres with 0.1 M ammonium nitrate (NH4NO3) solution. The three types of spheres (i.e., the as-synthesized PAA/CaP spheres and the CaP spheres before and after treatment in NH4NO3 solution) were evaluated. The morphologies of the spheres were examined by eld-emission scanning electron microscopy (FE-SEM, JSM-6330F, JEOL, Tokyo, Japan) and high-resolution transmission electron microscopy (HR-TEM, JEOL JEM-3010, Japan). The chemical structures and crystalline phases of the samples were characterized by Fourier-transform infrared spectroscopy (Nicolet Magma 550 series II, Midac, USA) and X-ray diffraction (XRD, M18XHF-SRA, MacScience Co., Yokohama, Japan), respectively. In addition, their surface areas were measured by the multipoint BrunauerEmmettTeller (BET) method with a Micrometrics ASAP 2010 gas sorption analyzer at the temperature of liquid nitrogen. Before measurement, the samples were degassed at 100 C for at least 8 h. 3. Results and discussion The use of colloid droplets of PAACa2+ complex as the structuring unit allowed the synthesis of PAA/CaP spheres with a narrow size distribution, as shown in Fig. 1 (A). The average diameter of the spheres obtained was 166 48 nm, which was calculated by measuring the diameters of 30 different, arbitrarily selected particles from the SEM images. These PAA/CaP spheres were then heat-treated at 550 C for 3 h to remove the PAA phase. It was observed that this high temperature

heat-treatment did not alter the spherical shape of the CaP particles, as shown in Fig. 1 (B), since the CaP nanocrystals were homogenously distributed in the PAA matrix on the nanoscale. However, their average diameter was slightly decreased to 146 43 nm, owing to the shrinkage caused by the thermal decomposition of the PAA phase and the partial sintering of the CaP nanocrystals. The chemical structures of the PAA/CaP and CaP spheres before and after treatment in an ammonium nitrate (NH4NO3) solution were characterized by FT-IR analysis. The spectra of the as-synthesized PAA/ CaP spheres revealed the bands associated with both the organic PAA phase (i.e., broad absorption band at ~3384 cm 1, small band at ~2944 cm 1, and relatively sharp bands in the range of 12501750 cm 1) [12] and inorganic CaP phase (i.e., absorption bands at ~4001250 cm 1) [13], as shown in Fig. 2 (A). In addition, a strong band at ~1563 cm 1 was observed, which was attributed to the asymmetrical stretching vibrations of the PAA carboxylate anions, indicating the complexation between the carboxylic groups of the PAA macromolecules and calcium ions via electrostatic interactions [14]. After heat-treatment at 550 C for 3 h, all of the bands associated with the PAA phase disappeared, while those associated with the CaP phase at ~400700 cm 1 and 9001200 cm 1, which are characteristic of the 13 and 4 modes for the PO3 groups, 4 respectively, became more distinctive due to the increase in crystallinity, as shown in Fig. 2 (B). A band associated with the OH stretching vibrations of the hydroxyl groups was also observed at 3573 cm 1. These observations indicate that the prepared spheres are mainly comprised of CaP nanocrystals. However, the CO2-derived bands at ~870 and 1400 3 1500 cm 1 were also observed, implying the presence of CO2 groups in 3 the CaP lattice [13]. In addition, it was observed that the treatment in the ammonium nitrate (NH4NO3) solution did not alter the chemical structure of the CaP spheres, as shown in Fig. 2 (C).

Fig. 2. FT-IR spectra of (A) the as-synthesized PAA/CaP spheres, (B) the CaP spheres after heat-treatment at 500 C for 3 h, and (C) the CaP spheres after treatment in ammonium nitrate solution.

Fig. 3. XRD patterns of (A) the as-synthesized PAA/CaP spheres, (B) the CaP spheres after heat-treatment at 500 C for 3 h, and (C) the CaP spheres after treatment in ammonium nitrate solution.

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Fig. 4. (A) SEM micrograph and (B) TEM micrograph of the CaP spheres after treatment in ammonium nitrate solution.

The crystalline structures of the PAA/CaP and CaP spheres before and after treatment in the ammonium nitrate (NH4NO3) solution were characterized by XRD analysis. The as-synthesized PAA/CaP sample displayed only a broad peak at ~2535 C, as shown in Fig. 3 (A), indicating that the CaP phase was poorly crystallized. On the other hand, the sample subjected to heat-treatment at 550 C for 3 h displayed strong peaks that corresponded well to those of hydroxyapatite crystal (JCPDS le No. 09-0432), as shown in Fig. 3 (B), owing to the increase in crystallinity. In addition, an additional peak at ~37.4 C was observed, implying the possible presence of calcium oxide (CaO) as a secondary, presumably due to the incorporation of the carbon dioxide generated during the thermal decomposition of the PAA phase into the CaP phase [15]. However, this CaO phase was found to be readily removed by treating the spheres in the NH4NO3 solution, as shown in Fig. 3 (C). It was also observed that the treatment in the ammonium nitrate solution did not cause the destruction of their spherical shape, as shown in Fig. 4 (A). However, it should be noted that the spheres had rough surfaces, which was attributed to the formation of nanopores formed by the removal of CaO. The generation of nanopores in the CaP spheres was more closely examined by TEM, as shown in Fig. 4 (B). The nanopores were uniformly distributed throughout the CaP spheres. In addition, the surface area (58.7 m2/g) of the CaP spheres after treatment in ammonium nitrate solution was larger than that (31.5 m2/g) of the untreated spheres, conrming the formation of the nanopores via the removal of CaO. It is worth mentioning that the present method provides a useful and simple technique to synthesize CaP spheres with a narrow size distribution and nanopores. Particularly, the spherical shape is thought to allow for good blood and nutrient circulation, as well as the fast in-growth of osteoblastic cells and bone tissue, when used as a bone ller material, while the nanopores may provide sites for the loading of drugs or growth factors. In addition, these spheres with high surface areas would nd very useful applications as a bioactive coating material for metallic substrates.

4. Conclusions We herein demonstrated a novel and simple approach for the synthesis of nanoporous CaP spheres in a cost-effective way, in which PAACa2+ complex colloids were used as the structuring unit. The nanopores were generated by removing the CaO phase formed during the heat treatment process. The CaP spheres showed good sinterability with an average diameter of 146 43 nm and specic surface area of 58.7 m2/g.

Acknowledgements This research was supported by a grant from the Fundamental R&D Program for Core Technology of Materials funded by Ministry of Knowledge Economy, Republic of Korea.

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