Materials Letters 62 (2008) 45524554

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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

Microwave-assisted preparation of calcium sulfate nanowires

Liang Li, Ying-Jie Zhu , Ming-Guo Ma
State Key Laboratory of High Performance Ceramics and Superne Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, PR China Graduate School of the Chinese Academy of Sciences, PR China

a r t i c l e

i n f o

a b s t r a c t
We have successfully developed a new synthetic route for the rapid preparation of calcium sulfate nanowires by thermal transformation of calcium dodecyl sulfate (CDS) in organic solvents of ethylene glycol (EG) and N, N-dimethylformamide (DMF). The products are characterized by X-ray powder diffraction (XRD) and transmission electron microscopy (TEM), and determined to be single-phase CaSO40.5H2O consisting of single-crystalline nanowires with aspect ratio up to about 62. In this method, the different types of organic solvents used have no obvious inuences on the morphology, phase, and formation time of the product. The microwave heating can remarkably shorten the reaction time compared with conventional heating methods. 2008 Elsevier B.V. All rights reserved.

Article history: Received 22 May 2008 Accepted 22 August 2008 Available online 31 August 2008 Keywords: Nanomaterials Microstructure Calcium sulfate Nanowire Microwave

1. Introduction Calcium sulfate abundantly exists in nature and is a very important industrial material which is used as food additive, paper-making material, timbering, medical material, inorganic ller or intensier in composites, etc. [13]. Furthermore, calcium sulfate is aseptic, biocompatible and biodegradable, which is an ideal substitute of bone transplantation material [47], and antibiotic-carrier material [810]. Calcium sulfate hemihydrate (CaSO40.5H2O) and calcium sulfate dihydrate (CaSO42H2O) are the most frequently used ones in plentiful types of calcium sulfate (CaSO4nH2O, n = 02). In experiments and clinical uses, it is an easy and common route to obtain CaSO42H2O by mixing CaSO40.5H2O with water [1013]. The fabrication and morphology control of calcium sulfate nanostructures are still challenging. Different morphologies of nanosized calcium sulfate, such as nanoparticles [1417], nanorods [17,18], nanowires (or nanobers) [1517,19], nanotubes [17,20], and nanosheets [16], have been prepared. Most of them were performed in w/o microemulsion or reverse micelles at room temperature [15,1719]. Other methods have also be used to synthesize nanosized calcium sulfate as well, for example, Sawant et al. obtained calcium sulfate nanoparticles by using liquidliquid separation method, a kind of supersaturated precipitation method [14]. Gao et al. synthesized calcium sulfate nanotubes by

solvothermal method [20]. However, preparation and morphology control of calcium sulfate in organic media or at elevated temperatures have been less reported. To the best of our knowledge, there has been no report on the microwave preparation of calcium sulfate nanostructures. In this paper, we report a microwave-assisted method for the preparation of single-crystalline calcium sulfate (CaSO40.5H2O) nanowires by using calcium dodecyl sulfate as the precursor. 2. Experimental details All chemicals were purchased and used as received without purication. Ethylene glycol (EG), N,N-dimethylformamide (DMF) and CaCl2 were analytical grade reagents, and sodium dodecyl sulfate (SDS) was chemical pure. Calcium dodecyl sulfate (CDS) was obtained by mixing CaCl2 and SDS saturated aqueous solutions. The precipitate was collected by centrifugation and washed with deionized water several times, then dried in vacuum at 60 C. In a typical experiment, 285 mg CDS was dissolved in 50 mL EG. Then the solution was heated at 100 C by the microwave heating under magnetic stirring for 15 min (sample 1). Sample 2 was prepared by using DMF instead of EG compared with sample 1. Sample 3 was prepared by oil bath at 100 C in EG until it turned white turbid. The products were separated by centrifugation, washed with absolute alcohol, and dried at 60 C. Microwave oven used was a focused single-mode microwave synthesis system (2.45 GHz, Discover, CEM, USA). X-ray powder diffraction (XRD) was performed on a Rigaku D/max 2550 V X-ray diffractometer with a high-intensity Cu K radiation ( = 1.54178 ) and a graphite monochromator. Transmission electron microscopy (TEM) micrographs were taken on a JEOL JEM-2100F eld emission

Corresponding author. State Key Laboratory of High Performance Ceramics and Superne Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, PR China. Tel.: +86 21 52412616; fax: +86 21 52413122. E-mail address: y.j.zhu@mail.sic.ac.cn (Y.-J. Zhu). 0167-577X/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.matlet.2008.08.040

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Fig. 3. Scheme for the formation of calcium sulfate nanowires.

Fig. 1. Typical XRD pattern of calcium sulfate nanowires.

transmission electron microscope with an accelerating voltage of 200 kV.

3. Results and discussion All as-prepared samples have the similar XRD patterns, as shown in Fig. 1. All the reections can be indexed to a single-crystalline phase of CaSO40.5H2O with a monoclinic structure (JCPDS No. 41-0224). The morphologies of the samples were investigated by TEM (Fig. 2). One can see that all three samples consisted of nanowires. Selected area electron diffraction (SAED) patterns taken from different positions from an individual nanowire or different nanowires were essentially the same. Fig. 2c shows a typical single nanowire and its corresponding SAED pattern (inset of Fig. 2c), indicating the single-crystalline structure of CaSO40.5H2O nanowires. Samples 1 and 2 prepared by microwave heating but in different organic solvents had similar morphologies (Fig. 2ac and d,e), indicating that the organic solvents of EG and DMF have little inuence on the morphology of products. The as-prepared nanowires of the two samples had diameters of about 130 nm and lengths up to 8 m. The aspect ratios of nanowires were up to about 62. We also investigated the relationship between heating method and reaction time by comparing samples 1 and 3. These two samples were prepared both in EG solution at

100 C with different heating methods. When microwave heating was used (sample 1), it took only 15 min for the formation of CaSO40.5H2O nanowires. In comparison, much longer time (60 h) was needed for the formation of CaSO40.5H2O nanowires using oil bath heating (sample 3). The results indicate that the reaction time was signicantly inuenced by heating methods. Herein, microwave-assisted heating method is proved to be advantageous for fast preparation of materials, as previously reported [21]. In this paper, we suppose the possible reaction process in the organic solvent for the formation of CaSO40.5H2O nanowires, as shown in Fig. 3. It is a chain-break decomposition reaction instead of the usual precipitation reaction for the formation of calcium sulfate. The bond between alkane group (dodecyl) and sulfate group in CDS was destroyed by thermal effect and calcium sulfate was precipitated in organic medium. The precursor CDS acted as both the reactant and template for the formation of CaSO40.5H2O nanowires. The microwave heating provides the reaction energy to ensure the reaction take place. Microwave heating is a highly effective heating method, leading to rapid formation of CaSO40.5H2O nanowires.

4. Conclusions In this paper, we have successfully developed a new synthetic route for the rapid preparation of CaSO40.5H2O nanowires by microwave-assisted thermal transformation of the calcium dodecyl sulfate. This microwave-assisted method does not need any seed, template or other reagents, thus is a simple and fast pathway for largescale and low-cost production of calcium sulfate nanowires. If the proper sources are chosen, the method demonstrated in this paper may be extended to the synthesis of other 1D nanomaterials.

Fig. 2. TEM micrographs of calcium sulfate nanowires: (a)(c) sample 1, the inset shows corresponding SAED pattern; (d) and (e) sample 2; (f) sample 3.

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Acknowledgments Financial support from the National Natural Science Foundation of China (50772124), the Program of Shanghai Subject Chief Scientist (07XD14031), the Key Project for Innovative Research (SCX0606) and Director Fund of Biomaterials Research Center from Shanghai Institute of Ceramics is gratefully acknowledged. References
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