Materials Letters 59 (2005) 916 919 www.elsevier.

com/locate/matlet

A simple solgel technique for preparing hydroxyapatite nanopowders

Wang Fenga,b, Li Mu-sena,*, Lu Yu-penga, Qi Yong-xina
b

School of Materials Science and Engineering, Shandong University, 73 Jingshi Road, Jinan 250061, China School of Chemistry and Environment Engineering, Shandong University of Science and Technology, Jinan 250031, China Received 17 June 2004; accepted 25 August 2004 Available online 14 December 2004

Abstract HA powder was prepared using a solgel method with phosphoric pentoxide (P2O5) and calcium nitrate tetrahydrate (Ca(NO3)2d 4H2O). The effect of sintering temperatures on crystalline degree and composition of the HA phase, and also the effect of aging times on crystal size of the HA powder were studied using XRD and TEM. It was found that at sintering temperatures ranging from 600 to 900 8C, the dominant phase in the powders was HA with small amounts of calcium oxide and h-tricalcium phosphate (h-TCP) at 800 and 900 8C, and only HA phase was observed at 600 and 700 8C. 1015 nm HA powders were obtained using this technique. This technique has an advantage over other solgel methods in more simple and shorter time because of no requiring pH value control and long hydrolysis time. D 2004 Elsevier B.V. All rights reserved.
Keywords: Biomaterial; HA; Nanopowders; Solgel

1. Introduction In recent years, inorganic bioceramic hydroxyapatite (HA, Ca10(PO4)6(OH)2), being the main inorganic composition of natural bone, has been extensively investigated for medical applications due to its excellent biocompatibility and tissue bio-activity properties [1,2]. For this reason, many HA synthesis techniques have been developed. These include mechanochemical synthesis [3], combustion preparation [4], and various techniques of wet chemistry, such as direct precipitation from aqueous solutions [5], electrochemical deposition [6], solgel procedures [7], hydrothermal synthesis [8], and emulsion or micro-emulsion routes [9], etc. The most commonly

* Corresponding author. Tel.: +86 531 8392412; fax: +86 531 2955999. E-mail address: wf890916@163.com (L. Mu-sen). 0167-577X/$ - see front matter D 2004 Elsevier B.V. All rights reserved. doi:10.1016/j.matlet.2004.08.041

used technique for the preparation of HA powders is the precipitation technique. Various precipitation methods yield HA crystals in the nanometric, sub-nanometric and micrometric size range. However, the precipitation technique has some disadvantages, for example, needing the high pH value to avoid the formation of a Ca-deficient HA and the high sintering temperature to form the crystalline HA. The solgel process is a wet chemical method that needs no high pH value and no too high sintering temperature. This method offers a molecular mixing of the calcium and phosphorus which is capable of improving the chemical homogeneity. Moreover, the high reactivity of the solgel powders allows a reduction of the processing temperature and of any degradation phenomena during sintering [10]. Many reported solgel processes [1114] require a strict pH control, vigorous agitation and a long time for hydrolysis. Here we will report a simple solgel method that does not require controlling pH value and also vigorously stirring and long time for hydrolysis of phosphates.

W. Feng et al. / Materials Letters 59 (2005) 916919

917

2. Experimental Fig. 1 shows the experimental procedure and the reagents used in this study. A designed amount of phosphoric pentoxide (P2O5, AR) was dissolved in absolute ethanol to form a 0.5 mol/l solution. A designed amount of calcium nitrate tetrahydrate (Ca(NO3)2d 4H2O, AR) was also dissolved in absolute ethanol to form a 1.67 mol/l solution. The two solutions were mixed in a Ca/P molar ratio of 1.67 as an initial mixed precursor solution. The mixture was continuously stirred about 10 min at ambient temperature, then was heated in a water bath at 60 8C for 1 h, here a white transparent gel was obtained. The gel was divided into 10 parts. 4 parts were aged for 4 h at ambient temperature, then dried at 80 8C for 24 h in an air oven. The dried gels were individually heated at 10 8C min1 to 600,700,800,900 8C in a muffle furnace, then placed in air cooling to ambient temperature. The sintered products were crushed using an agate mortar and pestle to obtain resultant powders. Other 6 parts were treated for the different aging time (4 h, 48 h, 72 h) respectively, then sintered at the temperatures (700 8C and 800 8C) in order to investigate the effect of aging time on formation and size of HA powders. Powders produced were characterized by X-ray diffraction (XRD). The XRD patterns were recorded using CuKa radiation generated at 40 kV and 100 mA, in the

Intensity (a.u.)
20

40

60

2 (Degrees)
Fig. 2. X-ray diffraction pattern of HA powders. The powders were aged 4 h and sintered at 700 8C.

range of 208b2hb608 at a scan speed of 48/min. Morphological observations of powders were performed in a transmission electron microscope (TEM) (A type H800, made in Japan).

3. Results and discussion 3.1. XRD analyses Fig. 2 shows the XRD patterns for a powder aged 4 h and sintered at 700 8C. The d spacings are compared with the JCPDS [15] standard for HA in Table 1. It can be seen that there is a good match with the standard both in terms of intensity and position of the lines. In addition to the HA

P2O5 + C2H5OH Mixing

Ca(NO3)4H2O + C2H5OH

Table 1 Plane spacings and intensities obtained from XRD d (nm) experimental 0.3445 0.3085 0.2812 0.2774 0.2719 0.2632 0.2292 0.2261 0.2144 0.2060 0.1944 0.1891 0.1841 0.1802 0.1778 0.1753 0.1722 0.1643 0.1611 0.1542 JCPDS 0.3440 0.3080 0.2814 0.2778 0.2720 0.2631 0.2295 0.2262 0.2148 0.2065 0.1943 0.1890 0.1841 0.1806 0.1780 0.1754 0.1722 0.1644 0.1611 0.1542 Intensity experimental 33 14 100 48 62 22 9 23 7 7 36 17 41 19 15 20 19 7 6 8 JCPDS 40 18 100 60 60 25 8 20 10 8 30 16 40 20 12 16 20 10 8 6 (hkl) 002 210 211 112 300 202 212 310 311 122 222 312 213 321 410 402 004 322 313 420

Gelation

Aging

Drying

sintering

Crushing

HA powder
Fig. 1. A flow sheet of the solgel synthesis of HA powders.

Experimental data from HA powder aged for 4 h and sintered at 700 8C.

918

W. Feng et al. / Materials Letters 59 (2005) 916919

900C

sintered at 700 and 800 8C, respectively. The XRD results for all powders sintered at 700 8C are similar to Fig. 2, that is, no other phase line presents besides HA lines. The XRD results for all powders sintered at 800 8C for different aging times are shown in Fig. 4. It can be seen that additional crystalline phases (h-TCP and CaO) are clear ranging from aging 4 h to 72 h. It suggests that aging time has less effect on forming pure HA powder than sintering temperature. 3.2. TEM analyses

Intensity (a.u.)

800C

700C

600C

20

40

60

2 (Degrees)
Fig. 3. X-ray diffraction pattern of HA powders, showing the effect of the sintering temperature. The diffraction lines corresponding to HA and h-TCP are indicated by * and +, respectively. The CaO lines are indicated by o.

Fig. 5 shows the morphologies of the HA powders sintered at 700 8C and for different aging times(4 h, 48, 72 h). All the HA samples showed nano-sized ellipse-like morphology. However, the powders aged 4 h were only 1015 nm size, the powders aged 48 h were 1525 nm, and the powders aged 72 h were 5080 nm with not well dispersing. It suggests that the powders synthesized for long aging time were larger than those for short aging time, that is, aging could contribute to powder growth and agglomerate. The first stage after making the sol is gelation, where sufficient polymerization has occurred to form a crosslinking of the molecules making up the skeletal structure. The next stage is aging. The third stage is drying, during which excess solvent is removed. The final stage is sintering, during which the porous structure is eliminated, the residual organisms are removed, and the minerals are crystallized. Especially noticing the aging stage, the

lines, no other line appears. It suggests that pure crystalline HA phase can be produced at 700 8C. Fig. 3 demonstrates that the sintering temperature plays an important role in the formation of HA. As the sintering temperature is increased from 600 to 900 8C, several of the HA lines become more distinct at higher temperatures, and also the widths of the lines become more narrow, which suggests an increase in the crystallite degree. It can also be seen that additional crystalline phases (h-TCP and CaO) appear at 800 and 900 8C, and no other crystalline phase presents besides HA at 600 and 700 8C. It could be concluded that HA could be decomposed into h-TCP and CaO as the sintering temperature is at 800 8C or above. The reaction is proposed as follows: Ca10 PO4 6 OH2 3Ca3 PO4 2 CaO H2 O 1

4h

Intensity (a.u.)

48h

72h

20

40

60

So to obtain the pure HA, the sintering temperature should be below 800 8C. In order to investigate the effect of aging time on the formation of pure HA, the samples aged 4, 48, 72 h were

2 (Degrees)
Fig. 4. X-ray diffraction pattern of HA powders, showing the effect of the aging time. The diffraction lines corresponding to HA and h-TCP are indicated by the * and +, respectively. The CaO lines are indicated by o.

W. Feng et al. / Materials Letters 59 (2005) 916919

919

100nm

100nm

100nm

(a)

(b)

(c)

Fig. 5. TEM images of HA powders sintered at 700 8C. (a) Aged for 4 h, (b) aged for 48 h, (c) aged for 72 h.

resulting cross-linked structure of the molecules would increase during aging. As the aging time increases, the cross-linked structure also increases. While details of this cross-linked structure are not known, according to the results of this study, it seems reasonable to assume that the larger the cross-linked structure, the larger the final HA powder would be. Further work is required to carry out in order to understand the synthesis mechanism of the HA powders produced by this simple solgel technique.

References
[1] P. Layrotte, A. Ito, T. Tateishi, J. Am. Ceram. Soc. 81 (1998) 1421. [2] P. Li, C. Ohtsuki, T. Kokubo, K. Nakanishi, N. Soga, T. Nakamura, T. Yamamuro, J. Am. Ceram. Soc. 75 (1992) 2094. [3] W. Kim, Q.W. Zhang, F. Saito, J. Mater. Sci. 35 (2000) 5401. [4] A.C. Tas, J. Eur. Ceram. Soc. 20 (2000) 2389. [5] A. Lopez-Macipe, R. Rodriguez-Clemente, A. Hidalgo-Lopez, I. Arita, M.V. Garcia-Garduno, E. Rivera, V.M. Castano, J. Mater. Synth. Process. 6 (1998) 121. [6] L.Y. Huang, K.W. Xu, J. Lu, J. Mater. Sci., Mater. Med. 11 (2000) 667. [7] W.J. Weng, J.L. Baptista, Biomaterials 19 (1998) 125. [8] M. Yoshmura, H. Suda, K. Okmoto, K. Loku, J. Mater. Sci. 29 (1994) 3399. [9] G.K. Lim, J. Wang, S.C. Ng, L.M. Gan, J. Mater. Chem. 9 (1999) 1635. [10] G. Bezzi, G. Celotti, E. Landi, T.M.G. La Torretta, I. Sopyan, A. Tampieri, Mater. Chem. Phys. 78 (2003) 816. [11] C.S. Chai, K.A. Gross, B. Ben-Nissan, Biomaterials 19 (1998) 2291. [12] T.K. Anee, M. Ashok, M. Palanichamy, S. Naray-ana Kalkura, Mater. Chem. Phys. 80 (2003) 725. [13] C.M. Lopatin, V. Pizziconi, T.L. Alford, T. Laursen, Thin Solid Films 326 (1998) 227. [14] C.J. Brinker, G.W. Scherer, Solgel science, Academic Press, Boston, MA, 1990. [15] JCPDS Card No. 9-432, 1994.

4. Conclusion This solgel method provides a simple route for synthesis of hydroxyapatite nanopowders. The crystalline degree and morphology of the resulting nanopowders are dependent on the sintering temperature and aging time. The crystalline degree of the HA nanopowders increases with the increase of firing temperature, and HA can decompose at 800 8C and above 800 8C. The crystal size of the HA nanopowders increases with the increase of aging time. The size of HA nanopowders sintered at 700 and aged for 4 h is 1015 nm.