Abstract
Phase pure, stable nanocrystalline brushite particles with average diameter in the range of 23–87 nm were obtained by the reverse microemulsion technique employing a mixture of surfactants (Aliquat 336 & Tween 80) as template directing agents, and calcium nitrate tetrahydrate and biammonium hydrogen phosphate as precursors. Particle sizes and morphologies were tuned by adjusting the reaction parameters, precursor concentration and temperature. FTIR, TEM, and XRD were used to characterize morphological changes of as synthesized nanoparticles. FTIR and XRD analyses confirmed the formation of brushite nanoparticles. Variations in the reaction temperature resulted in changes in the particle morphology and distribution. At high temperatures (60°C), the sample exhibited high monodispersity and spherical morphology with the average grain size of 42 nm. At low temperatures (6°C), nanoflakes were formed. The results suggest that a reverse microemulsion system provides facile media for control of the phase and morphology of nanoscale calcium phosphate biominerals. A mechanism providing an insight into the formation of brushite particles has also been proposed.
Similar content being viewed by others
References
Abbona, F., Madsen, H. E. L., & Boistelle, R. (1986) The initial phases of calcium and magnesium phosphates precipitated from solutions of high to medium concentrations. Journal of Crystal Growth, 74, 581–590. DOI: 10.1016/0022-0248(86)90205-8.
Arifuzzaman, S. M., & Rohani, S. (2004) Experimental study of brushite precipitation. Journal of Crystal Growth, 267, 624–634. DOI: 10.1016/j.jcrysgro.2004.04.024.
Bailey, R. T., & Holt, C. (1989). Fourier transform infrared spectroscopy and characterization of biological calcium phosphates. In D. W. L. Huskins (Ed.), Calcified tissue (pp. 93–119). Boca Raton, FL, USA: CRC Press.
Barone, J. P., & Nancollas, G. H. (1977) The seeded growth of calcium phosphates. The effect of solid/solution ratio in controlling the nature of the growth phase. Journal of Colloid and Interface Science, 62, 421–431. DOI: 10.1016/0021-9797(77)90093-5.
Berry, E. E., & Baddiel, C. B. (1967) The infra-red spectrum of dicalcium phosphate dihydrate (brushite). Spectrochimica Acta Part A: Molecular Spectroscopy, 23, 2089–2097. DOI: 10.1016/0584-8539(67)80097-7.
Bohner, M., Merkle, H. P., & Lemaître, J. (2000) In vitro aging of calcium phosphate cement. Journal of Materials Science: Materials in Medicine, 11, 155–162. DOI: 10.1023/A:1008927624493.
Boskey, A. L., & Posner, A. S. (1973) Conversion of amorphous calcium phosphate to microcrystalline hydroxyapatite. A pH-dependent, solution-mediated, solid-solid conversion. The Journal of Physical Chemistry, 77, 2313–2317. DOI: 10.1021/j100638a011.
Cai, Y., Pan, H., Xu, X., Hu, Q., Li, L., & Tang, R. (2007) Ultrasonic controlled morphology transformation of hollow calcium phosphate nanospheres: A Smart and biocompatible drug release system. Chemistry of Materials, 19, 3081–3083. DOI: 10.1021/cm070298t.
Chen, X., Sun, X., & Li, Y. (2002) Self-assembling vanadium oxide nanotubes by organic molecular templates. Inorganic Chemistry, 41, 4524–4530. DOI: 10.1021/ic020092o.
Fowler, C. E., Li, M., Mann, S., & Margolis, H. C. (2005) Influence of surfactant assembly on the formation of calcium phosphate materials-A model for dental enamel formation. Journal of Material Chemistry, 15, 3317–3325. DOI: 10.1039/b503312h.
Guo, G., Sun, Y., Wang, Z., & Guo, H. (2005) Preparation of hydroxyapatite nanoparticles by reverse microemulsion. Ceramic International, 31, 869–872. DOI: 10.1016/j.ceramint.2004.10.003.
Hlabse, T., & Walton, A. G. (1965) The nucleation of calcium phosphate from solution. Analytica Chimica Acta, 33, 373–377. DOI: 10.1016/S0003-2670(01)84906-0.
Khor, K. A., & Cheang, P. (1997) Plasma sprayed hydroxyapatite (HA) coatings produced with flame spheroidised powders. Journal of Materials Processing Technology, 63, 271–276. DOI: 10.1016/S0924-0136(96)02634-9.
Kumar, M., Dasarathy, H., & Riley, C. (1999a) Electrodeposition of brushite coatings and their transformation to hydroxyapatite in aqueous solutions. Journal of Biomedical and Materials Research, 45, 302–310. DOI: 302-310.10.1002/(SICI)1097-4636(19990615)45:4<302::AID-JBM4>3.0.CO;2-A.
Kumar, M., Xie, J., Chittur, K., & Riley, C. (1999b) Transformation of modified brushite to hydroxyapatite in aqueous solution: effects of potassium substitution. Biomaterials, 20, 1389–1399. DOI: 10.1016/S0142-9612(99)00043-5.
Li, M., Schnablegger, H., & Mann, S. (1999) Coupled synthesis and self-assembly of nanoparticles to give structures with controlled organization. Nature, 402, 393–395. DOI: 10.1038/46509.
Li, Y. D., Li, X. L., He, R. R., Zhu, J., & Deng, Z. X. (2002) Artificial lamellar mesostructures to WS2 nanotubes. Journal of the American Chemical Society, 124, 1411–1416. DOI: 10.1021/ja012055m.
Lim, H. N., Kassim, A., Huang, N. M., Hashim, R., Radiman, S., Khiew, P. S., & Chiu, W. S. (2009) Fabrication and characterization of 1D brushite nanomaterials via sucrose ester reverse microemulsion. Ceramics International, 35, 2891–2897. DOI: 10.1016/j.ceramint.2009.03.044.
Montastruc, L., Azzaro-Pantel, C., Biscans, B., Cabassud, M., & Domenech, S. (2003) A thermochemical approach for calcium phosphate precipitation modeling in a pellet reactor. Chemical Engineering Journal, 94, 41–50. DOI: 10.1016/S1385-8947(03)00044-5.
Nielson, A. E., & Söhnel, O. (1971) Interfacial tensions electrolyte crystal-aqueous solution, from nucleation data. Journal of Crystal Growth, 11, 233–242. DOI: 10.1016/0022-0248(71)90090-X.
Oliveira, C., Ferreira, A., & Rocha, F. (2007) Dicalcium phosphate dihydrate precipitation: Characterization and crystal growth. Chemical Engineering Research and Design, 85(A12), 1655–1661. DOI: 10.1205/cherd06237.
Pennel, G., Leroy, G., Rey, C., Sombret, B., Huvenne, J. P., & Bres, E. (1997) Infrared and Raman microspectrometry study of fluoro-fluoro-hydroxy and hydroxy-apatite powders. Journal of Material Science: Materials in Medicine, 8, 271–276. DOI: 10.1023/A:1018504126866.
Roop Kumar, R., Prakash, K. H., Yennie, K., Cheang, P., & Khor, K. A. (2005) Synthesis and characterisation of hydroxyapatite nano-rods/whiskers. Key Engineering Materials, 284–286, 59–62. DOI: 10.4028/www.scientific.net/KEM.284-286.59.
Sainz-Díaz, C. I., Villacampa, A., & Otálora, F. (2004) Crystallographic properties of the calcium phosphate mineral, brushite, by means of First Principles calculations. American Mineralogist, 89, 307–313.
Singh, S., Bhardwaj, P., Singh, V., Aggarwal, S., & Mandal, U. K. (2008) Synthesis of nanocrystalline calcium phosphate in microemulsion-effect of nature of surfactants. Journal of Colloid and Interface Science, 319, 322–329. DOI: 10.1016/j.jcis.2007.09.059.
Tas, A. C. (2000) Synthesis of biomimetic Ca-hydroxyapatite powders at 37.C in synthetic body fluids. Biomaterials, 21, 1429–1438. DOI: 10.1016/S0142-9612(00)00019-3.
Tiselius, A., Hjertén, S., & Levin, Ö. (1995) Protein chromatography on calcium phosphate columns. Archives of Biochemistry and Biophysics, 65, 132–155. DOI: 10.1016/0003-9861(56)90183-7.
Tortet, L., Gavarri, J. R., Nihoul, G., & Dianoux, A. J. (1997) Study of protonic mobility in CaHPO4·2H2O (brushite) and CaHPO4 (monetite) by infrared spectroscopy and neutron scattering. Journal of Solid State Chemistry, 132, 6–16. DOI: 10.1006/jssc.1997.7383.
Uota, M., Arakawa, H., Kitamura, N., Yoshimura, T., Tanaka, J., & Kijima, T. (2005) Synthesis of high surface area hydroxyapatite nanoparticles by mixed surfactant-mediated approach. Langmuir, 21, 4724–4728. DOI: 10.1021/la050029m.
Welch, S., Tuanton, A. E., & Banfield, J. F. (2002) Effect of microorganisms and microbial metabolites on apatite dissolution. Geomicrobiology Journal, 19, 343–367. DOI: 10.1080/01490450290098414.
Xiao, X. F., & Liu, R. F. (2006) Effect of suspension stability on electrophoretic deposition of hydroxyapatite coatings. Material Letters, 60, 2627–2632. DOI: 10.1016/j.matlet.2006.01.048.
Xie, J., Riley, C., Kumar, M., & Chittur, K. (2002) FTIR/ATR study of protein adsorption and brushite transformation to hydroxyapatite. Biomaterials, 23, 3609–3616. DOI: 10.1016/S0142-9612(02)00090-X.
Xu, J., Butler, I. S., & Gilson, D. F. R. (1999) FT-Raman and high-pressure infrared spectroscopic studies of dicalcium phosphate dihydrate (CaHPO4·2H2O) and anhydrous dicalcium phosphate (CaHPO4). Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 55, 2801–2809. DOI: 10.1016/S1386-1425(99)00090-6.
Zhang, Y., & Lu, J. (2008) A mild and efficient biomimetic synthesis of rodlike hydroxyapatite particles with a high aspect ratio using polyvinylpyrrolidone as capping agent. Crystal Growth & Design, 8, 2101–2107. DOI: 10.1021/cg060880e.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Singh, S., Singh, V., Aggarwal, S. et al. Synthesis of brushite nanoparticles at different temperatures. Chem. Pap. 64, 491–498 (2010). https://doi.org/10.2478/s11696-010-0032-8
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.2478/s11696-010-0032-8