The results of a microscopy, SEM-EDS, XRD, FTIR, and Raman spectra study of the nacres of the Pinctada martensii pearls from Zhanjiang city, China shows that they can be classified as the high-quality, medium-quality, and inferior-quality pearls. Aragonite, the main inorganic mineralogy in the nacres, was crystallized and grown up in the compartments formed by the silk and radial organic sheets originating from organic matters secreted by the mantle of mollusks. The crystalline orientations of aragonite tablets were changed from the (002), (012) and (102) crystalline plane nets in the early to the (002) crystalline plane net only in the later. The formation processes of the microstructure of the nacres could be divided into three stages. In the early stage, the precursor particles of aragonite nucleated and grew up fast; then, porous aragonite aggregates consisting of the fine aragonite crystals were formed. In the middle stage, the aragonite crystals directionally grew up to form the aragonite tablets and microlayers. The surface of the aragonite tablets and microlayers are rough and few porous, and the edges of the crystals were serrated. In the last stage, the aragonite tablets in the aragonite microlayer mixed perfectly together to form high-quality aragonite layer whose surface was smooth and perfect. 1. Introduction The nacres of pearl, products of the biomineralization of the mollusks, are natural nano-organic-inorganic composite materials. Their special physical and chemical properties have excited more and more attentions of material scientists, mineralogists, and biologists. For instance, the nacres of pearl are widely used in the production of the pearl wool and pearl fiber because their break resistance performance can reach about 3000 times of that of the pure inorganic materials [1]. The special physical and chemical properties of the nacres of pearl depend on their unique microstructure whose formation process are typical self-assembly process of nanomaterials. Additionally, the degree of order of aragonite crystals in the nacres highly impacts the quality of the pearl. Currently, based on the above reasons, the research of the microstructure of the nacres of pearl has become an international hotspot and frontier subject. Up to now, to explain the formation mechanism of the microstructure of the nacres of pearl, the compartment theory [2], the bridge theory [3, 4], and the template theory [5, 6] have been established. Although the established modes are effective on the studies of the configuration and formation process of microstructural
References
[1]
A. M. Belcher, P. K. Hansma, G. D. Stucky, and D. E. Morse, “First steps in harnessing the potential of biomineralization as a route to new high-performance composite materials,” Acta Materialia, vol. 46, no. 3, pp. 733–736, 1998.
[2]
H. Nakahara, M. Kakei, and G. Bevelander, “Electron microscopic and amino acid studies on the outer and inner shell layers of Haliotis rufescens,” Venus, vol. 41, no. 1, pp. 33–46, 1982.
[3]
N. Watabe, “Crystal growth of calcium carbonate in the invertebrates,” Progress In Crystal Growth And Characterization, vol. 4, no. 1-2, pp. 99–147, 1981.
[4]
T. E. Sch?ffer, C. Ionescu-Zanetti, R. Proksch et al., “Does abalone nacre form by heteroepitaxial nucleation or by growth through mineral bridges?” Chemistry of Materials, vol. 9, no. 8, pp. 1731–1740, 1997.
[5]
S. Weiner and L. Hood, “Soluble protein of the organic matrix of mollusk shells: a potential template for shell formation,” Science, vol. 190, no. 4218, pp. 987–989, 1975.
[6]
S. Weiner and L. Addadi, “Acidic macromolecules of mineralized tissues: the controllers of crystal formation,” Trends in Biochemical Sciences, vol. 16, no. 7, pp. 252–256, 1991.
[7]
G. S. Zhang and X. D. Xie, “Preferential orientation of aragonite crystals in nacre of mollusc shells,” Journal of Inorganic Materials, vol. 15, no. 4, p. 768, 2000.
[8]
G. Zhang and X. Xie, “Utrastructure and formation theory of nacre shells,” Journal of Mineralogy and Petrology, vol. 20, no. 1, pp. 11–16, 2000.
[9]
N. Watabe, “Studies on shell formation. XI. Crystal-matrix relationships in the inner layers of mollusk shells,” Journal of Ultrasructure Research, vol. 12, no. 3, pp. 351–370, 1965.
[10]
S. Manne, C. M. Zaremba, R. Giles et al., “Atomic force microscopy of the nacreous layer in mollusc shells,” Proceedings of the Royal Society B, vol. 256, no. 1345, pp. 17–23, 1994.
[11]
X. Zhang, W. Wu, and J. Wang, “Dynamic analysis of preferential orientation of aragonite crystals in nacre from mollusk shell,” Chinese Science Bulletin, vol. 52, no. 24, pp. 3452–3456, 2007.
[12]
F. Song, A. K. Soh, and Y. L. Bai, “Structural and mechanical properties of the organic matrix layers of nacre,” Biomaterials, vol. 24, no. 20, pp. 3623–3631, 2003.
[13]
E. Zhang, M. Xin, and M. S. Peng, “A study of compositional characteristics of Chinese cultured pearls,” Acta Petrolog. Et Mineral, vol. 26, no. 4, pp. 381–386, 2007.
[14]
G. S. Zhang and X. H. Li, “Characteristics of FTIR spectra of biogenic aragonite in mollusk shells,” Spectroscopy and Spectral Analysis, vol. 25, no. 10, pp. 1588–1590, 2005.
[15]
G. S. Zhang and S. L. Ding, “Effect of griding on IR spectra of aragonite,” Mineral Resource Geology, vol. 19, no. 110, pp. 429–431, 2005.
[16]
R. W. Gauldie, S. K. Sharma, and E. Volk, “Micro-Raman spectral study of vaterite and aragonite otoliths of the coho salmon, Oncorhynchus kisutch,” Comparative Biochemistry and Physiology, vol. 118, no. 3, pp. 753–757, 1997.
[17]
Y. L. Hao, Situ Raman Spectra of Freshwater Cultured Pearls and the Phase Transformation of Its Inorganic Cystals, Guangxi University, Nanning, China, 2005.
[18]
S. M. dePaula, M. F. G. Huila, K. Araki, and H. E. Toma, “Confocal Raman and electronic microscopy studies on the topotactic conversion of calcium carbonate from Pomacea lineate shells into hydroxyapatite bioceramic materials in phosphate media,” Micron, vol. 41, no. 8, pp. 983–989, 2010.
[19]
S. Raz, S. Weiner, and L. Addadi, “Formation of high-magnesian calcites via an amorphous precursor phase: possible biological implications,” Advanced Materials, vol. 12, no. 1, pp. 38–42, 2000.
[20]
G. Falini, S. Fermani, M. Gazzano, and A. Ripamonti, “Polymorphism and architectural crystal assembly of calcium carbonate in biologically inspired polymeric matrices,” Journal of the Chemical Society, Dalton Transactions, no. 21, pp. 3983–3987, 2000.
[21]
J. J. J. M. Donners, B. R. Heywood, E. W. Meijer, R. J. M. Nolte, and N. A. J. M. Sommerdijk, “Control over calcium carbonate phase formation by dendrimer/surfactant Templates,” Chemistry, vol. 8, no. 11, pp. 2561–2567, 2002.
[22]
A. Sugawara and T. Kato, “Aragonite CaCO3 thin-film formation by cooperation of Mg2+ and organic polymer matrices,” Chemical Communications, no. 6, pp. 487–488, 2000.
[23]
J. C. Marxen and W. Becker, “Calcium binding constituents of the organic shell matrix from the freshwater snail Biomphalaria glabrata,” Comparative Biochemistry and Physiology, vol. 127, no. 2, pp. 235–242, 2000.
[24]
V. T. C. Chang, R. J. P. Williams, A. Makishima, N. S. Belshawl, and R. K. O'Nions, “Mg and Ca isotope fractionation during CaCO3 biomineralisation,” Biochemical and Biophysical Research Communications, vol. 323, no. 1, pp. 79–85, 2004.
[25]
B. Pokroy, J. P. Quintana, E. N. Caspi, A. Berner, and E. Zolotoyabko, “Anisotropic lattice distortions in biogenic aragonite,” Nature Materials, vol. 3, no. 12, pp. 900–902, 2004.
[26]
S. Weiner, Y. Levi-Kalisman, S. Raz, and L. Addadi, “Biologically formed amorphous calcium carbonate,” Connective Tissue Research, vol. 44, no. 1, pp. 214–218, 2003.
[27]
M. Suzuki, K. Saruwatari, T. Kogure et al., “An acidic matrix protein, Pif, is a key macromolecule for nacre formation,” Science, vol. 325, no. 5946, pp. 1388–1390, 2009.
[28]
M. Fritz, A. M. Belcher, M. Radmacher et al., “Flat pearls from biofabrication of organized composites on inorganic substrates,” Nature, vol. 371, no. 6492, pp. 49–51, 1994.
[29]
Y. F. Ma, Y. H. Gao, D. N. Ren, and Q. L. Feng, “The effect of soluble matrix proteins from aragonite pearls on the crystallization of CaCO3,” Acta Petrol. Et Mineral, vol. 28, no. 6, pp. 605–610, 2009.