Correlation between intrinsic dipole moment and pyroelectric coefficient of Fe-Mg tourmaline

Abstract

Single-crystal X-ray diffraction structural data of four Fe-Mg tourmalines with different Fe contents from Xinjiang, Sichuan, and Yunnan Provinces, China, were collected at room temperature and −100°C. The intrinsic dipole moments of polyhedra and the total intrinsic dipole moment of the unit cell were calculated. By comparing the intrinsic electric dipole moments of the X, Y, Z, T, and B site polyhedra, it is found that the T site polyhedron makes the greatest contribution to the total intrinsic dipole moment. The pyroelectric coefficients of four Fe-Mg tourmalines were experimentally determined, and the influence of intrinsic dipole moments on their pyroelectric properties was investigated. The experimental results show that, compared with the case at room temperature, the intrinsic dipole moments change with the total Fe content at −100°C in a completely different way. With the decrease of temperature, the total intrinsic dipole moments of tourmaline decrease. Over the same temperature interval, the pyroelectric coefficients increase with the increase in intrinsic dipole moment.

Keywords

tourmaline / pyroelectricity / dipole moment / polyhedra

References

[1] Hawthorne FC, Henry DJ. Classification of the minerals of the tourmaline group. Eur. J. Mineral., 1999, 11(2): 201

[2] Lang SB. A 2400 year history of pyroelectricity: from ancient Greece to exploration of the solar system. Br. Ceram. Trans., 2004, 103(2): 65.

[3] Donnay G. Structural mechanism of pyroelectricity in tourmaline. Acta Crystallogr., Sect. A, 1977, 33(6): 927.

[4] Nakamura T, Kubo T. Tourmaline group crystals reaction with water. Ferroelectrics, 1992, 137(1): 13.

[5] Liao LB. Crystal Chemistry and Crystal Physics, 1999, Beijing, Geological Publishing House, 138

[6] Li Y, Huang ZH, Liu YG, Fang MH. Characterization of dielectric performance of tourmaline single crystals from Yunnan, China. CrystEngComm, 2012, 14(21): 7153.

[7] Jin ZZ, Ji ZJ, Liang JS, Wang J, Sui TB. Observation of spontaneous polarization of tourmaline. Chin. Phys., 2003, 12(2): 222.

[8] Tatli A, Pavlovic AS. Thermal expansion of tourmaline single crystals from 80 to 300 K. Phys. Rev. B, 1988, 38(14): 10072.

[9] Hawkins KD, Mackinnon IDR, Schneeberger H. Influence of chemistry on the pyroelectric effect in tourmaline. Am. Mineral., 1995, 80, 491

[10] Lang SB. Sourcebook of Pyroelectricity, 1974, London, Gordon and Breach, 375

[11] Dyar MD, Taylor ME, Lutz TM, Francis CA, Guidotti CV, Wise M. Inclusive chemical characterization of tourmaline: Mössbauer study of Fe valence and site occupancy. Am. Mineral., 1998, 83, 848

[12] Pieczka A, Kraczka J. Oxidized tourmalines:a combined chemical, XRD, and Mössbauer study. Eur. J. Mineral., 2004, 16(2): 309.

[13] Zhao CC, Liao LB, Xia ZG, Sun XN. Temperature-dependent Raman and infrared spectroscopy study on iron-magnesium tourmalines with different Fe content. Vib. Spectrosc., 2012, 62, 28.

[14] Zhao CC, Liao LB, Yuan JY, Cheng Y. Influence of temperature, the content and valence of Fe in tourmaline on their polyhedron distortion. J. Chin. Ceram. Soc., 2013, 41(1): 103

[15] Zhao CC, Liao LB. Mössbauer spectroscopic study of Fe-Mg tourmalines with different Fe contents. Sci. China Earth Sci., 2012, 55(9): 1489.

[16] Grice JD, Robinson GW. Feruvite, a new member of the tourmaline group, and its crystal structure. Can. Mineral., 1989, 27(2): 199

[17] Rosenberg PE, Foit FF Jr. Synthesis and characterization of alkali-free tourmaline. Am. Mineral., 1979, 64, 180

[18] Brese NE, O’Keeffe M. Bond-valence parameters for solids. Acta Crystallogr. Sect. B, 1991, 47, 192.

[19] Phys. Rev. Lett., 2002, 89(7)

[20] Ertl A, Hughes JM, Pertlik F, Foit FF Jr. Wright SE, Brandstätter F, Marler B. Polyhedron distortions in tourmaline. Can. Mineral., 2002, 40(1): 153.

[21] McKeown DA. Raman spectroscopy, vibrational analysis, and heating of buergerite tourmaline. Phys. Chem. Miner., 2008, 35(5): 259.