Diffuse α-β transition in surface layer of natural quartz

Category: 15-4
G.A. Sobolev, V.I. Vettegren, S.M. Kireenkova, Ju.A. Morozov, A.I. Smul'skaja, R.I. Mamalimov, V.B. Kulik


UDC 550.32


G.A. Sobolev(1), V.I. Vettegren(2), S.M. Kireenkova(1), Ju.A. Morozov(1), A.I. Smul'skaja(1), R.I. Mamalimov(2), V.B. Kulik(2)


(1) Schmidt Institute of Physics of the Earth, Russian Academy of Sciences, Moscow, Russia

(2) Ioffe Physical Technical Institute RAS, St. Petersburg, Russia


Abstract. Temperature dependence of a-phase concentration was investigated by infrared and Raman spectroscopy in the surface layers and volume of plates cut from the quartz crystal being the part of drusen deposits Dodo in the Polar Urals. It was found that in the volume the temperature dependence behaves as expected for the first-order phase transition, namely, before 800 K, it remains constant and at higher temperatures, tends to zero. In the surface layers ~0.15 and ~1 mm thick, the a-phase concentration decreases monotonically by ~10% with the increase in temperature up to 780  K. In the layer at a depth of ~6 mm, temperature dependence of a-phase concentration has two minima at ~370 and ~570 K, where the concentration is reduced by approximately half. The observed relation between a-phase concentration and increase in temperature was explained by crystal lattice distortion near spiral dislocations in the surface layers of quartz. Tensile stresses appear in the surface layer about 1 mm thick and reach 170 MPa at 780 K. The cracks are formed under the influence of the stresses which cause fracture of the sample. The initiation of tensile stress was explained by increase in the layer volume located at a distance of ~6 mm from the surface due to increase of b-phase concentration in it.


Keywords: quartz, phase transition, internal stresses.


Almeida R.M. and Pantano C.G. Structural investigation of silica gel films by infrared spectroscopy, J. Appl. Phys., 1990, vol. 68, pp. 4225–4232.

Ayensu A. Interaction between dislocations and precipitated water bubbles during high temperature creep of quartz, J. Materials Sci., 1997, vol. 32, pp. 123–128.

Bakker R.J. and Jansen J.B. A mechanism for preferential H2O linkage from fluid inclusions in quartz, based on TEM observations, Contrib. Mineral Petrol., 1994, vol. 116, pp. 7–20.

Bogatikov O.A., Inorganic Nanoparticles in Nature, Vestnik Ross. Akad. Nauk, 2003, vol. 73, no. 5, pp. 426–428.

Bommei H.E., Mason W.P., and Warner A.W. Dislocations, relaxations, and inelasticity of crystal quartz, Phys. Rev., 1956, vol. 102, no. 1, pp. 6471.

Chanturiya V.A., Trubetskoi K.N., Viktorov S.D., and Bunin I. Zh., Nanochastitsy v protsesse vskrytiya i razrusheniya materialov (Nanoparticles during Material Rupture and Failure), Moscow: IPKO RAN, 2006.

Dove P.M., Han N., and De Yoreo J.J. Mechanisms of classical crystal growth theory explains quartz and silicate dissolution behavior, PNAS, 2005, vol. 102, no. 43, pp. 15357–15362.

Etchepare J., Merian M., and Kaplan P. Vibrational normal modes of SiO2 a and b quartz, J. Chem. Phys., 1974, vol. 60, no. 5, pp. 18731876.

Iishi K. and Yamacuchi H. Study of the Force Field and the Vibrational Normal Modes in the a-b Quartz Phase Transition, American Mineralogist., 1975, vol. 60, pp. 907–912.

Ipatova I.P., Maradudin A.A., and Wallis R.F. The temperature dependence of the width of the fundamental lattice-vibrations absorption peak in ionic crystal. II. Approximate numerical results, Phys. Rev., 1967, vol. 155, no. 3, pp. 882895.

Kamp P.C. Smectite-illite-muscovite transformations, quartz dissolution, and silica release in shales, Clays and Clay Minerals., 2008, vol. 56, pp. 6681.

Kenzig W., Ferroelectrics and Antiferroelectrics, Berlin: Springer-Verlag, 1957.

Kireenkova S.M. and Sobolev G.A., On the Possibility of Studying Natural Processes on the Nanoscale in the Physics of the Earth, Geofiz. Issled., 2005, no. 1, pp. 108–115.

Kristiansen K., Valtiner M., Greene G.W., Boles J.R., and Israelachvili J.N. Pressure solution – The importance of the electrochemical surface potentials, Geochim. Cosmochim. Acta., 2011, vol. 75, pp. 6882–6892.

Kulik V.B., Sobolev G.A., Vettegren V.I., and Kireenkova S.M., A Study of Nanocrystals in Rocks Subjected to Natural and Engineered Mechanical and Thermal Impacts, Izv. Phys. Earth, 2011, vol. 47, no. 10, pp. 873–878. 

Landsberg G. S., Optika (Optics), Moscow: FIZMATLIT, 2003.

Nikitin A. N., Vasin R. N., Balagurov A. M., Sobolev G. A., and Ponomarev A. V., Investigation of thermal and deformation properties of quartzite in a temperature range of polymorphous α-β transition by neutron diffraction and acoustic emission methods, Phys. Part. Nucl. Lett., 2006, vol. 3, no.1, pp. 46-53.

Nikitin A. N., Markova G. V., Balagurov A. M., Vasin R. N., and Alekseeva O. V., Investigation of the structure and properties of quartz in the α-β transition range by neutron diffraction and mechanical spectroscopy, Crystallogr. Rep., 2007, vol. 52, no. 3, pp. 428-435.

Kuzmenko A.B. Kramers-Kronig constrained vibriational analysis of optical spectra, Rev. Sci. Instr., 2005, vol. 76. 083108.

Lakshtanov D.L., Sinogeikin S.V., and Bass J.D. High-temperature phase transitions and elasticity of silica polymorphs, Phys. Chem. Minerals., 2007, vol. 34, pp. 11–22.

Lang A.R. and Miuscov V.F. Dislocations and Fault Surfaces in Synthetic Quartz, J. Appl. Phys., 1967, vol. 38, pp. 24772483.

Madelung O. Festkorpertheorie. Berlin: Springer, 1972. 416 s.

Meyer E.E., Greene G.W., Alcantar N.A., Israelachvili J.N., and Boles J.R. Experimental investigation of the dissolution of quartz by a muscovite mica surface: Implications for pressure solution, J. Geophys. Res., 2006, vol. 111. B08202.

Raz U., Girsperger S., and Thompson A.B. Thermal expansion, compressibility and volumetric changes of quartz obtained by single crystal dilatometry to 700°C and 3.5 kilobars (0.35 GPa), e-collection.library.ethz.ch/view/eth:25671. 2002.

Sarma D.S., Mohan M.R., and Prasad P.S.R. Infrared Spectroscopic studies on the Mobility of Metamorphic Fluid in Quartz veins of Dharwar Craton, Open Mineralogy J., 2010, vol. 4, pp. 1–8.

Savin M. and Reichenbach G. Infrared spectra of muscovite as affected by chemical composition, heating and particle size, Clay minerals., 1978, vol. 13, pp. 241–254.

Sobolev G.A., Genshaft Yu.S., Kireenkova S.M., Morozov Yu.A., Smul’skaya A.I., Vettegren V.I., and Kulik V.B., Effects of High Pressure and Temperature on the Properties of Nanocrystals in Rocks: Evidences from Raman Spectroscopy, Izv. Phys. Earth, 2011, vol. 47, no. 6, pp. 465–474

Sobolev G.A., Kireenkova S.M., Morozov Yu.A., Smul’skaya A.I., Vettegren V.I., Kulik, V.B., and Mamalimov R.I. Study of nanocrystals in the dynamic slip zone, Izv. Phys. Earth, 2012, vol. 48, no. 9-10, pp. 684-692.

Sobolev G.A., Kireenkova S.M., Morozov Y.A., Smul'skaya A.I., Tsel'movich V.A., Vettegren V.I., and Kulik V.B. Nanostructures in deep xenolite before and after straining, Izv. Phys. Earth, 2009, vol. 45, no. 9, pp. 731–739.

Sobolev G.A., Ponomarev A.V., Nikitin A.N., Balagurov A.M., and Vasin R.N. Dynamics of the Polymorphic α-β-Transition in Quartzite from Data of Neutron Diffractometry and Acoustic Emission, Izv. Phys. Earth, 2004, vol. 40, no. 10, pp. 788-797.

Sobolev G.A., Vettegren V.I., Kireenkova S.M., Kulik V.B., Morozov Yu.A., Smul’skaya A.I., and Pikulin V.A., Raman Spectroscopy of Nanocrystals in Rock, Izv. Phys. Earth, 2007, vol. 43, no. 6, pp. 447–454.

Spitzer W.G., Kleinman D.A. Infrared lattice bands of quartz, Phys. Rev., 1961, vol. 121, no. 5, pp. 1324–1335.

Velde B. Infrared spectra of synthetic micas in the series muscovite-MgAl celadonite, American Mineralogist., 1978, vol. 63, pp. 343–349.

Vettegren V.I., Mamalimov R.I., and Sobolev G.A., Diffuse phase transition in a surface quartz layer with variations in temperature, Phys. Solid State, 2013,vol. 55, no. 10, pp. 2102-2107

Vettegren V.I., Mamalimov R.I., Sobolev G.A., Kireenkova S.M., Morozov Yu.A., and Smul’skaya A.I., IR Spectroscopy of Quartz Nanocrystals Formed during Intense Crushing of a Heterogeneous Material (Granite), Phys. Solid State, 2011, vol. 53, no. 12, pp. 2495–2499.

Vettegren V.I., Mamalimov R.I., Sobolev G.A., Kireenkova S.M., Morozov Yu.A., and Smul’skaya A.I.Temperature-induced phase transition in quartz nanocrystals dispersed in pseudotachylite, Phys. Solid State, 2013, vol. 55, no. 5, pp. 1063-1069


Yamagishi H., Nakashima S., and Ito Y. High temperature infrared spectra of hydrous microcrystalline quartz, Phys. Chem. Minerals., 1997, vol. 24, pp. 66–74.