Abstract
The results of study of mechanical losses by dynamic methods for silicate, borate, and chalcogenide glasses, metallic glass and glycerol at heating in the glass transition region were analyzed. Essential differences between the dynamic viscosity values η* calculated by means of the Maxwell equation based on the relaxation time at the maximum of losses (ωτ = 1) for labile states of glass, and the experimental values of η for the metastable liquid at the same temperature were revealed. The ratio η*/η was systematized in the framework of kinetic theory of glass transition and thermodynamics. An interpretation of the regularities was proposed based on the theory of dynamic properties of liquids. It was shown that different widths of spectra of relaxation times were the most probable reason of the difference between η* and η. The width of spectrum is determined by the degree of ordering of states of compared metastable liquid and glass at the same temperature; it depends on the thermal prehistory of each state. A wider spectrum of relaxation times corresponds to a more ordered state. For the considered glasses, the ratio of the temperature corresponding to viscosity value η* of the metastable liquid to the temperature of α-relaxation maximum (T α) is 1.03 ± 0.01 at T α variation from 190 to 1550 K. It is the evidence that all the relaxation frequencies, constituting both “narrow” and “broad” spectrum are associated with one and the same molecular mechanism. Mechanical losses in the metastable supercooled glycerol are described by the Maxwell equation with high precision for η values from 1013 to 105 Pa s.
Similar content being viewed by others
References
Qiao, J.C. and Pelletier, J.M., Dynamic mechanical relaxation in bulk metallic glasses, J. Mater. Sci. Technol., 2014, vol. 30, no. 6, pp. 523–545.
Volkenstein, M.V. and Ptitsyn, O.B., The relaxation theory of glass transition, Dokl. Akad. Nauk SSSR, 1955, vol. 103, no. 5, pp. 795–798.
Volkenstein, M.V. and Ptitsyn, O.B., The relaxation theory of glass transition: I. The solution of the basic equation and its investigation, Zh. Tekh. Fiz., 1956, vol. 26, no. 10, pp. 2204–2222.
Nemilov, S.V., Maxwell equation and classical theories of glass transition as a basis for direct calculation of viscosity at glass transition temperature, Glass Phys. Chem., 2013, vol. 39, no. 6, pp. 609–623.
Bartenev, G.M., On the relationship between the glass transition temperature of silicate glass and the rate of cooling and heating, Dokl. Akad. Nauk SSSR, 1951, vol. 76, no. 2, pp. 227–230.
Moynihan, C.T. Montrose, C.J., et al., Structural relaxation in vitreous materials, Ann. NY Acad. Sci., 1976, vol. 279, pp. 15–35.
Moynihan, C.T., Easteal, A.J., Wilder, J., and Tucker, J., Dependence of the glass transition temperature on heating and cooling rate, J. Phys. Chem., 1974, vol. 78, no. 26, pp. 2673–2677.
Mandel’shtam, L.I. and Leontovich, M.A., On the theory of sound absorption in liquids, Zh. Eksp. Teor. Fiz., 1937, vol. 7, no. 3, pp. 438–449.
Solov’ev, V.A., in Osnovy molekulyarnoi akustiki (Principles of Molecular Acoustics), Mikhailov, I.G., Solov’ev, V.A., and Syrnikov, Yu.P, Eds., Moscow: Nauka, 1964, pp. 236–282.
Meister, S., Marhoeffer, C.J., Sciamanda, R., Cotter, L., and Litovitz, T., Ultrasonic viscoelastic properties of associated liquids, J. Chem. Phys., 1960, vol. 31, no. 5, pp. 854–870.
Litovitz, T.A. and Davis, C.M., in Physical Acoustics, Vol. II A Mason W.P., Ed., New York, Academic, 1965, pp. 281–349.
Harrison, G., The Dynamic Properties of Supercooled Liquids, London: Academic, 1976.
Zdaniewsky, W.A., Rindone, G.E., and Day, D.E., The internal friction of glasses, J. Mater. Sci., 1979, vol. 14, pp. 763–775.
Nemilov, S.V., The review of possible interrelations between ionic conductivity, internal friction and the viscosity of glasses and glass forming melts within the framework of Maxwell equations, J. Non-Cryst. Solids, 2011, vol. 357, no. 4, pp. 1243–1263.
Nemilov, S.V., Maxwell equation for electrical conductivity of dielectrics as the basis for direct relationship between the ionic electrical conductivity and mechanical losses in glasses: New problems of the physical chemistry of glass, Glass Phys. Chem., 2012, vol. 38, no. 1, pp. 27–40.
Nemilov, S.V., Ageing kinetics and internal friction of oxide glasses, Glass Sci. Technol., 2005, vol. 78, no. 6, pp. 269–278.
Nemilov, S.V., Structural relaxation in oxide glasses at room temperature, Phys. Chem. Glasses: Eur. J. Glass Sci. Technol., Part B, 2007, vol. 48, no. 4, pp. 291–295.
Nemilov, S.V., The results of application of Maxwell’s equations in glass science, Glass Phys. Chem., 2014, vol. 40, no. 5, pp. 473–485.
Postnikov, V.S., Fizika i khimiya tverdogo sostoyaniya (Physics and Chemistry of Solid State), Moscow: Metallurgy, 1978.
Lillie, H.R., Stress release in glass: A phenomenon involving viscosity as a variable with time, J. Am. Ceram. Soc., 1936, vol. 19, no. 1, pp. 45–54.
Tropin, T.V., Schulz, G., Schmelzer, J.W.P., and Schick, C., Heat capacity measurements and modeling of polystyrene glass transition in a wide range of cooling rates, J. Non-Cryst. Solids, 2015, vol. 409, no. 1, pp. 63–75.
Volkenstein, M.V., On the structural and kinetic characteristics of the vitreous state, in Stekloobraznoe sostoyanie (Proc. 3rd All-Union Conference on the Vitreous State, Leningrad, November 16–20, 1959), PoraiKoshitz, E.A., Ed., Leningrad: Akad. Nauk SSSR, 1960, pp. 132–138.
Garden, J.-L., Guillow, H., Richard, J., and Wondraczek, L., Affinity and its derivatives in the glass transition process, J. Chem. Phys., 2012, vol. 137, no. 2, p. 024505.
Macedo, P.B., Simmons, J.H., and Haller, W., Spectrum of relaxation times and fluctuation theory: Ultrasonic studies on an alkali-borosilicate melt, Phys. Chem. Glasses, 1968, vol. 9, no. 5, pp. 156–164.
Balashov, Yu.S., Andreev, I.V., Mironova, M.L., and Chernyshova, G.L., High-temperature mechanical relaxation in phase-separated sodium borosilicate glasses, Fiz. Khim. Stekla, 1978, vol. 4, no. 1, pp. 116–117.
MDL®SciGlass-7.8: Database, Institute of Theoretical Chemistry, Shrewsbury, MA, 2012.
Leko, V.K. and Mazurin, O.V., Svoistva kvartsevogo stekla (Properties of Silica Glass), Leningrad: Nauka, 1985.
Loryan, S.G., Kostanyan, K.A., Saringyulyan, R.S., Kafyrov, V.M., and Bagdasaryan, E.Kh., Viscosity of silica glasses in the softening range, Elektron.Tekh., Ser. 6: Mater., 1976, no. 2, pp. 53–59.
Andreev, I.V., Balashov, Yu.S., and Ivanov, N.V., Hightemperature internal friction of some stabilized oxide glasses, Fiz. Khim. Stekla, 1981, vol. 7, no. 3, pp. 371–373.
Nemilov, S.V., Relaxation processes in inorganic melts and glasses: an elastic continuum model as a promising basis for the description of the viscosity and electrical conductivity, Glass Phys. Chem., 2010, vol. 36, no. 3, pp. 253–285.
Mazurin, O.V. and Potselueva, L.N., Determination of glass transition temperature from the temperature dependences of viscosity of glass forming melts, Fiz. Khim. Stekla, 1978, vol. 4, no. 5, pp. 570–580.
Andreev, I.V., Balashov, Yu.S., and Mazurin, O.V., The study of rheological properties of window glass by means of dynamic mechanic method, Fiz. Khim. Stekla, 1980, vol. 6, no. 2, pp. 203–210.
Bartenev, G.M. and Lomovskoi, V.A., Relaxation processes in alkali-silicate plate glass and their structure origin, Neorg. Mater., 1993, vol. 29, no. 7, pp. 997–1003.
Bartenev, G.M. and Lomovskoi, V.A., Relaxation properties of alkali silicate glasses from mechanical measurements, Neorg. Mater., 1996, vol. 32, no. 5, pp. 607–619.
Andreev, I.V., Balashov, Yu.S., and Lomovskoi, V.A., High-temperature mechanical relaxation in sodium borate glasses, Fiz. Khim. Stekla, 1984, vol. 10, no. 4, pp. 505–507.
Jansen-Falkenburg, I.A., van Gemert, W.J.Th., and Stevels, J.M., Mechanical relaxation in vitreous borates in the transition range, J. Non-Cryst. Solids, 1978, vol. 29, no. 1, pp. 119–129.
Lomovskoi, V.A., Andreev, I.V., and Balashov, Yu.S., Internal friction in the region of glass transition of lead borate glasses, Fiz. Khim. Stekla, 1984, vol. 10, no. 4, pp. 503–504.
Bilanich, V.S. and Gorvat, A.A., High-temperature relaxation transition in arsenic chalcogenides, Fiz. Khim. Stekla, 1998, vol. 24, no. 6, pp. 825–829.
Nemilov, S.V., Viscosity and elastic properties of melts and glasses of As–S system and their valence structure, Fiz. Khim. Stekla, 1979, vol. 5, no. 4, pp. 398–409.
Chang, S.S., Bestul, A.B., and Horman, J.A., Critical configurational entropy of glass transition, Trav. VII Congress Int. du Verre, Bruxelles, 1965, 26 1.13.
Wang, W.H., Dong, C., and Shek, C.H., Bulk metallic glasses, Mater. Sci. Eng., 2004, vol. 44, pp. 45–89.
Khonik, V.A., Understanding of the structural relaxation of metallic glasses within the framework of the interstitialcy theory, Metals, 2015, vol. 5, no. 2, pp. 504–529.
Khonik, V.A., Internal friction of metallic glasses: mechanisms and conditions of their realization, J. Phys. IV, 1996, vol. 6, no. C8, pp. 591–600.
Spivak, L.V. and Khonik, V.A., On the nature of lowtemperature anomalies of inelastic properties of metal glasses, Zh. Tekh. Fiz., 1997, vol. 67, no. 10, pp. 35–46.
Damson, B., Weller, M., Feuerbacher, M., Grushko, B., and Urban, K., Mechanical spectroscopy of i-Al–Pd–Mn and d-Al–Ni–Co, Mater. Sci. Eng., 2000, vols. 294–296, pp. 806–809.
Khonik, V.A., Mitrofanov, Yu.P., Makarov, A.S., Konchakov, R.A., Afonin, G.V., and Tsyplakov, A.N., Structural relaxation and shear softening of Pdand Zrbased bulk metallic glasses near the glass transition, J. Alloys Compd., 2015, vol. 628, pp. 27–31.
Scarfone, R. and Sinning, H.-R., A mechanical spectroscopy study of the Zr69.5Cu12Ni11Al7.5 alloy, J. Alloys Compd., 2000, vol. 310, nos. 1–2, pp. 229–232.
Wide, G., Gorler, G.P., and Willnecker, R., Calorimetric, thermomechanical, and rheological characterizations of bulk glass-forming Pd40Ni40P20, J. Appl. Phys., 2000, vol. 87, no. 3, pp. 1141–1152.
Duine, P.A., Sietsma, J., and Beukel, A., Defect production and annihilation near equilibrium in amorphous Pd40Ni40P20 investigated from viscosity data, Acta Metall. Mater., 1992, vol. 40, no. 4, pp. 743–751.
Volkert, C.A. and Spaepen, F., Viscosity and structure relaxation in Pd40Ni40P19Si1, Mater. Sci. Eng., 1988, vol. 97, pp. 449–452.
Mazurin, O.V., Steklovanie (The Glass Transition), Leningrad: Nauka, 1985.
Mitrofanov, Yu.P., Peterlechner, M., Binkowski, I., Zadorozhnyy, M.Yu., Golovin, I.S., Divinski, S.V., and Wilde, G., The impact of elastic and plastic strain on relaxation and crystallization of Pd–Ni–P-based bulk metallic glasses, Acta Mater., 2015, vol. 90, pp. 318–329.
Sinning, H.-R., Observation of the glass transition of metallic glasses by low-frequency internal friction measurements with a collette pendulum, Mater. Sci. Forum, 1993, vols. 119–121, pp. 535–540.
Wei Hua Wang, The elastic properties, elastic models and elastic perspectives of metallic glasses, Prog. Mater. Sci., 2012, vol. 57, no. 3, pp. 487–656.
Qiao, J., Casalini, R., Pelletier, J.-M., and Kato, H., Characteristics of the structural and Johari–Goldstein relaxations in Pd-based metallic glass-forming liquids, J. Phys. Chem. B, 2014, vol. 118, no. 13, p. 3720–3730.
Schröter, K., Wilde, G., Willnecker, R., Weiss, M., Samwer, K., and Donth, E., Shear modulus and compliance in the range of the dynamic glass transition for metallic glasses, Eur. Phys. J. B, 1998, vol. 5, no. 1, pp. 1–5.
Tammann, G. and Hesse, W., Die Abhängigkeit der Viscosität von der Temperatur bei unterkühlter Flüssigkeiten, Zs. Anorg. Allg. Chem., 1926, vol. 156, no. 4, pp. 245–257.
Parks, G.S. and Gilkey, W., Studies on glass. Some viscosity data on liquid glucose and glucose-glycerol solutions, J. Phys. Chem., 1928, vol. 33, no. 9, pp. 1428–1437.
Laughlin, W.T., Viscous flow and volume relaxation in simple glass-forming liquids, Sc. D. Thesis, Cambridge: Massachusetts Inst. Technol., 1969.
Kobeko, P.P., Kuvshinskii, E.V., and Shishkin, N.P., The study of amorphous state. XIII. Viscosity, electrical conductivity and dielectric losses in alcohols and glycerol, Zh. Tekh. Fiz., 1938, vol. 8, no. 8, pp. 715–724.
Piccirelli, R. and Litovitz, T.A., Ultrasonic shear and compressional relaxation in liquid glycerol, J. Acoust. Soc. Am., 1957, vol. 29, no. 9, pp. 1009–1020.
Schröter, K. and Donth, E., Viscosity and shear response at the dynamic glass transition of glycerol, J. Chem. Phys., 2000, vol. 113, no. 20, pp. 9101–9108.
Samatowicz, D., Kulik, A., and Benoit, W., Investigation of glycerol phase transition by the internal friction method, Mater. Sci. Forum, 1993, vols. 119–121, pp. 529–534.
Jeong, Youn H., Nagel, S.R., and Bhattacharya, S., Ultrasonic investigation of the glass transition in glycerol, Phys. Rev. A: At., Mol., Opt. Phys., 1986, vol. 34, no. 1, pp. 602–608.
Nemilov, S.V., Thermodynamic and Kinetic Aspects of the Vitreous State, Boca Raton, FL: CRC Press, 1995.
Schulz, A.K., Sur le comportement dilatometrique et la refraction de la glicerine aux etats liquide, crystallin et vitreux vers les basses temperatures, J. Chim. Phys. Phys.-Chim. Biol., 1954, vol. 51, no. 6, pp. 324–327.
Author information
Authors and Affiliations
Corresponding author
Additional information
The article is published in the original.
Rights and permissions
About this article
Cite this article
Nemilov, S.V., Balashov, Y.S. The peculiarities of relaxation processes at heating of glasses in glass transition region according to the data of mechanical relaxation spectra (Review). Glass Phys Chem 42, 119–134 (2016). https://doi.org/10.1134/S1087659616020139
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1134/S1087659616020139