Dependence of the width of the glass transition interval on cooling and heating rates.

In a preceding paper [J. W. P. Schmelzer, J. Chem. Phys. 136, 074512 (2012)], a general kinetic criterion of glass formation has been advanced allowing one to determine theoretically the dependence of the glass transition temperature on cooling and heating rates (or similarly on the rate of change of any appropriate control parameter determining the transition of a stable or metastable equilibrium system into a frozen-in, non-equilibrium state of the system, a glass). In the present paper, this criterion is employed in order to develop analytical expressions for the dependence of the upper and lower boundaries and of the width of the glass transition interval on the rate of change of the external control parameters. It is shown, in addition, that the width of the glass transition range is strongly correlated with the entropy production at the glass transition temperature. The analytical results are supplemented by numerical computations. Analytical results and numerical computations as well as existing experimental data are shown to be in good agreement.

[1]  Jürn W. P. Schmelzer,et al.  The Vitreous State: Thermodynamics, Structure, Rheology, and Crystallization , 2013 .

[2]  J. Schmelzer Kinetic criteria of glass formation and the pressure dependence of the glass transition temperature. , 2012, The Journal of chemical physics.

[3]  J. Schmelzer,et al.  Glasses and the Glass Transition , 2011 .

[4]  O. Mazurin,et al.  Glasses and the Glass Transition: SCHMELZER:GLASSTRANSITION O-BK , 2011 .

[5]  Jürn W. P. Schmelzer,et al.  On the dependence of the properties of glasses on cooling and heating rates: I. Entropy, entropy production, and glass transition temperature , 2011 .

[6]  C. Schick,et al.  On the dependence of the properties of glasses on cooling and heating rates II: Prigogine–Defay ratio, fictive temperature and fictive pressure , 2011 .

[7]  C. Schick,et al.  Fast scanning power compensated differential scanning nano-calorimeter: 1. The device , 2010 .

[8]  C. Schick,et al.  Ultrafast thermal processing and nanocalorimetry at heating and cooling rates up to 1 MK/s. , 2007, The Review of scientific instruments.

[9]  O. Mazurin Problems of compatibility of the values of glass transition temperatures published in the world literature , 2007 .

[10]  J. Schmelzer,et al.  Freezing-in and production of entropy in vitrification. , 2006, The Journal of chemical physics.

[11]  I. Gutzow,et al.  Kinetics of vitrification, glass relaxation and devitrification: a unified treatment , 2002 .

[12]  V. Yamakov,et al.  Generic Phenomenological Theory of Vitrification , 2001 .

[13]  V. Yamakov,et al.  Thermodynamics and kinetics of the glass transition: A generic geometric approach , 2000 .

[14]  C. Schick,et al.  Relation between freezing-in due to linear cooling and the dynamic glass transition temperature by temperature-modulated DSC , 1998 .

[15]  H. Ritland Density Phenomena in the Transformation Range of a Borosilicate Crown Glass , 1954 .

[16]  A. Q. Tool,et al.  RELATION BETWEEN INELASTIC DEFORMABILITY AND THERMAL EXPANSION OF GLASS IN ITS ANNEALING RANGE , 1946 .

[17]  W. Bragg,et al.  The effect of thermal agitation on atomic arrangement in alloys , 1935 .