The glass transition of a liquid to a solid-like state may occur with either cooling or compression. The transition comprises a smooth increase in the viscosity of a material by as much as 17 orders of magnitude within a temperature range of 500 K without any pronounced change in material structure. This transition is in contrast to the freezing or crystallization transition, which is a first-order phase transition in the Ehrenfest classification and involves discontinuities in thermodynamic and dynamic properties such as volume, energy, and viscosity. In many materials that normally undergo a freezing transition, rapid cooling will avoid this phase transition and instead result in a glass transition at some lower temperature. Other materials, such as many polymers, lack a well defined crystalline state and easily form glasses, even upon very slow cooling or compression. The tendency for a material to form a glass while quenched is called glass forming ability. This ability depends on the composition of the material and can be predicted by the rigidity theory.
Below the transition temperature range, the glassy structure does not relax in accordance with the cooling rate used. The expansion coefficient for the glassy state is roughly equivalent to that of the crystalline solid. If slower cooling rates are used, the increased time for structural relaxation (or intermolecular rearrangement) to occur may result in a higher density glass product. Similarly, by annealing (and thus allowing for slow structural relaxation) the glass structure in time approaches an equilibrium density corresponding to the supercooled liquid at this same temperature. T is located at the intersection between the cooling curve (volume versus temperature) for the glassy state and the supercooled liquid.
The configuration of the glass in this temperature range changes slowly with time towards the equilibrium structure. The principle of the minimization of the Gibbs free energy provides the thermodynamic driving force necessary for the eventual change. At somewhat higher temperatures than T, the structure corresponding to equilibrium at any temperature is achieved quite rapidly. In contrast, at considerably lower temperatures, the configuration of the glass remains sensibly stable over increasingly extended periods of time.
Thus, the liquid-glass transition is not a transition between states of thermodynamic equilibrium. It is widely believed that the true equilibrium state is always crystalline. Glass is believed to exist in a kinetically locked state, and its entropy, density, and so on, depend on the thermal history. Therefore, the glass transition is primarily a dynamic phenomenon. Time and temperature are interchangeable quantities (to some extent) when dealing with glasses, a fact often expressed in the time–temperature superposition principle. On cooling a liquid, internal degrees of freedom successively fall out of equilibrium. However, there is a longstanding debate whether there is an underlying second-order phase transition in the hypothetical limit of infinitely long relaxation times.
In a more recent model of glass transition, the glass transition temperature corresponds to the temperature at which the largest openings between the vibrating elements in the liquid matrix become smaller than the smallest cross-sections of the elements or parts of them when the temperature is decreasing. As a result of the fluctuating input of thermal energy into the liquid matrix, the harmonics of the oscillations are constantly disturbed and temporary cavities ("free volume") are created between the elements, the number and size of which depend on the temperature. The glass transition temperature T defined in this way is a fixed material constant of the disordered (non-crystalline) state that is dependent only on the pressure. As a result of the increasing inertia of the molecular matrix when approaching T, the setting of the thermal equilibrium is successively delayed, so that the usual measuring methods for determining the glass transition temperature in principle deliver T values that are too high. In principle, the slower the temperature change rate is set during the measurement, the closer the measured T value T approaches. Techniques such as dynamic mechanical analysis can be used to measure the glass transition temperature.