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 without any pronounced change in material structure. The consequence of this dramatic increase is a glass exhibiting solid-like mechanical properties on the timescale of practical observation. 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.
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. Tg 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. It should be noted here that at somewhat higher temperatures than Tg, 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.