Melting

Criteria

Among the theoretical criteria for melting, the Lindemann and Born criteria are those most frequently used as a basis to analyse the melting conditions.

The Lindemann criterion states that melting occurs because of "vibrational instability", e.g. crystals melt; when the average amplitude of thermal vibrations of atoms is relatively high compared with interatomic distances, e.g. <δu²>^1/2 > δ_LR_s, where δu is the atomic displacement, the Lindemann parameter δ_L ≈ 0.20...0.25 and R_s is one-half of the inter-atomic distance. The "Lindemann melting criterion" is supported by experimental data both for crystalline materials and for glass-liquid transitions in amorphous materials.

The Born criterion is based on a rigidity catastrophe caused by the vanishing elastic shear modulus, i.e. when the crystal no longer has sufficient rigidity to mechanically withstand the load, it becomes liquid.

Another melting criterion is based on configuron percolation theory (CPT) and accounts for their mobility in materials. In crystals, configurons which are quasiparticles in form of broken chemical bonds, are delocalized and propagate freely through the periodic lattice, enabling collective condensation and emergence of latent heat for the phase change at the melting point T_m. In contrast to that structural disorder of glasses induces Anderson localization of configurons, suppressing condensation and producing a continuous, second-order-like glass transition at T_g. Both transitions from solid to melt phases arise from configuron percolation, but their order is determined by configuron mobility.

Supercooling

Under a standard set of conditions, the melting point of a substance is a characteristic property. The melting point is often equal to the freezing point. However, under carefully created conditions, supercooling, or superheating past the melting or freezing point can occur. Water on a very clean glass surface will often supercool several degrees below the freezing point without freezing. Fine emulsions of pure water have been cooled to −38 °C without nucleation to form ice. Nucleation occurs due to fluctuations in the properties of the material. If the material is kept still there is often nothing (such as physical vibration) to trigger this change, and supercooling (or superheating) may occur. Thermodynamically, the supercooled liquid is in the metastable state with respect to the crystalline phase, and it is likely to crystallize suddenly.

Glasses

Glasses are amorphous solids, which are usually fabricated when the molten material cools very rapidly to below its glass transition temperature, without sufficient time for a regular crystal lattice to form. Solids are characterised by a high degree of connectivity between their molecules, and fluids have lower connectivity of their structural blocks. Melting of a solid material can also be considered as a percolation via broken connections between particles e.g. connecting bonds. In this approach melting of an amorphous material occurs, when the broken bonds form a percolation cluster with T_g dependent on quasi-equilibrium thermodynamic parameters of bonds e.g. on enthalpy (H_d) and entropy (S_d) of formation of bonds in a given system at given conditions:

${\displaystyle T_g=\frac{H_d}{S_d+R\ln (\frac{1-f_c}{f_c})},}$

where f_c is the percolation threshold and R is the universal gas constant.

Although H_d and S_d are not true equilibrium thermodynamic parameters and can depend on the cooling rate of a melt, they can be found from available experimental data on viscosity of amorphous materials.

Even below its melting point, quasi-liquid films can be observed on crystalline surfaces. The thickness of the film is temperature-dependent. This effect is common for all crystalline materials. This pre-melting shows its effects in e.g. frost heave, the growth of snowflakes, and, taking grain boundary interfaces into account, maybe even in the movement of glaciers.

Related concept

In ultrashort pulse physics, a so-called nonthermal melting may take place. It occurs not because of the increase of the atomic kinetic energy, but because of changes of the interatomic potential due to excitation of electrons. Since electrons are acting like a glue sticking atoms together, heating electrons by a femtosecond laser alters the properties of this "glue", which may break the bonds between the atoms and melt a material even without an increase of the atomic temperature.

In genetics, melting DNA means to separate the double-stranded DNA into two single strands by heating or the use of chemical agents, polymerase chain reaction.

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