Dependence of Heat Transport in Solids on Length-Scale, Pressure, and Temperature: Implications for Mechanisms and Thermodynamics.

Accurate laser-flash measurements of thermal diffusivity (D) of diverse bulk solids at moderate temperature (T), with thickness L of ~0.03 to 10 mm, reveal that D(T) = D ∞(T)[1 - exp(-bL)]. When L is several mm, D ∞(T) = FT -G + HT, where F is constant, G is ~1 or 0, and H (for insulators) is ~0.001. The attenuation parameter b = 6.19D ∞ -0.477 at 298 K for electrical insulators, elements, and alloys. Dimensional analysis confirms that D → 0 as L → 0, which is consistent with heat diffusion, requiring a medium. Thermal conductivity (κ) behaves similarly, being proportional to D. Attenuation describing heat conduction signifies that light is the diffusing entity in solids. A radiative transfer model with 1 free parameter that represents a simplified absorption coefficient describes the complex form for κ(T) of solids, including its strong peak at cryogenic temperatures. Three parameters describe κ with a secondary peak and/or a high-T increase. The strong length dependence and experimental difficulties in diamond anvil studies have yielded problematic transport properties. Reliable low-pressure data on diverse thick samples reveal a new thermodynamic formula for specific heat (∂ln(cP )/∂P = -linear compressibility), which leads to ∂ln(κ)/∂P = linear compressibility + ∂lnα/∂P, where α is thermal expansivity. These formulae support that heat conduction in solids equals diffusion of light down the thermal gradient, since changing P alters the space occupied by matter, but not by light.