Thermal Conductivity in Nanoporous Aerogels: A Critical Review of Gas and Solid Conduction Models and Structure-Property Relations.

Sol-gel processing provides an unusually controllable route to nanoporous solids, making silica aerogels the leading reference systems for extremely low thermal conductivity due to their high porosity, nanoscale pore sizes, and tunable solid frameworks. Under near-ambient conditions, thermal transport is multi-scale and multiphase, arising primarily from coupled solid conduction through the skeletal network and gas conduction within the pore space. Accordingly, aerogel design has emphasized suppressing solid-phase transport by reducing network connectivity, increasing tortuosity, and enhancing boundary scattering, while also limiting gaseous conduction through the control of pore size and gas pressure. This critical review provides an integrated overview of these mechanisms and the theory-to-experiment toolbox used to quantify the separate and combined contributions of the solid and gas phases to the effective thermal conductivity. We link key structural and environmental parameters (porosity, pore size distribution, density, backbone morphology, and pressure) to dominant transport regimes and the assumptions embedded in common models. Classical approaches, including effective-medium and percolation-based models, are assessed alongside phonon-scaling descriptions that incorporate characteristic length scales. Particular attention is given to the Knudsen effect and pressure-sensitive gas-conduction models, which are central to interpreting performance at atmospheric conditions and under vacuum or low-pressure operation. This review highlights inconsistencies across datasets and modeling practices, identifies persistent knowledge gaps, and outlines practical directions toward processable structure-property guidelines for manufacturing aerogels with targeted thermal performance, with regard to conduction-dominated heat transport mechanisms.