Silica aerogels are a special class of porous materials in which both the pore size and interconnected particle size have nanometer dimensions. This structure imparts unique optical, thermal, acoustic, and electrical properties to these materials. Transmission electron microscopy and small angle x-ray scattering show that this nanostructure is sensitive to variations in processing conditions that influence crosslinking chemistry and growth processes prior to gelation. Recently, Lawrence Livermore National Laboratory (LLNL) has demonstrated that a Rapid Supercritical Extraction (RSCE) process can be used to prepare near-net shape silica aerogels in hows rather than days. Preliminary data from RSCE silica aerogels show that they have improved mechanical properties and slightly lower surface areas than their conventionally dried counterparts, while not compromising their optical and thermal performance.