Chapter 6 describes a range of methods to determine different aspects of the electronic structure of materials. These include both core level photoemission (and the associated 'chemical' shifts) and valence band photoemission, notably including angle-resolved photoelectron spectroscopy (ARPES). The use of X-ray absorption near-edge structures (XANES) and the related technique of X-ray magnetic circular dicroism (XMCD) using circularly-polarised radiation is also described, as is the use of X-ray emission spectroscopy (XES) and resonant inelastic X-ray scattering (RIXS) and Compton scattering. Finally, the use of photoemission and photoionisation to investigate gas-phase molecular structure is described.

Chapter 5 describes techniques to determine the localstructure of materials both on an atomic and microscopic scale that do not rely on X-ray crystal diffraction. These include small angle scattering (SAXS) and wide angle scattering (WAXS), near-edge and extended X-ray absorption fine structure spectroscopy (XAFS, NEXAFS, EXAFS) but also photoelectron diffraction and X-ray fluorescence holography.

One important characteristic of all aerogels is their large specific surface area. Almost in every paper on aerogels, not only the envelope density is reported but also the specific surface area in terms of inner surface per unit mass. We first present some fundamental relations for the specific surface area of particulate aerogels, such as silica or RF aerogels, and fibrillar aerogels such as cellulose. We then define terms and present selected experimental results to compare the models with reality.Techniques to measure the surface area by nitrogen adsorption and the fundamental equations behind them such as the famous BET theory or the t-plot method are derived and compared with experimental results.

Numerous daily-life materials exhibit a porous structure, e.g., foams made from different polymers (polystyrene, polyurethane), clays, tiles, bricks, oxide ceramics, bones, sponges, wood or diatoms. In many cases, the mechanical properties can be described by simple scaling laws with the relative or envelope density being the decisive factor. It is generally agreed that similar scaling laws apply to aerogels and xerogels, but the special nanostructured nature of aerogels and the mode used to form them out of a solution of monomers or polymers make an essential difference. A brief discussion of the conventional approach for closed and open cell foams or honeycombs based on the famous book written by Lorna J.Gibson and Michael F. Ashby on porous materials is given and extended to aerogels. Beforewe discuss aerogels, we briefly give for newcomers in the field of mechanical properties some textbook knowledge about mechanical testing. The chapter deals then with elastic and plastic properties of aerogels, compares modelling with experimental results and discusses deviations from classical porous media theory observed in aerogels.

The general thermodynamic concept of solutions is applied to polymer solutions. The famous Flory–Huggins theory is explained and binodal and spinodal lines are determined as they depend on the degree of polymerisation. Polymer solutions can exhibit not only an upper critical point but also a lower critical point. Some aerogels seem to exhibit such a phase behaviour.

Aerogels are famous for theirlow thermal conductivity making them the super-isolation materials of the future. The extreme small conductivity, which can be even close to the conductivity of vacuum isolation panels, poses, however, problems to many conventional measurement techniques, since even smallest heat leaks might give erroneous results by easily 20–30%. This chapter therefore is divided into several sections: first, general aspects of heat conduction are treated; and second, models are discussed explaining the thermal conductivity, specific heat and thermal diffusivity of porous materials, especially aerogels. The experimental techniques to measure thermal conductivity of isolating materials are discussed in detail and the theoretical background explained.

A wide class of aerogels starts from solution of monomers in which the monomers react, forming oligomers, polymers, particles and eventually a spanning cluster or a solid network embedded in a solution: a wet gel. Meanwhile,the two classical aerogels prepared in this way are the silica and resorcinol-formaldehyde ones. In the first section, silica aerogels, silica being the most often used precursor, are treated: the reaction between them in a solution, hydrolysis and polycondensation, the growth of fractal and compact structures, their gelation and ageing after the gel point has passed. Finally, the chemistry of silica aerogels with lower functional silanes is briefly discussed. In the second section, the chemistry of resorcinol (R) and formaldehyde (F) is presented, as well as the reaction between both molecules under basic and acidic conditions and how polymers develop from monomers. The effect of various process parameters, the ratio of R to F or the concentration of a catalyst, the dilution ratio with water and the influence of temperature on gelation are treated in detail. Finally, some thoughts on the thermodynamics of RF gels are presented.

Aerogel technology provides lightweight materials with an outstanding combination of properties. One major problem for the preparation of aerogels is how to eliminate the liquid solvent from the wet gel while avoiding shrinkage, cracking and collapse of the gel structure. Several techniques have been used and are still under development. The chapter discusses three techniques to dry a wet gel: ambient or evaporative drying, freeze drying and supercritical drying. All aspects of each drying technique are explained in detail, andvarious effects of drying routines on the final aerogel structure and thus properties are discussed.

Pressure-driven flow through porous media is a well-investigated subject of fluid and gas dynamics. Since aerogels possess a nanostructure and porosities above 90%, the flow through the pores needs special consideration. We only discussgas flow through aerogels. First, there is of course the conventional viscous flow determined mainly by the pressure gradient and the viscosity, as in Hagen–Poisseuille flow. In such a flow situation, the molecules interact with each other more frequently than with pore walls. Knudsen flow is determined by the interaction of molecules with pore walls, meaning collision events between themselves are negligible. The third possibility is a sliding of molecules along the surface of the pore walls determined by the friction coefficient between molecules and the pore surface. The essential characteristic property determining the flow through a porous body is the so-called permeability. The chapter derives not only the basic flow equations for porous mediabut also discusses experimental approaches to determine gas phase permeability and compare experimental results with theoretical models.