R.W. Pekala

Organic aerogels from the polycondensation of resorcinol with formaldehyde

The polycondensation of resorcinol with formaldehyde under alkaline conditions results in the formation of surface functionalized polymer “clusters”. The covalent crosslinking of these “clusters” produces gels which are processed under supercritical conditions to obtain low density, organic aerogels ( ⩽ 0.1 g cm−3). The aerogels are transparent, dark red in colour, and consist of interconnected colloidal-like particles with diameters of approximately 10 nm. The polymerization mechanism, structure and properties of the resorcinol-formaldehyde aerogels are similar to the sol-gel processing of silica.

Aerogels derived from multifunctional organic monomers

Traditional inorganic aerogels are mad via the hydrolysis and condensation of metal alkoxides. Recently, we reported the synthesis of organic aerogels based upon the aqueous polycondensation of (1) resorcinol with formaldehyde and (2) melamine with formaldehyde. The former materials can also be pyrolyzed in an inert atmosphere to form vitreous carbon aerogels. In both the inorganic and organic systems, the structure and properties of the dried aerogel are dictated by polymerization conditions. Factors such as pH, reactant ratio, and temperature influence the crosslinking chemistry and growth processes taking place prior to gelation. The ability to tailor the structure and properties of aerogels at the nanometer scale opens up exciting possibilities for these novel materials. This paper addresses the chemistry-structure-property relationships of organic aerogels. 22 refs., 7 figs.

Thermal Conductivity of Monolithic Organic Aerogels

The total thermal conductivity λ of resorcinol-formaldehyde aerogel monoliths has been measured as a function of density ρ in the range from ρ = 80 to 300 kilograms per cubic meter. A record-low conductivity value in air at 300 K of λ ≈ 0.012 watt per meter per kelvin was found for ρ ≈ 157 kilograms per cubic meter. Caloric measurements under variation of gas pressure as well as spectral infrared transmission measurements allowed the determination of solid conductivity, gaseous conductivity, and radiative conductivity as a function of density. The development of such low conductivity materials is of great interest with respect to the substitution of environmentally harmful insulating foams made from chlorofluorocarbons.

Thermal properties of organic and inorganic aerogels

Aerogels are open-cell foams that have already been shown to be among the best thermal insulating solid materials known. This paper examines the three major contributions to thermal transport through porous materials, solid, gaseous, and radiative, to identify how to reduce the thermal conductivity of air-filled aerogels. We found that significant improvements in the thermal insulation property of aerogels are possible by (i) employing materials with a low intrinsic solid conductivity, (ii) reducing the average pore size within aerogels, and (iii) affecting an increase of the infrared extinction in aerogels. Theoretically, polystyrene is the best of the organic materials and zirconia is the best inorganic material to use for the lowest achievable conductivity. Significant reduction of the thermal conductivity for all aerogel varieties is predicted with only a modest decrease of the average pore size. This might be achieved by modifying the sol-gel chemistry leading to aerogels. For example, a thermal resistance value of R = 20 per inch would be possible for an air-filled resorcinol-formaldehyde aerogel at a density of 156 kg/m 3 , if the average pore size was less than 35 nm. An equation is included which facilitates the calculation of the optimum density for the minimum total thermal conductivity, for all varieties of aerogels.

Organic aerogels: microstructural dependence of mechanical properties in compression

Aerogels are a unique class of ultrafine cell size (<1000 A), low-density foams. These materials have continuous porosity and a microstructure composed of interconnected colloidal-like particles or chains with characteristic diameters of 100 A. Traditional aerogels are inorganic, made via the hydrolysis and condensation of metal alkoxides (e.g. tetraisopropoxy titanate). Recently, the authors reported the development of organic aerogels from the sol-gel polymerization of resorcinol with formaldehyde. Because these new aerogels are composed of a highly crosslinked aromatic polymer, they can be pyrolyzed in an inert atmosphere to form vitreous carbon aerogels. This work describes how the microstructure of these organic aerogels can be manipulated and controlled. The microstructural dependence of the compressive mechanical properties of both resorcinol-formaldehyde and carbon aerogels is examined in detail.

Correlation between structure and thermal conductivity of organic aerogels

Abstract Organic aerogels are derived from the sol-gel polymerization of resorcinol with formaldehyde. While these materials are usually produced as monoliths, this paper describes a new method for the production of organic aerogel microsphere powders. Supercritical drying provides highly porous aerogels which have an open-cell structure consisting of interconnected solid particles with typical diameters of 10 nm. The structure is controlled by the sol-gel polymerization conditions. This paper addresses the correlation between structure and thermal conductivity of these novel materials. Thermal conductivity measurements have been performed on both monoliths and powders using a hot-wire device. The measurements under variation of gas pressure as well as spectral infrared transmission measurements allow the determination of the solid, gaseous and radiative thermal conductivity as a function of density and catalyst concentration. The results show that the thermal conductivity components are clearly correlated with the aerogel structure: porosity and connectivity between the particles determine the solid conductivity, while the pore size influences the gaseous conductivity and radiative transport depends on the mass specific infrared absorption of the building units.

New organic aerogels based upon a phenolic-furfural reaction☆

The aqueous polycondensation of (1) resorcinol with formaldehyde and (2) melamine with formaldehyde are two proven synthetic routes for the formation of organic aerogels. Recently, we have discovered a new type of organic aerogel based upon a phenolic-furfural (PF) reaction. This sol-gel polymerization has a major advantage over past approaches since it can be conducted in alcohol (e.g., 1-propanol), thereby eliminating the need for a solvent exchange step prior to supercritical drying from carbon dioxide. The resultant aerogels are dark brown in color and can be converted to a carbonized version upon pyrolysis in an inert atmosphere. BET surface areas of 350--600 m{sup 2}/g have been measured, and transmission electron microscopy reveals an interconnected structure of irregularly-shaped particles or platelets with {approximately}10 nm dimensions. Thermal conductivities as low as 0.015 W/m-K have been recorded for PF aerogels under ambient conditions. This paper describes the chemistry-structure-property relationships of these new materials in detail.

Thermal and electrical conductivity of monolithic carbon aerogels

The thermal and electrical conductivity of monolithic carbon aerogels was investigated at room temperature. Results showed both the solid thermal conductivity and the electrical conductivity scale with the density in the range between 60 and 650 kg m−3. The scaling exponents for the two conductivities have identical values of 1.5. For a density of 82 kg m−3 a thermal conductivity of 0.029 W m−1 K−1 in air and 0.018 W m−1 K−1 after evacuation was found.

Carbon Aerogels and Xerogels

The aqueous polycondensation of resorcinol with formaldehyde proceeds through a sol-gel transition and results in the formation of highly crosslinked, transparent gels. If the solvent is simply evaporated from the pores of these gels, large capillary forces are exerted and a collapsed structure known as a xerogel is formed. In order to preserve the gel skeleton and minimize shrinkage, the aforementioned solvent or its substitute must be removed under supercritical conditions. The microporous material that results from this operation is known as an aerogel. Because resorcinol-formaldehyde aerogels and xerogels consist of a highly crosslinked aromatic polymer, they can be pyrolyzed in an inert atmosphere to form vitreous carbon monoliths. The resultant porous materials are black in color and no longer transparent, yet they retain the ultrafine cell size (< 50 nm), high surface area (600--800 m[sup 2]/g), and the interconnected particle morphology of their organic precursors. The thermal, acoustic, mechanical, and electrical properties of carbon aerogels/xerogels primarily depend upon polymerization conditions and pyrolysis temperature. In this paper, the chemistry-structure-property relationships of these unique materials will be discussed in detail.

Origin of porosity in resorcinol-formaldehyde aerogels☆

Porod analysis of small-angle X-ray scattering results was used to study the structure of resorcinol-formaldehyde aerogels as a function of monomer and catalyst concentration. Based on an analysis of the shape of the scattering curves, the catalyst dependence of the pore and solid chords and previous work on scattering from precursor solutions, it is concluded that the structure of the aerogels results from nanoscale phase separation in the solution precursor. Remnants of a possible kinetic polymerization process were found at length scales so small that porosity arising from these processes is not penetrated by nitrogen.