SummaryAtomic force microscopy (AFM) in aqueous solution was used to investigate native nacre of the marine snail Haliotis laevigata on the microscopic scale and the interaction of purified nacre proteins with calcium carbonate crystals on the nanoscopic scale. These investigations were controlled by scanning electron microscopy (SEM), light microscopy (LM) and biochemical methods. For investigations with AFM and SEM, nacre was cleaved parallel to the aragonite tablets in this biogenic polymer/mineral composite. Multilamellar organic sheets consisting of a core of chitin with layers of proteins attached on both sides lay between the aragonite layers consisting of confluent aragonite tablets. Cleavage appeared to occur between the aragonite tablet layer and the protein layer. AFM images revealed a honeycomb-like structure to the organic material with a diameter of the 'honeycombs' equalling that of the aragonite tablets. The walls of the structures consisted of filaments, which were suggested to be collagen. The flat regions of the honeycomb-like structures exhibited a hole with a diameter of more than 100 nm. When incubated in saturated calcium carbonate solution, aragonite needles with perfect vertical orientation grew on the proteinacous surface. After treatment with proteinase K, no growth of orientated aragonite needles was detected. Direct AFM measurements on dissolving and growing calcite crystals revealed a surface structure with straight steps the number of which decreased with crystal growth. When the purified nacre protein perlucin was added to the growth solution (a super-saturated calcium carbonate solution) new layers were nucleated and the number of steps increased. Anion exchange chromatography of the water-soluble proteins revealed a mixture of about 10 different proteins. When this mixture was dialysed against saturated calcium carbonate solution and sodium chloride, calcium carbonate crystals precipitated together with perlucin leaving the other proteins in the supernatant. Thus perlucin was shown to be a protein able to nucleate calcium carbonate layers on calcite surfaces, and in the presence of sodium chloride, is incorporated as an intracrystalline protein into calcium carbonate crystals.
Porous silicon oxycarbide (SiOC) ceramics in particular bulk and cellular structures are produced via polymer pyrolysis. By using optimal pyrolysis parameters (i.e., heating rate, maximum temperature) the addition of either solid fillers or chemically active additives is efficient in preventing the collapse of pore structure and controlling pore formation through decomposition. Fast pyrolysis can lead to crack formation and a loss of specific surface area at temperatures above 600°C, whereas slow pyrolysis is able to preserve mesopores up to 1200°C combined with high surface areas. These SiOC ceramics with bimodal pore size distribution are potential candidates for adsorption/separation processes under severe conditions.
A new direct foaming method to produce macroporous cellular ceramics using surfactants as foam stabilizers is presented. The technology relies on the transition of a stabilized aqueous ceramic powder suspension containing a homogeneously dispersed alkane or air–alkane phase into cellular ceramics. The stabilization of the powder suspension and the emulsion is realized with particular emphasis on the interaction of both mechanisms providing enduring stability of the system up to high foaming degrees. Anionic, cationic, and nonionic surfactants were studied with their stabilization and foaming effects. The presence and influence of air bubbles was proved to be of negligible importance. Foaming is then provided by the evaporation of the emulsified alkane droplets, leading to the expansion of the emerging foam and giving rise to solids foams with cell sizes from 0.5 to 3 mm and porosities up to 97.5% after sintering. The microstructures of these filigree ceramics are stable and rigid with dense struts and uniform distributions of the solid phase and the porosity.
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