Thermal and Temporal Aging of Two Step Acid-Base Catalyzed Silica Gels in Water/Ethanol Solutions

Dissolution and reprecipitation of silica during aging in water improve the wet gels mechanical stiffness and strength, and hence shrinkage during supercritical drying is reduced. We have investigated how the strength and stiffness of a 2-step TEOS acid-base catalyzed wet gel can be improved by aging in a solution of water/ethanol (20–40 vol%) at various temperatures (20–70°C) and time (2 h and 24 h) and how this influences the aerogels properties. The linear shrinkage during supercritical drying was reduced from 29% to 2% by introducing the aging step in the 20 vol% water/ethanol solution for 24 h at 60°C.We have also in previous works introduced the idea of preparing ambient pressure dried silica aerogels by increasing the wet gels stiffness by aging in a TEOS solution until shrinkage during drying is almost eliminated. The gels aged in the water/ethanol solutions were further aged in a TEOS/ethanol solution and the effect of the increasing water content in the pore liquid was studied. A xerogel density of 0.20 g/cm³ is reported for gels with a shear modulus (G) of 30 MPa.     

Thermal and Temporal Aging of Silica Gels in Monomer Solutions

In previous work we have introduced the idea of preparing ambient pressure dried silica aerogels by increasing the wet gels' stiffness by aging in a TEOS solution until shrinkage during drying is almost eliminated. The present work elucidates the possibilities for obtaining ambient pressure dried aerogels employing this idea, however, cheap water soluble sodium silicate (water glass) precursors have been used to increase the economic feasibility of the process.We have shown how the G modulus of water glass based gels can be increased by aging in TEOS solution and gels with a density down to 0.2 g/cm3 can be obtained. These wet gels show a higher reactivity towards TEOS compared to TEOS based gels. We have also introduced the idea of aging wet gels in a solution where the monomers are provided from water glass instead of TEOS and some initial results on G modulus and density are included.     

Deposition of silica thin films formed by sol–gel method

Deposition of silica thin films on silicon wafer was investigated by in situ mass measurements with a microbalance configured for dip coating. Mass change was recorded with respect to deposition time when the substrate was fully immersed in the silica sol. Mass gain during deposition was higher than predicted from monolayer coverage of silica nano particles. This implied that deposition was facilitated by gelling of the nanoparticles on the substrate. The rate of deposition was enhanced by increasing the particle concentration in the sol and by decreasing the particle size from 12 to 5 nm. Increasing the salt concentration of the silica sol at constant pH enhanced the deposition of the silica particles. Reducing the pH of the sol from 10 to 6 decreased the deposition rate due to aggregation of the primary silica particles.     

Mechanical properties of mixed conducting La0.5Sr0.5Fe1−x Co x O3−δ (0≤x≤1) materials

Young’s modulus, strain–stress behavior, fracture strength, and fracture toughness of (0≤×≤1) materials have been investigated in the temperature range 20–1,000°C. Young’s moduli of and , measured by resonant ultrasound spectroscopy, were 130±1 and 133±3 GPa, respectively. The nonlinear stress–strain relationship observed by four-point bending at room temperature was inferred as a signature of ferroelastic behavior of the materials. Above the ferroelastic to paraelastic transition temperature, the materials showed elastic behavior, but due to high-temperature creep, a nonelastic respond reappeared above ∼800°C. The room temperature fracture strength measured by four-point bending was in the range 107–128 MPa. The corresponding fracture toughness of , measured by single edge V-notch beam method, was 1.16±0.12 MPa·m^1/2. The measured fracture strength and fracture toughness were observed to increase with increasing temperature. The fracture mode changed from intragranular at low temperature to intergranular at high temperature. Tensile stress gradient at the surface of the materials caused by a frozen-in gradient in the oxygen content during cooling was proposed to explain the low ambient temperature fracture strength and toughness.     

Sol-Gel Derived Binder for Inorganic Composites

A new low cost inorganic binder system for large volume products like fiber insulation, building materials, etc. has been developed based on sol-gel technology. The precursor for the binder system is an amorphous mineral raw material containing silica as the major component. The sol was prepared by dissolving the amorphous mineral material in formic acid and the mineral was dissolved in a few hours dependent on the molarity of the formic acid. The sol stability was dependent on the solids content and the pH. The gel formation was studied using light scattering and NMR. The results show a growing particle size of particles mainly consisting of silica while the other cations were dissolved in the pore liquid. During the drying of the wet gels, salts of these cations were crystallized in the pores and further decomposed during heating. The derived binder shows good wetting properties to mineral fiber surfaces and a good strength of paper-binder composites. The new binder system applicable to approximately 800°C has a great potential as a substitute for some traditional organic systems.     

Structure, Stoichiometry, and Phase Purity of Calcium Substituted Lanthanum Manganite Powders

Calcium-doped lanthanum manganite La_1−xCa_xMnO₃, synthesized by the glycine/nitrate method, was characterized by high resolution synchrotron X-ray powder diffraction, electron diffraction, and infrared spectroscopy. A strong correlation was observed between the cooling rate from the calcination temperature and the powder quality, indicating the importance of a homogeneous oxygen stoichiometry. The structure refinement reveals that La_1−xCa_xMnO₃withx=0.2, 0.3, 0.4, and 0.6 has orthorhombic symmetry with space groupPnma. The MnO₆octahedra are fairly symmetrical, but the octahedra are tilted about 20° relative to the ideal perovskite structure. Infrared spectroscopy revealed that only the O–Mn–O bending mode is significantly influenced by the substitution of La with Ca. In La_0.8Ca_0.2MnO₃we found diffraction evidence of a superstructure in domains in some of the grains. We propose that the superstructure in La_0.8Ca_0.2MnO₃is due to ordering of Ca²⁺ions onA(La³⁺) sites in the perovskiteABO₃structure.     

Influence of volatile chlorides on the molten salt synthesis of ternary oxide nanorods and nanoparticles

A molten salt synthesis route, previously reported to yield BaTiO3, PbTiO3, and Na2Ti6O13 nanorods, has been re-examined to elucidate the role of volatile chlorides. A precursor mixture containing barium (or lead) and titanium was annealed in the presence of NaCl at 760 or 820 degrees C. The main products were respectively isometric nanocrystalline BaTiO3 and PbTiO3. Nanorods were also detected, but electron diffraction revealed that the composition of the nanorods was respectively BaTi2O5/BaTi5O11 and Na2Ti6O13 for the two different systems, in contradiction to the previous studies. It was shown that NaCl reacted with BaO (PbO) resulting in loss of volatile BaCl2 (PbCl2) and formation and preferential growth of titanium oxide-rich nanorods instead of the target phase BaTiO3 (or PbTiO3). The molten salt synthesis route may therefore not necessarily yield nanorods of the target ternary oxide as reported previously. In addition, the importance of NaCl(g) for the growth of nanorods below the melting point of NaCl was demonstrated in a special experimental setup, where NaCl and the precursors were physically separated.     

Melting of Bi sublattice in nanosized BiFeO3 Perovskite by resonant X-ray diffraction

Free-standing BiFeO3 perovskite particles with a size ranging from polycrystalline bulk down to 5?nm have been studied by high-energy resonant (Bi K edge) x-ray diffraction coupled to differential atomic pair distribution function analysis. Nanosized BiFeO3 particles are found to exhibit extra, i.e., beyond the usual thermal, structural disorder that increases progressively with diminishing their size. In particles of size smaller than approximately 18?nm the disorder destroys the structural coherence of the Bi?sublattice and disturbs that of the Fe-based sublattice in the perovskite structure, substantially affecting the magnetoelectric properties it carries. The new structural information helps better understand the unusual behavior of perovskites structured at the nanoscale.     

Preparation of transparent,monolithic silica xerogels with low density

A new process to make monolithic and transparent silica xerogels with similar properties as silica aerogels by drying at ambient pressure has been studied. The xerogels are produced by strengthening the gel structure by additional precipitation of silica after the initial gelation. The additional precipitation of silica is achieved by ageing the alcogels in solutions of tetraethoxysilane (TEOS) and the aging is followed by a relatively rapid drying (<48 h) at ambient pressure. Due to the increased strength of the alcogels it is shown that the shrinkage during drying can be reduced and hence low density xerogels are obtained even if new monomers are added.