Solvent Dependence of the Hydrolysis Products of Mn2Sb4(OEt)16

The hydrolysis-condensation pathways of Mn2Sb4(OEt)16 in various ethanol-toluene solvents have been studied for h < 1.5 (h = H2O/Mn2Sb4(OEt)16). The hydrolysis was performed by slow addition of H2O diluted with the ethanol-toluene solvent. Mn2Sb4(OEt)16 and its hydrolysis products were studied by FT-IR spectroscopy, SEM-EDS and single-crystal X-ray diffraction. The hydrolysis pathway for a given h-value was found to depend on the solvent composition. In ethanol-rich solvent mixtures, Mn7Sb4O4(OEt)18(HOEt)2 was obtained in maximum yield at h = 1.14, and in toluene-rich solvents, Mn8Sb4O4(OEt)20 was obtained in maximum yield at h = 1.0. In both cases, the remaining Sb was found as nonhydrolyzed Sb(OEt)3. The structures of the heterometallic ethoxides Mn2Sb4(OEt)16, Mn7Sb4O4(OEt)18(HOEt)2 and Mn8Sb4O4(OEt)20 have been determined earlier by single-crystal X-ray diffraction. According to FT-IR evidence the molecular structures of the latter two are retained almost intact in solution, whereas the first one changes appreciably. The hydrolysis products of Mn2Sb4(OEt)16 are compared with those of Ni2Sb4(OEt)16, and the structural and compositional changes in different solvents and at different h-values are discussed.     

Preparation of La0.75Sr0.25MnO3 Nano-Phase Powders and Films from Alkoxide Precursors

The first purely alkoxide-based sol-gel route to nano-phase powders and thin films of perovskite La_0.75Sr_0.25MnO₃ is described. The phase and microstructure evolution on heat treatment of free gel films to form the target nano-phase oxide were investigated by TGA, IR spectroscopy, powder XRD, SEM and TEM-EDS. The xerogel consisted of a hydrated oxo-carbonate, without remaining alkoxo groups or solvent. Heating at 5°C·min^–1 decomposed the carbonate groups and yielded the pure perovskite La_0.75Sr_0.25MnO₃ at 760°C. The cell dimensions were virtually unchanged from the first observation of perovskite at 680°C, to 1000°C, 4 h. The monoclinic cell of La_0.75Sr_0.25MnO₃ obtained at 1000°C, 4 h, had the dimensions a = 5.475(1), b = 5.504(2), c = 7.771(1) Å, = 90.50(2), fitting the literature data quite well. Crack-free, homogenous, 150 nm thick La_0.75Sr_0.25MnO₃ films were prepared by spin-coating Si/SiO₂/TiO₂/Pt and polycrystalline -Al₂O₃ substrates with a 0.6 M alkoxide solution, followed by heating at 5°C·min^–1 to 800°C, 30 min.     

Surface structure of cubic ionic crystals studied by optical second-harmonic generation

Polarization and azimuthal dependencies of optical second-harmonic generation at the surface of cubic ionic crystals have been measured on polished surfaces of BaF₂ (111) and (100), CaF₂ (111) and NaCl (111), using a fundamental wavelength of 532 nm. The results are interpreted in terms of available theory, which shows that for transparent cubic media only the dipolar surface contribution depends on the crystal orientation. For BaF₂ (111) and NaCl (111) the crystallineC _3vgeometry could be identified but not for CaF₂ (111). Although the nature of the electronic surface structure giving rise to a dipolar polarizability remains undetermined, the experimental result suggests that it may be due to impurity or defect states in the band gap at the surface.     

A Study of the Hydrolysis-Condensation Pathways of a Hetero Bimetallic Alkoxide,Ni2Sb4(OEt)16

The hydrolysis-condensation pathways of Ni-Sb-ethoxides in different toluene-ethanol solvents have been studied. The hydrolysis was performed by slow addition of controlled amounts of water, diluted in toluene-ethanol solvents. Characterization of the hydrolysis products was performed with single crystal X-ray determinations, IR-spectroscopy, UV-Vis spectroscopy and TGA. In this way, a number of different Ni-Sb-(oxo)-ethoxides have been isolated and characterized. It was thereby shown that the Ni:Sb ratio of the hetero bimetallic oxo-alkoxides varied much depending on the degree of hydrolysis and that the species formed vary with the solvent used and the speed at which the water is added.     

Low Cost Selective Solar Absorber Coatings: Characteristics of Carbon-In-Silica Synthesized with Sol-Gel Technique

Carbon-silica composite films have been fabricated using sol-gel synthesis of silica-carbon precursor composites, followed by carbonization in an inert atmosphere. Four categories of samples were studied. These were the tetraethyl orthosilicate-only (TEOS-only), methyl trimethoxysilane (MTES), acetic acid anhydride (Ac₂O) and soot (SOOT) samples. The carbon-silica films, spin-coated on aluminium and steel substrates, have been investigated for selective solar absorber functionality. Optical measurements were performed on these samples to determine solar absorptance and thermal emittance of each. The morphology of the films was studied by electron microscopy. Electron energy-loss spectroscopy (EELS) mapping was used to determine the carbon distribution. An optimum performance of 0.88 for solar absorptance and 0.41 for thermal emittance has been achieved. The sol-gel technique produced films with very flat surfaces and uniform thicknesses in the 1 μm range. The fine structure showed homogeneous mixing of the carbon and silica in the TEOS-only samples while the separate additions of MTES and Ac₂O resulted in segregation of composition of the silica and carbon at nano-scale. The addition of 20 wt% MTES or 15 wt% Ac₂O to the TEOS-only sols also helped to reduce the cracks in the TEOS-only samples. The addition of soot in place of the carbon precursor did not yield a net advantage.     

Tunneling through weak interactions: comparison of through-space-, H-bond-, and through-bond-mediated tunneling

Results from ab initio electronic structure theory calculations on model systems allow for the detailed comparison of tunneling through covalently bonded contacts, hydrogen bonds, and van der Waals contacts. Considerable geometrical sensitivity as well as an exponential distance dependence of the tunneling is observed for tunneling through various nonbonded contacts. However, the fundamental result from the present study is that at most a modest difference is observed between tunneling mediated by H-bonds and tunneling mediated by van der Waals contacts at typical distances for each type of interaction. These results are considered in relation to the pathways model of Beratan and Onuchic, and implications for understanding long-range tunneling in biological systems are discussed.