Study of the hydrolysis and condensation of γ-Aminopropyltriethoxysilane by FT-IR spectroscopy

The hydrolysis and condensation reactions of γ-APS have been studied in different acid content aqueous solution by using Fourier Transform infrared (FT-IR) spectroscopy. The hydrolysis of γ-APS under the studied conditions can be followed by the increase of the ethanol band located at 882 cm⁻¹ and the decrease of the band due to the ρ(CH₃) of γ-APS molecules located at 959 cm⁻¹. Hydrolysis reaction is faster by increasing both H₂O and acid concentrations, and it is completed when 3 moles of H₂O per mole of γ-APS are used. The increase of the vibrational band located at 1146 cm⁻¹ shows that condensation of the hydrolysed γ-APS molecules take place forming linear chains in poorly cross-linked structures. Besides, both 8-membered cyclic siloxane formations and poorly cross-linked structures are formed and increase as the water and acid content are increased. On the other hand, highly connected cross-linked structures do not appear due to the steric hindrance of the non-hydrolysable aminopropyl group. The silanol band shows that hydrolysis is faster than condensation except for samples with the lowest H₂O content.     

Optimized hydrogen positions for aluminium and iron containing hydroxide minerals

The structures of a number of hydroxide and oxyhydroxide minerals have previously been reported without the hydrogen positions explicitly defined. Here we use two atomic scale computer simulation techniques, one based on classical ionic potentials, the other on density functional theory (DFT), to predict these positions. The aim is not only to provide data that can be used as the basis for future experimental structure optimizations but also model parameters that can be used to predict complex hydroxide structures. The efficacy of the approach is demonstrated through the comparison of predicted and experimental data for minerals whose hydrogen positions are known.     

Probing the thermal decomposition process of layered double hydroxides through in situ <Superscript>57</Superscript>Fe Mössbauer and in situ X-ray diffraction experiments

The thermal decomposition properties of Mg–Fe hydrotalcites were studied through in situ ⁵⁷Fe Mössbauer spectroscopy and in situ X-ray diffraction. Abrupt changes in the quadrupolar splitting measured in the Mössbauer spectra revealed a phase transition from the starting lamellar structure to a new crystalline arrangement. By analyzing the Mössbauer parameters we show that the material is highly disordered in the 300–400 °C temperature range. This hypothesis is confirmed by the X-ray results whose diffractograms indicated the collapse of the lamellar structure and the formation of a solid solution.     

Hydrogen adsorption studies in micro-size cobalt dots

Hydrogen desorption curves were obtained from a sample composed of a square arrangement of Co dots with average diameter of 4.4 μm, separated by a distance of 11.6 μm. A macroscopic sample of Co dots grown on a 2.5 × 2.5 cm Si substrate was made by standard lithographic techniques and used in these experiments. Thermal programmed desorption (TPD) was performed under ultra-high vacuum conditions. Hydrogen TPD curves were obtained from a 1 × 1 cm Co dots samples displaying a maximum of intensity at 425 K. Hydrogen TPD curve was also obtained from 1 cm× 1 cm samples of Co films and Co foils for comparison. The hydrogen TPD curves have decreasing intensity from the Co foils to the Co dots and finally to the Co films. This indicates that there are more sites for hydrogen adsorption on the Co dots than in the Co films. This is a surprising result because there is approximately 8.7 times less Co atoms exposed in the Co dots that in the Co film sample. A desorption energy of 27 kcal/mol was obtained for the Co dots suggesting that hydrogen is adsorbed on an hcp hollow site of the Co dot crystalline structure.     

Preparation, sintering, and microstructures of strontium barium bismuth tantalate layered perovskite ceramics

The solid solutions of Ba-doped SrBi₂Ta₂O₉ layered perovskite ceramic powders have been successfully prepared via a two-step process using BiTaO₄ as a precursor. The lattice constants of the solid solutions monotonically increase with increasing barium-ion content. The sinterability of (Sr_1–xBa_x)Bi₂Ta₂O₉ powders is significantly improved by increasing the barium-ion content. When the specimens with high barium-ion contents are sintered at 1100°C, they thermally decompose to form rod-like grains and the matrix expands, leading to a lower density. The addition of barium ions to SrBi₂Ta₂O₉ also results in significant variation in the morphology of the sintered specimens and the occurrence of c-axis preferred orientation which is ascribed to the anisotropic growth of plate-like grains. The precise control of the barium-ion content as well as the sintering conditions is critical for obtaining densified barium-ion doped SrBi₂Ta₂O₉ ceramics with a pure, layered perovskite structure.