Formation of a crosslinked POSS network by an unusual hydrosilylation: Thermo‐oxidative stabilization of the α‐cristobalite phase in its amorphous regions

A semicrystalline inorganic–organic hybrid crosslinked network containing polyhedral oligomeric silsesquioxane (POSS) cores was constructed by the unusual hydrosilylation of the terminal vinyl groups of an internal acetylene‐containing silane linker by a POSS monomer. Products from the thermal treatments of this network in either argon or air at 250, 550, and 1000 °C, respectively, were characterized by Fourier transform infrared, Solid‐state ¹³C and ²⁹Si magic angle spinning NMR, X‐ray diffraction and XPS analyses. The highly symmetrically functionalized POSS silica clusters, in the fluorite silica phase, in the network were found to remain unchanged on thermal treatment possibly due to the shielding of the silica core by the functionalities and a cancellation of thermal stresses on the silica core. Stabilization of the metastable α‐cristobalite phase, which is typically formed on cooling by a β‐ to α‐transition of the β‐cristobalite phase formed above 1400 °C, was observed in the amorphous regions in the network sample treated only to 1000 °C in air. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Hybrid inorganic–organic poly(carborane‐siloxane‐arylacetylene) structural isomers with in‐chain aromatics: Synthesis and properties

Structural isomers of thermo‐oxidatively stable poly(carborane‐siloxane‐arylacetylene) (PCSAA), namely, m‐PCSAA and p‐PCSAA, were synthesized by the reaction of the dimagnesium salts of m‐diethynylbenzene or p‐diethynylbenzene with 1,7‐bis(chlorotetramethyldisiloxyl)‐m‐carborane. The developed polymers have exceptional thermo‐oxidative properties similar to their diacetylene counterpart poly(carborane‐siloxane‐acetylene), PCSA. Thermal treatment of either of the PCSAAs results in a fully crosslinked thermoset by 500 °C resulting from the cycloaddition reactions involving the acetylene and aryl functionalities and subsequent formation of bridging disilylmethylene entities as discerned from Fourier transform infrared, ¹³C and ²⁹Si solid‐state NMR, and XPS studies. X‐ray diffraction analysis revealed that the thermosets obtained from p‐PCSAA possess enhanced crystallinity when compared to that obtained from m‐PCSAA possibly due to more efficient packing interactions of the p‐diethynylbenzene groups during thermoset formation. The presence of the aryl groups in the backbone of the PCSAAs' chains appeared to have enhanced the storage and bulk moduli of their thermosets when compared to the thermoset of PCSA. Dielectric studies of m‐PCSAA and p‐PCSAA revealed segmental relaxation peaks, α, above their glass transition temperatures with p‐PCSAA exhibiting a broader peak with a slower relaxation rate than m‐PCSAA. © 2013 Wiley Periodicals, Inc.^? J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2638–2650     

Novel techniques for the prepartion of synthetic diamond

Abstract

The objectives of this work are two fold: (1) to study the effect of using oxygen-acetylene flame grown synthetic diamond as seed crystals for the high pressure-high temperature conversion of graphite into diamond and (2) to demonstrate the ability to produce small crystallites of diamond by a simple, electron beam evaporation technique. In each case, the production of diamond from graphite was confirmed.     

High pressure-high temperature synthesis of distorted perovskite-type Cu-based oxides

Abstract

We have synthesized the rhombohedrally distorted perovskite phase of LaCuO₃ by reacting mixtures of La₂O₃ and CuO in an oxygen rich atmosphere at 1500°C and 6.5 GPa. We find this phase to be metastable; at 410°C and ambient pressure, it undergoes an irreversible transition to a tetragonal structure. By selective replacement of some or all of the La or Cu with one or more of the following elements: Ba, Ca, Cr, Ni, Pb, Sc, Sr, Ti, Y, Zn, and Zr, over 150 different alloys have been formed. Magnetic susceptibility measurements have failed to reveal the presence of superconductivity in any of these new polymorphs.     

Electrically and magnetically tunable microwave device using (Ba, Sr) TiO3/Y3Fe5O12 multilayer

Ferroelectric (Ba_0.6Sr_0.4)TiO₃ (BST) thin films have been deposited by pulsed laser deposition onto single-crystal Y₃Fe₅O₁₂ (YIG) substrates with/without a MgO buffer layer. The structure and microwave properties of the BST films have been investigated as a function of substrate orientation and O₂ deposition pressures (50-800 mTorr). The crystallographic orientation of BST film varies with the deposition conditions. The dielectric properties of the ferroelectric were measured using interdigitated capacitors deposited on top of the BST film. BST films exhibit high tunability (20-40%) and high dielectric Q=1/cos' (30-50) with a dc bias field of 67 kV/cm at 10 GHz. A coplanar waveguide transmission line was fabricated from a (001)-oriented BST film on (111)YIG which exhibited a 17° differential phase shift with an applied dc bias field of 21 kV/cm (10 GHz). An equivalent differential phase shift was achieved with a magnetic field of 160 Gauss.     

Structural and magnetic properties of nano-crystalline RuFe alloys prepared by organometallic synthesis

Nanoparticles of Ru_1-xFe_x (0≤x≤1) in a carbon matrix were synthesized over the entire composition range using organometallic precursors. For Fe concentrations with x<0.70, a hexagonal close-packed phase was formed whereas a body-centered cubic phase was observed for x>0.70. The crystallite sizes varied between 5–10 nm. In addition, multi-wall carbon nanotubes formed during the pyrolysis of the precursors. Increasing superparamagnetic order was observed with increasing Fe content.     

Depth-resolved X-ray determination of surface strain in free-standing films of HVPE-grown GaN and <Superscript>71</Superscript>Ga NMR characterization

Free-standing GaN films grown by hydride vapor phase epitaxy (HVPE) on c-plane sapphire have been studied for in-plane anisotropic strain. Lattice parameters are obtained from high-resolution X-ray diffraction data and the film quality is determined by measuring the rocking curves and by ⁷¹Ga nuclear magnetic resonance (NMR). The in-plane strain was determined using grazing incidence X-ray diffraction and conventional X-ray measurements. It is found that the in-plane lattice parameter varies with depth and has estimated surface strain anisotropy of 4.0791×10^-3 up to a thickness of 0.3 μm. The ⁷¹Ga NMR experiments reveal different degrees of inhomogeneity amongst the three samples. This is shown by the appearance of an additional broad central-transition peak shifted to higher frequency by a Knight shift from conduction electrons in sample regions having high carrier concentrations. PACS 72.80.Ey; 61.10.-i; 61.72.Hh