Landau theory description of observed isotropic to anisotropic phase transition in mixed clay gels

A characteristic new cooperative dehydration transition, in 1:1 Laponite-MMT cogel, was observed at T(c) ≈ 60 °C, a temperature at which the storage modulus (G(')) and depolarization ratio (D(p)) showed sharp increase, and the isotropic cogel turned into an anisotropic one. The dehydration dynamics could be described through power-law relations: G(') ～ (T(c)-T)(-γ) and D(p) ～ (T(c)-T)(-β) with γ ≈ β = 0.40 ± 0.05. The x-ray diffraction data revealed that the crystallite size decreased from 17 nm (at 20 °C) to 10 nm (at 80 °C) implying loss of free and inter-planar water. When this cogel was spontaneously cooled below T(c), it exhibited much larger storage modulii values which implied the existence of several metastable states in this system. This phase transition could be modeled through Landau theory, where the depolarization ratio was used as experimental order parameter (ψ). This parameter was found to scale with temperature, as ψ ～ (T(c)-T)(-α), with power-law exponent α = 0.40 ± 0.05; interestingly, we found α ≈ β ≈ γ.     

Comparative studies on performance of radiation-induced and thermal cross-linked ion-exchange membrane for water electrolysis

Radiation-induced and thermal cross-linked sulfonated poly(ether sulfone) (SPS)–sulfonated poly(ether ether ketone) (SPK) composite ion-exchange membranes (SPS/SPK(γ) and SPS/SPK(T), respectively) were prepared. Their performances for water electrolysis were comparatively assessed. Thermal cross-linked membrane (SPS/SPK(T)) showed cross-linking of part functional groups (–SO₃H) and thus deterioration in membrane conductivity. While, radiation-induced cross-linked membrane (SPS/SPK(γ)) avoided any cross-linking between functional groups and thus conductivity. Electrolysis performances of these membranes were evaluated in comparison with Nafion117 membrane. Relatively low current efficiency (CE) for SPS/SPK and SPS/SPK(T) membranes was due to their high mass transfer (water) via electro-osmotic drag, which was negligible for SPS/SPK(γ) membrane. SPS/SPK(γ) membrane exhibited comparable stabilities and water splitting performance with Nafion117 membrane, which revealed its suitability as substitute for electrochemical applications.     

Synthesis,characterization and hydrogen sorption studies of mixed sodium‐potassium alanate

The aim of the present investigation is to synthesize mixed sodium potassium alanate (K₂NaAlH₆) and to explore its hydrogen sorption characteristics. K₂NaAlH₆ is synthesized through ball milling of KH and NaAlH₄ in the molar ratio 2:1 under hydrogen pressure of 10 bar. The temperature programmed desorption experiment shows that the synthesized K₂NaAlH₆ has peak desorption temperature of ∼352°C and reveals appreciable rehydrogenation kinetics under 6 bar hydrogen pressure at 300°C. The investigations are also focused on the catalytic effect of carbon nanostructures (CNS) namely, the graphene sheet (GS) and single wall carbon nanotube (SWCNT) and titanium halides (TiCl₃ and TiF₃) on K₂NaAlH₆. In the case of graphene and SWCNT catalyzed K₂NaAlH₆, the peak desorption temperature gets reduced to ∼347°C and ∼341°C respectively. The catalytic effects of CNS and titanium halide on K₂NaAlH₆ are also compared in the investigation. Between the two types of catalysts, halides are found to be better than CNS and out of the two halides, TiF₃ is found to be the best catalyst for hydrogen sorption in K₂NaAlH₆. The peak desorption temperature decreases significantly from 352°C to ∼324°C for TiF₃ catalyzed K₂NaAlH₆. Thus, the desorption activation energy reduces drastically from 124.43 kJ/mol (synthesized K₂NaAlH₆) to 88.05 kJ/mol for TiF₃ catalyzed K₂NaAlH₆.     

New exact solutions of the Einstein-Maxwell equations for magnetostatic fields

The symmetry reduction method based on the Fr′echet derivative of differential operators is applied to investigate symmetries of the Einstein-Maxwell field equations for magnetostatic fields, which is a coupled system of nonlinear partial differential equations of the second order. The technique yields invariant transformations that reduce the given system of partial differential equations to a system of nonlinear ordinary differential equations. Some of the reduced systems are further studied to obtain the exact solutions.     

Catalytic dehydrocoupling of thienyl/furyl-substituted carbosilanes – Synthesis and characterization of functional poly(hydrosilane)s [RMe2Si(CH2)xSiH]n, (R = 2-Th, 4-Me-2-Th, 2-Fu, 5-Me-2-Fu; x = 2 and 3)

The carbosilanes RMe₂Si(CH₂)_xSiH₃, [R = 2-Th (1a, 2a), 4-Me-2-Th (3a, 4a), 2-Fu (5a, 6a), 5-Me-2-Fu (7a, 8a); x = 2 and 3], with primary SiH₃ end groups undergo a facile dehydropolymerization under ambient conditions (50 °C, 48 h) in presence of Cp₂TiCl₂/2.2 n-BuLi catalyst to afford the corresponding poly(hydrosilane)s 1–8 bearing carbosilyl side chains appended with thienyl/furyl groups. These have been characterized by GPC, IR, multinuclear (¹H, ¹³C{¹H}, ²⁹Si{¹H}) NMR, UV and PL spectral studies.     

Diorgano-gallium and -indium complexes with salen ligands: Synthesis, characterization, crystal structure and C-C coupling reactions

The reactions of triorgano-gallium and -indium etherate with salen ligands in benzene afforded complexes of the type [R₂MOC₆H₄CR′NCH₂-]₂, (R/M/R′ = Me/Ga/H (1), Et/Ga/H (2), Me/In/H (3), Et/Ga/Me (4)) in nearly quantitative yields. These complexes have been characterized by elemental analysis, IR, UV-Vis, NMR (¹H and ¹³C{¹H}) and mass spectral data. The organogallium complexes showed photoluminescence in blue-green region. The complex, [(Me₂Ga)₂(O-(C₆H₄)CHN-CH₂-)₂] on recrystallization from benzene-hexane and dichloromethane gave orthorhombic and monoclinic forms, respectively. Both the forms are dimeric with gallium atoms acquiring a distorted tetrahedral configuration defined by two methyl groups, phenolate oxygen and azomethene nitrogen. The complexes [(Me₂Ga)₂(O-(C₆H₄)CHN-CH₂-)₂] and [(Me₂In)₂(O-(C₆H₄)CHN-CH₂-)₂] have been employed as alkylating agent for C-C coupling reaction of 1-bromonaphthalene in presence of PdCl₂(PPh₃)₂.     

Surface redox polymerized SPEEK–MO2–PANI (M = Si, Zr and Ti) composite polyelectrolyte membranes impervious to methanol

We reported sulfonated poly(ether ether ketone) (SPEEK, 61% degree of sulfonation)–metal oxides (MO₂:SiO₂, TiO₂ and ZrO₂)–polyaniline composite membranes. Metal oxides were incorporated into the swelled SPEEK membrane by sol–gel method and cured by thermal treatment. SPEEK–metal oxide membranes surfaces were modified with polyaniline (PANI) by a redox polymerization process. It was observed that water retention capacity of membrane was increased and methanol permeability was reduced due to synergetic effect of metal oxides and surface modification with polyaniline. These composite membranes showed extremely low methanol permeability (1.9–1.3 × 10⁻⁷ cm² s⁻¹), which was lower than till reported values either for SPEEK–metal oxide or SPEEK/PANI membranes. Relatively high selectivity parameter (SP) values at 343 K of these membranes, especially S–SiO₂–PANI and S–TiO₂–PANI, indicated their great advantages over Nafion117 (N117) membrane for targeting on moderate temperature applications due to the synergetic effect of MO₂ and PANI in SPEEK matrix. S–TiO₂–PANI and N117 showed comparable cell performance in direct methanol fuel cell (DMFC).     

Comparisons of multi-wavelength oscillations using Sagnac loop mirror and Mach-Zehnder interferometer for ytterbium doped fiber lasers

A multiwavelength Ytterbium-doped fiber ring laser operating at 1030 nm region is demonstrated using a Sagnac loop mirror and a Mach-Zehnder interferometer. We report the Performance comparisons of multi-wavelength oscillations in Yb³⁺ doped fiber lasers (YDFL) with typical commercial ytterbium doped silica fibers. By adjusting the polarization controller (PC), a widely tunable laser range of 22 nm from 1030 nm to 1050 nm is obtained. The Mach-Zehnder interferometer (MZI) design has exhibited simplicity in the operation for controlling the smallest wavelength spacing compared to Sagnac loop mirror method. In our observations, the smallest achieved stable wavelength spacing in Sagnac loop mirror setup and MZI setup were 2.1 nm and 0.7 nm, respectively. In case of nine-wavelength operation with a MZI setup, the stability, Full Width at Half Maximum (FWHM) and side mode suppression ratio (SMSR) of laser lines are not affected by increasing pump power, While for above four wavelength operation, the laser stability with Sagnac loop mirror becomes worse specially for higher input pump power and the power fluctuation among the wave-lengths would be also slightly larger.     

A comparative study of pure and potassium doped cadmium mercury thiocyanate single crystals grown in silica gel

Pure and potassium doped cadmium mercury thiocyanate single crystals have been obtained from silica gel by the process of diffusion. The X‐ray diffraction studies reveal the crystal lattice of both pure and doped crystals to be tetragonal. The crystalline perfection of the grown crystals were investigated by high resolution X‐ray diffraction analysis and the quality of the crystals are found to be extremely good. Transmission and Fourier transform infrared spectra were recorded for the grown crystals. The TG/DTA analyses show that the crystals are highly thermally stable. The mechanical strength of the crystals were studied by Vickers microhardness test and a study of their second harmonic generation efficiency in comparison with urea has been made by performing Kurtz powder test. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)