Synthesis and characterization of photo-crosslinkable main-chain liquid-crystalline polymers containing bis(benzylidene)cycloalkanone units

A series of new photo-crosslinkable main-chain liquid-crystalline polymers containing bis(benzylidene)cycloalkanone units have been studied. These units in the polymers function as mesogens as well as photoactive centres. Polyesters with three different bis(4-hydroxybenzylidene)cycloalkanones corresponding to three cycloalkanones, namely cyclopentanone, cyclohexanone and cycloheptanone, have been prepared. Three dicarboxylic acids with ether linkages, which were derived from oligoethylene oxides, namely triethylene glycol, tetraethylene glycol and pentaethylene glycol, have been used as spacers in these polymers. Polymerization was carried out by both solution and interfacial polycondensation; the latter method gave high-molecular-weight polymers. Structural characterizations were done by ultra-violet, infra-red and H-1 nuclear magnetic resonance spectroscopy. Liquid-crystalline properties were studied by differential scanning calorimetry and polarized-light optical microscopy. These polymers show a nematic mesophase. Liquid-crystalline transition temperatures were correlated with polymer structure. The decrease in transition temperature with increase in cycloalkanone ring size was explained in terms of the change in geometrical anisotropy of bis(benzylidene)cycloalkanone units. MNDO (modified neglect of differential overlap) calculations were performed on the model compounds, bis(4-acetyloxybenzylidene)cycloalkanone to elucidate the geometrical variation of the mesogenic units with cycloalkanone ring size. Studies of photolysis reveal the two kinds of photoreactions that proceed in these polymer systems, namely photoisomerization and photo-crosslinking. The former reaction disrupts the parallel stacking of the chromophores and is reflected as an increase in the ultra-violet spectral intensity. The favourability of these two reactions depends on the mobility of the polymer chains. When the photolysis was done below T-g, photo-crosslinking dominates over photoisomerization. Above T-g, photoisomerization is followed by photo-crosslinking. The photosensitivity of the polymers decreases with increase in size of the cycloalkanone ring.

Preparation and characterization of nanocrystalline powders of bismuth vanadate

The influence of mechanical activation on the formation of Bi2VO5.5 bismuth vanadate (BiV) phase, was investigated by ball-milling a stoichiometric mixture of bismuth oxide and vanadium pentoxide. The structural evolution of the desired BN phase, via an intermediate BiVO4,phase, was investigated using X-ray powder diffraction; (XRD), differential thermal analysis (DTA) and transmission electron microscopy (TEM). Milling for 54h. yielded monophasic gamma-BiV powders with an average crystallite size of 30 nm. The electron paramagnetic resonance (EPR) peaks associated with the V4+ ions are stronger and broader in nanocrystalline (n) BN than in the conventionally prepared microcrystalline (m) BN, suggesting theta significant portion of V5+ has been transformed to V4+ during milling. The optical bandgap of n-BiV was found to be higher than that of m-BiV. High density (97% of the theoretical density), fine-grained (average grain-size of 2 tun) ceramics with uniform grain-size distribution could be fabricated using n-BiV powders. These fine-grained ceramics exhibit improved dielectric, pyre and ferroelectric properties. (C) 1999 Elsevier Science S.A. All rights reserved.

Synthesis and characterization of some new dimesogenic compounds

We have synthesized four different types of dimesogenic compounds involving the cholesteryl moiety as one of the mesogenic constituents, and have investigated their liquid crystalline properties. The molecular structures of these dimesogens have been confirmed by spectral analyses; they exhibit a rich polymorphism, as revealed by optical microscopic and differential scanning calorimetric observations. The studies show that the mesomorphic behaviour is sensitive to the nature of the terminal alkyl chains, and to the structure of the 'second mesogen' that is attached to the cholesteryl unit through a polymethylene spacer.

Characterization of electrochemically deposited Cu-Ni black coatings

Electrochemically deposited Cu-Ni black coatings on molybdenum substrate from ethylenediaminetetraacetic acid (EDTA) bath solution are shown to exhibit good optical properties (alpha = 0.94, epsilon = 0.09). The deposit is characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Cu is present in metallic and +2 oxidation states in the as-prepared Cu-Ni black coating, whereas Ni2+ as well as Ni3+ species are observed in the same coating. Cu and Ni are observed in their metallic state after 10 and 20 min sputtering. X-ray initiated Auger electron spectroscopy (XAES) of Cu and Ni also agrees well with XPS investigations. (C) 2002 Elsevier Science Ltd. All rights reserved.

Synthesis and characterization of mono- and bis-D-pi-A cryptand derivatives for second-order nonlinear optics and its modulation with different metal ion inputs

Two new classes of mono- and bis-D-pi-A cryptand derivatives with a flexible and a rigid cryptand core have been synthesized. The linear and nonlinear optical properties of these molecules are probed. The three dimensional cavity of the cryptand moiety has been utilized to modulate the SHG intensity to different extents in solution with metal ion inputs such as Ni-II,Cu-II,Zn-II, and Cd-II. We also report that decomplexation events can be used to reversibly modulate their NLO responses.

Characterization of lithium borate–bismuth tungstate glasses and glass-ceramics by impedance spectroscopy

Transparent glasses in the system (1−x)Li2B4O7–xBi2WO6 (0≤x≤0.35) were prepared via melt quenching technique. Differential thermal analysis was employed to characterize the as-quenched glasses. Glass-ceramics with high optical transparency were obtained by controlled heat-treatment of the glasses at 720 K for 6 h. The amorphous nature of the as-quenched glass and crystallinity of glass-ceramics were confirmed by X-ray powder diffraction studies. High resolution transmission electron microscopy (HRTEM) shows the presence of nearly spherical nanocrystallites of Bi2WO6 in Li2B4O7 glass matrix. Capacitance and dielectric loss measurements were carried out as a function of temperature (300–870 K) in the frequency range 100 Hz–40 MHz. Impedance spectroscopy employed to rationalize the electrical behavior of glasses and glass-ceramics suggest the coexistence of electronic and ionic conduction in these materials. The thermal activation energies for the electronic conduction and ionic conduction were also estimated based on the Arrhenius plots.

Growth and characterization of ferroelectric glycine phosphite single crystals

Single crystals of a recent ferroelectric material, glycine phosphite were grown from aqueous solution employing the techniques of slow cooling and controlled evaporation. Powder X-ray diffraction studies as well as thermal analysis were carried out on the grown crystals. The morphology of the crystal has been determined using contact and optical goniometry. The mechanical hardness of the crystal was evaluated by Vickers indentation method. Thickness dependence of the dielectric properties has been investigated and the results can be interpreted in terms of a surface layer of lower dielectric constant.

Growth and Characterization of GaAs Epitaxial Layers by MOCVD

technique, on both semi-insulating and semi-conducting CraAs substrates with (100) orientation, offset by 2° towards (110) direction. Systematic variation of As/Ga was performed to gain an understanding of growth process, type of formation and other related physical properties. The films were characterized by using the variety of techniques, such as SEM, EDAX, HRTEM, XRD, and PL. Optical and electrical properties of undoped CyaAs epilayers are presented with reference to the growth conditions and AsH3/TMGa ratio. Photoluminescence measurements of GaAs epilayers were recorded at 4.2K and shows the emission of free exciton and confirmed their high purity. The dominant residual impurities in GaAs are presented by using PL. Finally, electrochemical depth profiling exhibited almost homogeneous background carrier distribution and excellent abruptness between the thin GaAs epilayer and substrate.

Studies on thin film materials on acrylics for optical applications

Deposition of durable thin film coatings by vacuum evaporation on acrylic substrates for optical applications is a challenging job. Films crack upon deposition due to internal stresses and leads to performance degradation. In this investigation, we report the preparation and characterization of single and multi-layer films of TiO2, CeO2, Substance2 (E Merck, Germany), Al2O3, SiO2 and MgF2 by electron beam evaporation on both glass and PMMA substrates. Optical micrographs taken on single layer films deposited on PMMA substrates did not reveal any cracks. Cracks in films were observed on PMMA substrates when the substrate temperature exceeded 80degreesC. Antireflection coatings of 3 and 4 layers have been deposited and characterized. Antireflection coatings made on PMMA substrate using Substance2 (H2) and SiO2 combination showed very fine cracks when observed under microscope. Optical performance of the coatings has been explained with the help of optical micrographs.

Microwave ECR Plasma Assisted MOCVD of Y(2)O(3) Thin Films Using Y(tod)(3) Precursor and Their Characterization

Yttrium oxide (Y(2)O(3)) thin films were deposited by microwave electron cyclotron resonance (ECR) plasma assisted metal organic chemical vapour deposition (MOCVD) process using indigenously developed metal organic precursors Yttrium 2,7,7-trimethyl-3,5-octanedionates, commonly known as Y(tod)(3) which were synthesized by an ultrasound method. A series of thin films were deposited by varying the oxygen flow rate from 1-9 sccm, keeping all other parameters constant. The deposited coatings were characterized by X-ray photoelectron spectroscopy, glancing angle X-ray diffraction and infrared spectroscopy. Thickness and roughness for the films were measured by stylus profilometry. Optical properties of the coatings were studied by the spectroscopic ellipsometry. Hardness and elastic modulus of the films were measured by nanoindentation technique. Being that microwave ECR CVD process is operating-pressure-sensitive, optimum oxygen activity is very essential for a fixed flow rate of precursor, in order to get a single phase cubic yttrium oxide in the films. To the best of our knowledge, this is the first effort that describes the use of Y(tod)(3) precursor for deposition of Y(2)O(3) films using plasma assisted CVD process.

Phase Characterization and Study of Molecular Order of a Three-Ring Mesogen by (13)C NMR in Smectic C and Nematic Phases

Molecules exhibiting a thermotropic liquid-crystalline property have acquired significant importance due to their sensitivity to external stimuli such as temperature, mechanical forces, and electric and magnetic fields. As a result, several novel mesogens have been synthesized by the introduction of various functional groups in the vicinity of the aromatic core as well as in the side chains and their properties have been studied. In the present study, we report three-ring mesogens with hydroxyl groups at one terminal. These mesogens were synthesized by a multistep route, and structural characterization was accomplished by spectral techniques. The mesophase properties were studied by hot-stage optical polarizing microscopy, differential scanning calorimetry, and small-angle X-ray scattering. An enantiotropic nematic phase was noticed for lower homologues, while an additional smectic C phase was found for higher homologues. Solid-state high-resolution natural abundance (13)C NMR studies of a typical mesogen in the solid phase and in the mesophases have been carried out. The (13)C NMR spectrum of the mesogen in the smectic C and nematic phases indicated spontaneous alignment of the molecule in the magnetic field. By utilizing the two-dimensional separated local field (SLF) NMR experiment known as SAMPI4, (13)C-(1)H dipolar couplings have been obtained, which were utilized to determine the orientational order parameters of the mesogen.

Combustion synthesis, characterization and Raman studies of ZnO nanopowders

Spherical shaped ZnO nanopowders (14-50 nm) were synthesized by a low temperature solution combustion method in a short time <5 min. Rietveld analysis show that ZnO has hexagonal wurtzite structure with lattice constants a = 3.2511(1) angstrom, c = 5.2076(2) angstrom, unit cell volume (V) = 47.66(5) (angstrom)(3) and belongs to space group P63mc. SEM micrographs reveal that the particles are spherical in shape and the powders contained several voids and pores. TEM results also confirm spherical shape, with average particle size of 14-50 nm. The values are consistent with the grain sizes measured from Scherrer's method and Williamson-Hall (W-H) plots. A broad UV-vis absorption spectrum was observed at similar to 375 nm which is a characteristic band for the wurtzite hexagonal pure ZnO. The optical energy band gap of 3.24 eV was observed for nanopowder which is slightly lower than that of the bulk ZnO (3.37 eV). The observed Raman peaks at 438 and 588 cm(-1) were attributed to the E(2) (high) and E(1) (LO) modes respectively. The broad band at 564 cm(-1) is due to disorder-activated Raman scattering for the A(1) mode. These bands are associated with the first-order Raman active modes of the ZnO phase. The weak bands observed in the range 750-1000 cm(-1) are due to small defects. (C) 2011 Elsevier B.V. All rights reserved.

Growth of InSb(1-x)Bix crystals by Rotatary Bridgman method and their characterization

The Rotatary Bridgman method was used to grow ternary InSb(1-x)SBix, crystals. In this method the ampoule was subjected to reversible rotation at a rate of 60rpm. High quality crystals of 8mm diameter and 25mm length were grown with 6.5 atomic percentage of Bi. The grown crystals were characterized employing various techniques such as energy dispersive spectroscopy, x-ray diffraction, differential scanning calorimetery, infrared spectroscopy and Hall measurement.

Cobalt-doped ZnO nanowires on quartz: Synthesis by simple chemical method and characterization

The synthesis of cobalt-doped ZnO nanowires is achieved using a simple, metal salt decomposition growth technique. A sequence of drop casting on a quartz substrate held at 100 degrees C and annealing results in the growth of nanowires of average (modal) length similar to 200 nm and diameter of 15 +/- 4 nm and consequently an aspect ratio of similar to 13. A variation in the synthesis process, where the solution of mixed salts is deposited on the substrate at 25 degrees C, yields a grainy film structure which constitutes a useful comparator case. X-ray diffraction shows a preferred 0001] growth direction for the nanowires while a small unit cell volume contraction for Co-doped samples and data from Raman spectroscopy indicate incorporation of the Co dopant into the lattice; neither technique shows explicit evidence of cobalt oxides. Also the nanowire samples display excellent optical transmission across the entire visible range, as well as strong photoluminescence (exciton emission) in the near UV, centered at 3.25 eV. (C) 2012 Elsevier B.V. All rights reserved.