Photocrosslinkable phosphorus containing homo‐ and copolyesters: Synthesis,characterization, and photosensitive properties

A new series of homo‐ and copolyphosphoramide esters containing pendant chlorine group was synthesized from dihydroxy chalcones, N‐(4‐chlorophenyl)phosphoramidic dichloride, and terephthaloyl chloride by interfacial polycondensation technique. The diol monomers were prepared by condensing 4‐hydroxy benzaldehyde and 3‐methoxy‐4‐hydroxybenzaldehyde with 4‐hydroxy acetophenone. The synthesized monomers and polymers were characterized by UV, IR and ¹H, ¹³C, and ³¹PNMR spectroscopic techniques. Molecular weight of the polymers was determined by gel permeation chromatography. The thermal properties of the polymers were studied by thermogravimetric analysis and differential scanning calorimetry under nitrogen atmosphere. The photo‐crosslinking ability of the polymers in various solvents was observed with UV spectrophotometer. The photocrosslinking proceeds via 2π +2π cycloaddition reaction of α, β‐unsaturated carbonyl group. The comparison study on the rate of photocrosslinking of homo and copolymers was also carried out. The chemical and physical properties of these polyesters are compared with those of the unsubstituted polyesters and the results are discussed herein. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Transformations of molecules and secondary building units to materials: a bottom-up approach

A variety of complex inorganic solids with open-framework and other fascinating architectures, involving silicate, phosphate, and other anions, have been synthesized under hydrothermal conditions. The past few years have also seen the successful synthesis and characterization of several molecular compounds that can act as precursors to form open-framework and other materials, some of them resembling secondary building units (SBUs). Transformations of rationally synthesized molecular compounds to materials constitute an important new direction in both structural inorganic chemistry and materials chemistry and enable possible pathways for the rational design of materials. In this article, we indicate the potential of such a bottom-up approach, by briefly examining the transformations of molecular silicates and phosphates. We discuss stable organosilanols and silicate secondary building units, phosphorous acids and phosphate secondary building units, di- and triesters of phosphoric acids, and molecular phosphate clusters and polymers. We also examine the transformations of metal dialkyl phosphates and molecular metal phosphates.     

Structural variations in layered alkaline earth metal cyclohexyl phosphonates

Two series of alkaline earth metal cyclohexyl phosphonates, M(C₆H₁₁PO₃H)₂(H₂O) (M = Ca, Sr and Ba) (1–3) and M(C₆H₁₁PO₃)(H₂O) (M = Mg, Ca, Sr, and Ba) (4–7) have been synthesized under mild reaction conditions. All new compounds have been characterized using elemental analysis, IR, TGA and powder X-ray diffraction techniques. The molecular structure of compound 2 determined using single crystal X-ray diffraction technique reveals a layered polymeric structure.     

Magnetoconvection in a square cavity with partially active vertical walls: Time periodic boundary condition

Magnetoconvection of an electrically conducting fluid in a square cavity with partially thermally active sidewalls is investigated numerically. Temperature of one of the thermally active regions of the side walls is periodic in time while the opposite wall is isothermal. The horizontal walls and the remaining parts of the side walls are thermally inactive. Nine different combinations of the relative positions of the active zones are considered. The governing equations are discretized by the control volume method with QUICK scheme and solved numerically by SIMPLE algorithm for the pressure–velocity coupling together with under relaxation technique. The tests were carried out for various values of amplitude, period, Grashof number, Hartmann number and Prandtl number. The heat transfer characteristics are presented in the form of streamlines, isotherms and velocity profiles both for transient and steady state. It is observed that the flow and the heat transfer rate in the cavity are affected by the sinusoidal temperature profile and by the magnetic field at lower values of Grashof number. The rate of heat transfer oscillates for increasing periods but it is maximum for Ω = 3 and it is found to be an increasing function of amplitude but decreases for higher values of Hartmann number. The heat transfer rate is maximum for the middle–middle thermally active locations while it is poor for the top heating and bottom cooling active locations. The average Nusselt number decreases with an increase of Hartmann number and increases with increase of Prandtl number and Grashof number.     

Magnetoconvection in an enclosure with partially active vertical walls

Magnetoconvection of an electrically conducting fluid in a square cavity with partially thermally active vertical walls is investigated numerically. The active part of the left side wall is at a higher temperature than the active part of the right side wall. The top, bottom and the inactive parts of the side walls are thermally inactive. Nine different combinations of the relative positions of the active zones are considered. The governing equations are discretized by the control volume method with QUICK scheme and solved numerically by SIMPLE algorithm for the pressure–velocity coupling together with underrelaxation technique. The results are obtained for Grashof numbers between 10⁴ and 10⁶, Hartmann numbers between 0 and 100 and Prandtl numbers 0.054–2.05. The heat transfer characteristics are presented in the form of streamlines and isotherms. The heat transfer rate is maximum for the middle–middle thermally active locations while it is poor for the top–bottom thermally active locations. The average Nusselt number decreases with an increase of Hartmann number and increases with an increase of Grashof number. For sufficiently large magnetic field Ha = 100 the convective mode of heat transfer is converted into conductive mode in the low region of Grashof number than in the high region.     

Is water a friend or foe in organometallic chemistry? The case of group 13 organometallic compounds

This Account summarizes the recent developments in the hydrolysis chemistry of Group 13 trialkyl and triaryl compounds. Emphasis has been placed on the results obtained by us on (a) 1H NMR investigations of controlled hydrolyses of AlMes3 and GaMes3, (b) low-temperature isolation of water adducts of triaryl compounds of aluminum and gallium, (c) synthesis and structural characterization of new polyhedral alumoxanes and galloxanes, and (d) the search for an easy way to synthesize well-defined crystalline methylalumoxanes by deprotonation of the hydroxides with alkyllithium reagents. The systematic studies on the hydrolysis of tBu3Al carried out by Barron et al. are also discussed in order to elucidate the roles of (i) reaction temperature, (ii) solvent medium, and (iii) source of water molecules, in building up hitherto unknown alumoxane clusters. The role of water impurity in organometallic reactions involving a Group 13 alkyl and other ligands (such as silanetriols and phosphorus acids) to build molecular clusters has also been discussed.     

Effect of substrate temperature on microstructure and optical properties of nanocrystalline alumina thin films

Aluminum oxide (Al₂O₃) thin films were deposited on silicon (100) and quartz substrates by pulsed laser deposition (PLD) at an optimized oxygen partial pressure of 3.0×10^?3 mbar in the substrate temperatures range 300–973 K. The films were characterized by X-ray diffraction, transmission electron microscopy, atomic force microscopy, spectroscopic ellipsometry, UV–visible spectroscopy and nanoindentation. The X-ray diffraction studies showed that the films deposited at low substrate temperatures (300–673 K) were amorphous Al₂O₃, whereas those deposited at higher temperatures (≥773 K) were polycrystalline cubic γ-Al₂O₃. The transmission electron microscopy studies of the film prepared at 673 K, showed diffuse ring pattern indicating the amorphous nature of Al₂O₃. The surface morphology of the films was examined by atomic force microscopy showing dense and uniform nanostructures with increased surface roughness from 0.3 to 2.3 nm with increasing substrate temperature. The optical studies were carried out by ellipsometry in the energy range 1.5–5.5 eV and revealed that the refractive index increased from 1.69 to 1.75 (λ=632.8 nm) with increasing substrate temperature. The UV–visible spectroscopy analysis indicated higher transmittance (>80%) for all the films. Nanoindentation studies revealed the hardness values of 20.8 and 24.7 GPa for the films prepared at 300 K and 973 K respectively.     

Development of ultrasensitive surfactants doped poly(3,4-ethylenedioxythiophene)/multiwalled carbon nanotube sensor for the detection of pyrethroids and an organochlorine pesticide

Fabrication of nano size poly(3,4-ethylenedioxythiophene)/multiwalled carbonnanotubes film on a glassy carbon electrode (PEDOT/MWCNT/GCE) in the presence of anionic and cationic surfactants is reported. The modified composite electrodes were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD) studies. SEM studies confirmed the formation of nano size film on the working electrode. Electroanalytical studies were carried out using the above prepared electrode by cyclic voltammetry (CV) and differential pulse stripping voltammetry (DPSV). This electrode exhibited higher sensitivity towards the reduction of cypermethrin (CYP), deltamethrin (DEL), fenvalerate (FEN) falling under pyrethroids family and an organochlorine pesticide dicofol (DCF). In CV, all the selected pesticides were found to exhibit one well-defined irreversible reduction peak at pH 13. Optimum conditions for DPSV were experimentally determined by varying several parameters. The practical application of the newly developed sensor was affirmed by quantification of the selected pesticides in spiked water samples.     

Significance of Al on the morphological and optical properties of Ti1−xAlxN thin films

TiN and Ti_1−xAl_xN thin films with different aluminum concentrations (x = 0.35, 0.40, 0.55, 0.64 and 0.81) were synthesized by reactive magnetron co-sputtering technique. The structure, surface morphology and optical properties were examined using Grazing Incidence X-ray Diffraction (GIXRD), Atomic Force Microscopy (AFM), Raman spectroscopy and spectroscopic ellipsometry, respectively. The structure of the films were found to be of rocksalt type (NaCl) for x = 0.0–0.64 and X-ray amorphous for x = 0.81. AFM topographies show continuous mound like structure for the films of x between 0.0 and 0.64, whereas the film with x = 0.81 showed smooth surface with fine grains. Micro-Raman spectroscopic studies indicate structural phase separation of AlN from TiAlN matrix for x > 0.40. Ti_1−xAl_xN has the tendency for decomposition with the increase of Al concentration whereas c-TiN and hcp-AlN are stable mostly. The optical studies carried out by spectroscopic ellipsometry measurements showed a change from metallic to insulating behavior with the increase in x. These films are found to be an insulator beyond x = 0.81.     

Study on growth,optical and dielectric properties of ‘Nd’ DOPED NBT-BT (0.94(Na0.5Bi0.5tio3)-0.06batio3) relaxor ferroelectric single crystals

Journal of Electroceramics - The present work describes the effect of Neodymium (Nd) in the NBT-BT (0.94Na0.5Bi0.5TiO3-0.06BaTiO3 (NBT-BT (94/06))?+?xNd (x?=?0, 0.4, 0.6,...