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251.
Chinnaswamy Thangavel Vijayakumar Palanichamy Sivasamy Bashyam Geetha Johannes Karl Fink 《Macromolecular Symposia》2002,181(1):245-252
Spiro phosphorus compounds play a vital role, in recent years, in imparting flame retardancy and intumescence to the polymers. To ascertain the mechanism of the intumescency, model spiro phosphorus compounds, i.e., 3,9-disubstituted-2,4,8,10-tetraoxa-3,9-diphosphaspiro-[5.5]-undecan- 3,9-dioxide, were chosen (compound I : substitution is chloro group and compound II : substitution is hydroxo group). The model compounds were investigated using Differential Thermal Analysis (DTA) and Thermal Volatilization Analysis (TVA), Vacuum Pyrolysis-MS and Off-line Pyrolysis followed by degradation product analysis by GC-MS. Dichlorospiro compound (I) showed an eruptive release of gases at 320°C and dihydroxo spiro compound (II) at about 350°C. The major components of the gas released were found to be HCl and H2O in the case of compound I and H2O in the case of compound II. The degradation product analysis showed the formation of wide varieties of substituted and condensed aromatic compounds in measurable quantities. From the acquired data, it is confirmed that the intumescence takes place within a narrow range of temperature (10°) and in this temperature limit extensive dehydrohalogenation and dehydration are taking place. Highly thermally reactive unsaturated hydrocarbons are produced which mainly undergo polymerization to aromatic compounds and finally to char. 相似文献
252.
T. Vijayakumar I. Hubert Joe C. P. Reghunadhan Nair Mojca Jazbinsek V. S. Jayakumar 《Journal of Raman spectroscopy : JRS》2009,40(1):52-63
The optimized geometry and structural features of the most prospective electro‐optic crystal 4‐(N,N‐dimethylamino)‐N‐methyl‐4′‐toluene sulfonate (DAST), and the vibrational spectral investigations have been comprehensively described with the near infrared Fourier transform (NIR FT) Raman and Fourier transform infrared (FT‐IR) spectra supported by the density functional theoretical (DFT) computations to elucidate the contribution of vibrational modes to the linear electro‐optic (LEO) effect. Mulliken population analysis and natural bond orbital (NBO) analysis have also been carried out to analyze the effects of intramolecular charge transfer (ICT), intramolecular hydrogen bonding and hyperconjugative interactions on the geometries. The influence of CT interaction between the phenyl ring and the dimethylamino group of the nonlinear optical (NLO) chromophore on the endocyclic and exocyclic angles, and the electronic effects such as hyperconjugation and back‐donation on the methyl hydrogen atoms have been examined. The concurrent intense activation of Raman and IR activities of the effective conjugation vibrational coordinate, which significantly contributes to the LEO effect resulting from the strong electron–phonon (e/ph) coupling, has been analyzed in detail. The effects of frontier orbitals, highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO), transition of electron density (ED) transfer and the influence of planarity in the stilbazolium ring on the first hyperpolarizability are also discussed. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
253.
Dr. Laidong Zhou Dr. J. David Bazak Dr. Baltej Singh Chang Li Dr. Abdeljalil Assoud Dr. Nancy M. Washton Dr. Vijayakumar Murugesan Prof. Linda F. Nazar 《Angewandte Chemie (International ed. in English)》2023,62(30):e202300404
We report a new sodium fast-ion conductor, Na3B5S9, that exhibits a high Na ion total conductivity of 0.80 mS cm−1 (sintered pellet; cold-pressed pellet=0.21 mS cm−1). The structure consists of corner-sharing B10S20 supertetrahedral clusters, which create a framework that supports 3D Na ion diffusion channels. The Na ions are well-distributed in the channels and form a disordered sublattice spanning five Na crystallographic sites. The combination of structural elucidation via single crystal X-ray diffraction and powder synchrotron X-ray diffraction at variable temperatures, solid-state nuclear magnetic resonance spectra and ab initio molecular dynamics simulations reveal high Na-ion mobility (predicted conductivity: 0.96 mS cm−1) and the nature of the 3D diffusion pathways. Notably, the Na ion sublattice orders at low temperatures, resulting in isolated Na polyhedra and thus much lower ionic conductivity. This highlights the importance of a disordered Na ion sublattice—and existence of well-connected Na ion migration pathways formed via face-sharing polyhedra—in dictating Na ion diffusion. 相似文献
254.