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151.
Recent X-ray diffraction studies on α-quartz (SiO2) by Kingmaet al [1], have shown the occurrence of a reversible, crystalline-to-crystalline, phase transition just prior to amorphization
at ≈ 21 GPa. This precursor transition has also been confirmed by our recent molecular dynamics simulation study [2]. In order
to investigate the possibility of a similar behaviour in other isostructural compounds, which also undergo pressure induced
amorphization, α-GeO2 and α-AlPO4 (berlinite form) were studied using energy dispersive X-ray diffraction. In either of these materials, no such phase transition
is detected prior to amorphization. The onset of amorphization and its reversal is found to be time dependent in GeO2. 相似文献
152.
Brad M. Rosen Virgil Percec 《Journal of polymer science. Part A, Polymer chemistry》2007,45(21):4950-4964
Atom transfer radical polymerization (ATRP) and single electron‐transfer living radical polymerization (SET‐LRP) both utilize copper complexes of various oxidation states with N‐ligands to perform their respective activation and deactivation steps. Herein, we utilize DFT (B3YLP) methods to determine the preferred ligand‐binding geometries for Cu/N‐ligand complexes related to ATRP and SET‐LRP. We find that those ligands capable of achieving tetrahedral complexes with CuI and trigonal bipyramidal with axial halide complexes with [CuIIX]+ have higher energies of stabilization. We were able to correlate calculated preferential stabilization of [CuIIX]+ with those ligands that perform best in SET‐LRP. A crude calculation of energy of disproportionation revealed that the same preferential binding of [CuIIX]+ results in increased propensity for disproportionation. Finally, by examining the relative energies of the basic steps of ATRP and SET‐LRP, we were able to rationalize the transition from the ATRP mechanism to the SET‐LRP mechanism as we transition from typical nonpolar ATRP solvents to polar SET‐LRP solvents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4950–4964, 2007 相似文献
153.
154.
Binyuan Liu Yang Li Boo‐Gyo Shin Do Yeung Yoon IL Kim Li Zhang Weidong Yan 《Journal of polymer science. Part A, Polymer chemistry》2007,45(15):3391-3399
Three novel functionalized polynorbornenes (PNB) with pendant dimethyl carboxylate group (carboxylates—acetate, propionate, and butyrate) are synthesized as a vinyl‐type with a palladium (II) catalyst in high yield. The effects of size of substitutents, molar ratio of monomer to catalyst, solvent polarity, reaction time, and temperature on the polymerization of exo‐norbornene dimethyl propionate were systematically investigated. The low molar ratio and temperature, as well as high polarity of solvent, and long reaction time, are favorable for the enhancement of the monomer conversion, especially, the solvent have an obvious effect on the catalyst activity. The resulting poly(cis‐norbornene‐exo‐2,3‐dimethyl carboxylates) (PNB‐dimethyl carboxylates) show good solubility in common organic solvent and high thermal stability up to 360 °C. The glass transition temperature was detected by DMA at 331, 324, and 318 °C for acetate, propionate, and butyrate, respectively. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3391–3399, 2007 相似文献
155.
Improved reaction conditions for the preparation of poly(p‐phenylene sulfide) (PPS) directly from bis(4‐bromophenyl) disulfide (BBD) have been established. Heating BBD with magnesium metal afforded only a low molecular weight polymer. PPS with a melting temperature around 280 °C was obtained from BBD in the presence of sodium carbonate or zinc metal. The best results were obtained with the addition of a catalytic amount of KI to the zinc–BBD mixture. Polymers prepared by the above methods are semicrystalline and dissolve in 1‐chloronaphthalene and have properties comparable to commercial PPS. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 900–904, 2006 相似文献
156.
Toshiyuki Oyama Akira Kitamura Eiichi Sato Masao Tomoi 《Journal of polymer science. Part A, Polymer chemistry》2006,44(8):2694-2706
The factors affecting pattern‐forming properties in reaction development patterning were examined with polyarylates with various bisphenol moieties. The developability of the photosensitive polyarylates was dependent on the properties of the subtituent (R) in the bisphenol moieties. The development time decreased in the following order: R?C(CH3)2 > fluorenyl unit ? phenolphthalein unit > C(CF3)2 > SO2. This order agreed with that of the reactivity between the polyarylates and ethanolamine, and these orders can be explained by pKa of the bisphenol used to prepare the polyarylates. The development with NH2? R′? OH resulted in successful positive‐tone pattern formation. However, pattern formation with the developers containing NH2? R′? OCH3 was unsuccessful. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 2694–2706, 2006 相似文献
157.
本文根据空心阴极放电中电子能量分布的物理图象,分析了原子从低激态向高激态弛豫的可能途径。建立高低激态集居数密度增量的关系。讨论高激态集居数密度增量获得可观量的条件。根据此条件分别选取钠原子的基态3s~2S_(1/2)和铜原子的亚稳态4s~2D_(3/2)为与激光共振的下能级,并激发具有较大自发发射几率的3s~2S_(1/2)→3p~2P°_(1/2)(和3p~2P°_(3/2))和4s~2D_(3/2)→4p~2P°_(1/2)跃迁,在远离上能级的高激态上观测到敏化荧光,并精确测得这些态的自发发射系数比值,而在更高激态上没有观测到敏化荧光,表明讨论中提出的条件是合理的。 相似文献
158.
159.
160.
Tom Kennedy 《Journal of statistical physics》1990,59(1-2):195-220
A fixed-point equation on an infinite-dimensional space is proposed as an alternative to the usual definition of the infinite-volume limit in discrete lattice spin systems in the high-temperature phase. It is argued heuristically that the free energy and correlation functions one obtains by solving this equation agree with the usual definitions of these quantities. A theorem is then proved that says that if a certain finite-volume condition is satisfied, then this fixed-point equation has a solution and the resulting free energy is analytic in the parameters in the Hamiltonian. For particular values of the temperature this finite-volume condition may be checked with the help of a computer. The two-dimensional Ising model is considered as a test case, and it is shown that the finite-volume condition is satisfied for0.77
critical. 相似文献