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81.
三苯甲基自由基及其二聚体稳定性的理论研究 总被引:1,自引:1,他引:0
采用量子化学AM1 MO方法优化了三苯甲基自由基及其两种二聚体的构型,并计算了反应物和二聚物的生成焓、活化能以及它们的电荷布居,计算结果表明,三苯甲基自由基是一种较稳定的自由基,在这个自由基中存在明显的共轭效应,分子中电子云呈平均化分布.它的二聚体1,4—环己二烯衍生物分子中的5个苯基排布在环己二烯环平面的两端,明显降低了苯基之间的空间排斥力,使二聚物—环己二烯衍生物分子的稳定性大大高于六苯乙烷.因此,三苯甲基自由基的二聚体是1,4—环己二烯衍生物而不是六苯基乙烷,得到了与实验事实一致的结果。 相似文献
82.
N. Fitier 《国际流体数值方法杂志》2003,42(12):1345-1361
There is a growing interest in developing numerical tools to investigate the onset of physical instabilities observed in experiments involving viscoelastic flows, which is a difficult and challenging task as the simulations are very sensitive to numerical instabilities. Following a recent linear stability analysis carried out in order to better understand qualitatively the origin of numerical instabilities occurring in the simulation of flows viscoelastic fluids, the present paper considers a possible extension for more complex flows. This promising method could be applied to track instabilities in complex (i.e. essentially non‐parallel) flows. In addition, results related to transient growth mechanism indicate that it might be responsible for the development of numerical instabilities in the simulation of viscoelastic fluids. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献
83.
Ecaterina Stela Dragan Simona Schwarz 《Journal of polymer science. Part A, Polymer chemistry》2004,42(10):2495-2505
The formation and characterization of some interpolyelectrolyte complex (IPEC) nanoparticles based on poly(sodium 2‐acrylamido‐2‐methylpropanesulfonate) (NaPAMPS), as a function of the polycation structure, polyanion molar mass, and polyion concentration, were followed in this work. Poly(diallyldimethylammonium chloride) and two polycations (PCs) containing (N,N‐dimethyl‐2‐hydroxypropyleneammonium chloride) units in the backbone (PCA5 and PCA5D1) were used as starting polyions. The complex stoichiometry, (n?/n+)iso, was pointed out by optical density at 500 nm (OD500), polyelectrolyte titration, and dynamic light scattering. IPEC nanoparticle sizes were influenced by the polycation structure and polyanion molar mass only before the complex stoichiometry, which was higher for the more hydrophilic polycations (PCA5 and PCA5D1) and for a higher NaPAMPS molar mass, and were almost independent of these factors after that, at a flow rate of the added polyion of about 0.28 mL × (mL PC)?1 × h?1. The IPEC nanoparticle sizes remained almost constant for more than 2 weeks, both before and after the complex stoichiometry, at low concentrations of polyions. NIPECs as stable colloidal dispersions with positive charges in excess were prepared at a ratio between charges (n?/n+) of 0.7, and their storage colloidal stability, as a function of the polycation structure and polyion concentration (from 0.8 to ca. 7.8 mmol/L), was demonstrated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2495–2505, 2004 相似文献
84.
Ibrahim Erol 《Journal of polymer science. Part A, Polymer chemistry》2004,42(13):3157-3169
A new type of methacrylate monomer, [2‐oxo‐2‐(4‐acetyl) phenyl amino] ethylene methacrylate (APEMA), was synthesized. The oxime, 2,4‐dinitrophenylhydrazone, and thiosemicarbazone derivatives of poly{[2‐oxo‐2‐(4‐acetyl) phenyl amino] ethylene methacrylate} [poly(APEMA)] were prepared with hydroxylamine hydrochloride, 2,4‐dinitrophenylhydrazine, and thiosemicarbazone hydrochloride, respectively. The radical homopolymerization of APEMA was performed at 65 °C in a 1,4‐dioxane solution with benzoyl peroxide as an initiator. The monomer and its homopolymer were characterized with Fourier transform infrared and NMR techniques. The thermal stabilities of poly(APEMA) and its derivatives were investigated with thermogravimetric analysis and differential scanning calorimetry. The ultraviolet stability of the polymers were compared. The solubility and inherent viscosity of the polymers were also determined. The number‐average and weight‐average molecular weights and polydispersity index of the polymers were determined with gel permeation chromatography. The antibacterial and antifungal effects of the monomer and the polymer and its derivatives were also investigated on various bacteria and fungi. The activation energies of the thermal degradation of the polymers were calculated with the Ozawa method. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3157–3169, 2004 相似文献
85.
Abraham Chemtob Valrie Hroguez Yves Gnanou 《Journal of polymer science. Part A, Polymer chemistry》2004,42(11):2705-2716
This study critically examines the similarities and differences between poly(ethylene oxide) (PEO) stabilized latices of polynorbornene and polybutadiene. Features such as the kinetics of copolymerization of norbornene and cyclooctadiene with a macromonomer of PEO, the particles' size and morphology, the type of copolymer formed, and the stability of these latices were investigated and the results obtained are considered. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 2705–2716, 2004 相似文献
86.
Seok‐Ho Hwang Kyung Soo Yoo Charles N. Moorefield Sang‐Won Lee George R. Newkome 《Journal of Polymer Science.Polymer Physics》2004,42(8):1487-1495
A series of metallodendrimers, assembled by means of bis(terpyridinyl)Ru(II) connectivity on poly(propylene imine) dendrimer scaffolds, with homogeneous or heterogeneous surfaces, were prepared. Differential scanning calorimetry and thermogravimetric analysis were used to determine their thermal behavior, glass‐transition temperatures, and the decomposition kinetics and temperatures; no synergy effects for these properties were observed for the heterogeneously surfaced constructs in contrast to the corresponding homogeneously coated materials, which exhibited different values depending on their surface functionalities. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1487–1495, 2004 相似文献
87.
Junchai Zhao Shichun Jiang Xiangling Ji Lijia An Bingzheng Jiang 《Journal of Polymer Science.Polymer Physics》2004,42(18):3496-3504
The surface morphologies of poly(styrene‐b‐4vinylpyridine) (PS‐b‐P4VP) diblock copolymer and homopolystyrene (hPS) binary blend thin films were investigated by atomic force microscopy as a function of total volume fraction of PS (?PS) in the mixture. It was found that when hPS was added into symmetric PS‐b‐P4VP diblock copolymers, the surface morphology of this diblock copolymer was changed to a certain degree. With ?PS increasing at first, hPS was solubilized into the corresponding domains of block copolymer and formed cylinders. Moreover, the more solubilized the hPS, the more cylinders exist. However, when the limit was reached, excessive hPS tended to separate from the domains independently instead of solubilizing into the corresponding domains any longer, that is, a macrophase separation occurred. A model describing transitions of these morphologies with an increase in ?PS is proposed. The effect of composition on the phase morphology of blend films when graphite is used as a substrate is also investigated. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3496–3504, 2004 相似文献
88.
V.B. Fainerman V.N. Kazakov S.V. Lylyk A.V. Makievski R. Miller 《Colloids and surfaces. A, Physicochemical and engineering aspects》2004,250(1-3):97-102
One of the essential differences in the design of bubble pressure tensiometers consists in the geometry of the measuring capillaries. To reach extremely short adsorption times of milliseconds and below, the so-called deadtime of the capillaries must be of the order of some 10 ms. In particular, for concentrated surfactant solutions, such as micellar solutions, short deadtimes are needed to minimize the initial surfactant load of the generated bubbles. A theoretical model is derived and confirmed by experiments performed for a wide range of experimental conditions, mainly in respect to variations in deadtime and bubble volume. 相似文献
89.
光参量啁啾脉冲放大(OPCPA)在饱和放大区存在一个增益稳定点,据此设计了一个输出稳定的三级OPCPA系统;第一、二、三级分别选用准相位匹配的周期极化钛氧磷酸钾(PPKTP)晶体、LBO晶体和KDP晶体作为增益介质。饱和放大时,增益随泵浦光强度变化时的增益输出稳定性明显改善,在泵浦光强度抖动低于6%的情况下,各级光参量放大器OPA输出的增益抖动小于1%。前级采用准相位匹配的PPKTP晶体作为增益介质,在远低于破坏阈值的30MW/cm2的泵浦功率密度下,可得到2×105的饱和放大增益和20%的能量转换效率。 相似文献
90.
以铝酸镧(001)单晶为基片,采用两步法制备Tl2Ba2CaCu2Oy(Tl 2212)高 温超导薄膜.首先,利用脉冲激光沉积(PLD)工艺沉积Ba2CaCu2Ox非晶前驱体薄膜;然后,前驱体薄膜在高温(720—850℃)下密封钢容器里铊化结晶形成Tl 2212薄膜.XRD结果表明Tl2212 薄膜是沿c轴方向生长的,其相组成为Tl 2212,摇摆曲线(0012)的半高宽为0.72° ,SEM图像显示其表面光滑平整,其零电阻温度为106.2K.
关键词:
Tl 2212超导薄膜
脉冲激光沉积 相似文献