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61.
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Bordiga S. Ugliengo P. Damin A. Lamberti C. Spoto G. Zecchina A. Spanò G. Buzzoni R. Dalloro L. Rivetti F. 《Topics in Catalysis》2001,15(1):43-52
Defective silicalite, an efficient and selective catalyst in the gas phase Beckmann rearrangement reaction, has been characterised by infrared spectroscopy and by molecular modelling techniques. We report a detailed IR study on the effect of outgassing treatments at increasing temperature on silanols bands and on framework modes. The effect of a temperature decrease up to 100 K (during the IR measurement) on the H-bonding interactions has also been investigated. The interaction of silanols with mesitylene, a probe molecule which cannot penetrate the channels, has been studied in order to distinguish between internal and external OH groups. Molecular mechanics and ab initio methods have also been used to model the structure and the vibrational features of a properly designed nest in order to support the assignments of the IR spectrum. 相似文献
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The glycerol region geometry of modeled saturated monoacid triglycerides was altered by bond rotations and minor angle distortions
to convert theoretical α-forms into bent β′- and β-forms. Direct α to β conversion involves lateral disruption of fatty chain
packing to generate side-chain character typical of the β-form. Such disruption, which could contribute to fat bloom, allows
additional molecular movement and shifts in molecular mechanics energy (MME) that may approximate thermal changes observed
by differential scanning calorimetry during α to β transformations. Energy calculations at 100 points throughout each transformation
identified plausible conversion routes. A two-stage conversion, α to either of two stereospecific β′-forms bent at glycerol
followed by subsequent conversion to β, showed less chain movement and more favorable MME than direct α to β conversion. The
preferred path, based on energy profiles of each conversion, involves a β′-D form and rotation of carbonyl to α-carbon bonds
in chain #2 and a side chain (chain #3). 相似文献
65.
为建立一种描述等幅周期荷载下软岩应变特性的本构模型,将Bingham模型中的常值黏壶元件替换成与循环次数相关的变系数黏壶元件,常值弹性元件替换为随周期荷载循环次数的增大而衰减的非定值弹性元件,即可得到反映周期荷载下软岩各种应变规律的Bingham本构模型。当循环荷载应力上限值σmax大于岩石的临界强度σs时,模型为可反映软岩3个应变阶段的改进4参数Bingam模型;反之则为反映软岩前两个应变阶段的非常值2参数Hook模型。将周期荷载分解为一个定值荷载和一个平均应力值为零的周期荷载,基于流变力学理论给出了定值荷载作用下基于该模型的本构方程式,再根据黏弹性力学理论,给出了平均应力值为零的周期荷载下基于该模型的本构方程式,最后将已获得的本构方程式叠加即得到周期荷载下软岩本构方程式。结果表明:所建立的本构方程式可较好描述周期荷载下不同软岩各类应变特征,对各类软岩的应变曲线拟合的相关系数均在0.868以上,且同一种岩石模型中弹性元件系数初始值随周期荷载的动应力幅值的增大而减小,岩石加速应变速率参数随动应力幅值的增大而增大。 相似文献
66.
Fatigue crack propagation (FCP) tests were conducted at various frequencies on nylon-6,6 specimens equilibrated over a range of moisture levels to determine the crack growth rates and the crack-tip temperatures as a function of water content. Frequency-sensitivity was correlated with the amount of crack-tip heating taking place, with crack-tip temperature being found to depend strongly on the estimated loss compliance, D″, of the material. The frequency-sensitivity of FCP in nylon was seen also to be affected by mean stress, suggesting that creep processes are often significant in FCP of nylon. 相似文献
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The electrodiffusion technique was performed in order to investigate the shear rate on a scraped surface heat exchanger. Microelectrodes were placed inside: the walls of the outer cylinder; the inlet and outlet bowls; the rotor and the blades. Highly viscous Newtonian fluid (Emkarox HV45 solutions) and non-Newtonian model fluid (aqueous solutions of CMC) were used. The electrodiffusion method allowed us to measure wall shear rates. Maximum shear rate was observed at the scraping surface and caused by blades scraping, high shear rate was also measured on the leading edge of the blades. In the other parts of the exchanger, shear rate remained low but the development of Taylor vortices completely modified the scraped surface heat exchangers behaviour inside the surface of the bowls. A dimensionless representation of the friction factor was established for the inner and outer wall surface of the exchanger. 相似文献
69.
A. Kloczkowski 《Polymer》2002,43(4):1503-1525
This paper examines the application of the statistical mechanics to the analysis of various physical properties of the elastomeric networks. The equilibrium properties of rubber-like networks are discussed, and also some dynamic properties, such as the relaxation spectrum of Gaussian networks. The paper covers a large spectrum of properties of polymer networks such as: fluctuations and chain dimensions in unimodal and bimodal network, effects of entanglements and constraints on the elastic properties of the network, segmental orientation, liquid-crystalline networks, small angle neutron scattering from networks, strain birefringence, elastic properties of filled networks, strain induced crystallization etc. The paper shows that the statistical mechanics can be successfully used to the analysis of almost all physical properties of rubber-like networks. 相似文献
70.