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31.
32.
Andrzej Kaim 《Journal of polymer science. Part A, Polymer chemistry》2007,45(2):232-241
The competitiveness of the combination and disproportionation reactions between a 1‐phenylpropyl radical, standing for a growing polystyryl macroradical, and a 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO) radical in the nitroxide‐mediated free‐radical polymerization of styrene was quantitatively evaluated by the study of the transition geometry and the potential energy profiles for the competing reactions with the use of quantum‐mechanical calculations at the density functional theory (DFT) UB3‐LYP/6‐311+G(3df, 2p)//(unrestricted) Austin Model 1 level of theory. The search for transition geometries resulted in six and two transition structures for the radical combination and disproportionation reactions, respectively. The former transition structures, mainly differing in the out‐of‐plane angle of the N? O bond in the transition structure TEMPO molecule, were correlated with the activation energy, which was determined to be in the range of 8.4–19.4 kcal mol?1 from a single‐point calculation at the DFT UB3‐LYP/6‐311+G(3df, 2p)//unrestricted Austin Model 1 level. The calculated activation energy for the disproportionation reaction was less favorable by a value of more than 30 kcal mol?1 in comparison with that for the combination reaction. The approximate barrier difference for the TEMPO addition and disproportionation reaction was slightly smaller for the styrene polymerization system than for the acrylonitrile polymerization system, thus indicating that a β‐proton abstraction through a TEMPO radical from the polymer backbone could diminish control over the radical polymerization of styrene with the nitroxide even more than in the latter system. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 232–241, 2007 相似文献
33.
通过非球面的零位补偿法,完成了对矩形大口径离轴非球面镜的检测。先用光学设计软件Zemax从理论上分析了在检测中会出现的现象,并结合计算机辅助装调技术,确定在检测过程中相对敏感的自由度,然后控制这些量,使补偿器和非球面的相对关系与理论设计相吻合,在Zygo相位干涉仪上测得最终结果。在λ=632.8nm时,中心圆口径与两个边缘圆口径面形误差RMS分别为0.022λ,0.037λ,0.032λ。检测结果,达到预期目的。 相似文献
34.
Robyn Pierce Kaye Stacey 《International Journal of Computers for Mathematical Learning》2004,9(1):59-93
This article suggests a framework to organise a cluster of variables that are associated with students' effective use of computer algebra systems (CAS) in mathematics learning. Based on a review of the literature and from the authors' own teaching experience, the framework identifies the main characteristics of students' interactions with CAS technology and how these may be used to monitor students' developing use of CAS; from this, the framework may be used to plan teaching in order to gain greater benefit from the availability of CAS. Four case studies describing students' development over a semester are reported. These demonstrate a variety of combinations of technical competencies and personal attributes. They indicate the importance of both the technical and personal aspects but suggest that negative attitudes rather than technical difficulties can limit the effective use of CAS. Finally practical suggestions are given for teaching strategies which may promote effective use of CAS.This revised version was published online in September 2005 with corrections to the Cover Date. 相似文献
35.
本文介绍了利用计算机技术、网络技术、三遥技术对广播电视发射技术指标进行实时自动测试的系统,以便进一步为安全优质播出提供技术保证。 相似文献
36.
A method of simulated annealing in optimization of a computer generated holo-gram(CGH)is presented.The characteristics of energy in annealing curve are analyzed.Thecooling schedule such as giving an initial temperature,the temperature function,the numberof interactions and stopping criterion are discussed.As an example,an optimization of phaserelief kinoform,a CGH with multiple phase levels,is implemented. 相似文献
37.
We couple a morphological study of an immiscible binary AB mixture with a micromechanical simulation to determine how the spatial distribution of the A and B domains and the interfacial region (interphase) affects the mechanical behavior of the blend. The morphological studies are conducted through a three-dimensional Cahn-Hilliard (CH) simulation. Through the CH calculations, we obtain the size and structure of the domains for different blend compositions. The output of the CH model serves as the input to the Lattice Spring Model (LSM), which consists of a three-dimensional network of springs. In particular, the location of the different phases is mapped onto the LSM lattice and the appropriate force constants are assigned to the LSM sites. A stress is applied to the LSM lattice and we calculate the elastic response of the material. We find that the local stress and strain fields are highly dependent on the morphology of the system. By integrating the morphological and mechanical models, we can isolate how modifications in the composition of the mixture affect the macroscopic behavior. Thus, we can establish how choices made in the components affect the ultimate performance of the material. 相似文献
38.
在GS-221高速摄影测量仪中,测角信息采集与处理速度的快慢是重要性能指标之一。本文讨论了如何在尽可能短的时间内对测角信息进行采集和处理的软件实现方法。 相似文献
39.
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
40.