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31.
32.
Ana L. Montero Luis A. Montero Ricardo Martínez S. Spange 《Journal of Molecular Structure》2006,770(1-3):99-106
A quantum chemical model (Abinitio HF-MO and DFT-B3LYP) of polyfurfuryl alcohol crosslinking is shown. Two pathways were considered: (a) a Diels–Alder (D–A) reaction between a dihydrofuran moiety and a furan ring; (b) the addition reaction of electrophilic specimens on conjugated double bonds. The ability for the formation of D–A adducts (dienes and dienophiles) was investigated by the frontier molecular orbital (FMO) theory. Energy gaps between the FMO's of diene and dienophile structures suggest that the occurrence of the D–A reaction is possible. The results suggest that the carbons of the exo double bonds attached to dihydrofuran rings are the sites most likely to be attacked by electrophilic species, while the C3 and C4 atoms display the opposite tendency due to their low HOMO electron densities. Results of a thermochemical approach to these reactions at the MP2 level was in agreement with reactivity modelled by MO predictions. 相似文献
33.
C. Devaux J.P. Chapel E. Beyou Ph. Chaumont 《The European physical journal. E, Soft matter》2002,7(4):345-352
Thin layers of polystyrene were grown from surface-grafted nitroxide initiators via controlled “living” free radical polymerization.
The “reactive” Langmuir-Blodgett deposition method allowed an effective control of the initiator layer density leading to
PS brushes with different and high grafting density and stretching. The influence of the grafting density on the layer structure
was studied. Comparison with theoretical predictions for monodispersed brushes in bad solvent was discussed. The thickness
was found to vary linearly with molecular weight and the density dependence was shown using wetting measurements. Special
features of controlled radical nitroxide polymerization from a surface were discussed. A direct comparison of the molecular
weight and polydispersity between surface and bulk polymers was made by de-grafting the brushes into a toluene/HF solution.
Finally, some evidence of a “surface Fischer” effect was shown from re-initiated layers.
Received 20 December 2001 相似文献
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35.
通过采用相位重匹配技术,设计了一种输入输出共轴的三弯曲型TM01-TE11模式转换器,该转换器由三段常曲率弯曲波导和两段直波导组成。用模式耦合理论建立了该类模式转换器的数值计算和优化设计方法,并设计了一个中心频率为7.0 GHz的模式转换器。该转换器的TM01-TE11转换效率在中心频率上大于99%,在6.5~7.5 GHz的频率范围内大于90%。应用时域有限差分法和有限元方法对所设计的模式转换器进行了仿真,仿真结果验证了设计理论和设计结果。 相似文献
36.
A vacuum-deposited aluminium layer (20 nm) is sandwiched between two layers of laminated oriented polypropylene (OPP) film whose thickness varies from 20 to 40 μm. Selected areas of this sealed system were transparentised by the redistribution of the aluminium layer without breaking the seal or causing damage to the OPP film using a 75 W Q-switched Nd:YAG laser. The resultant transparentised films contain aluminium particles, distorted polymer areas and intact areas of the vacuum-coated aluminium layer. This paper investigates the effect of microscopic features upon the overall transmissivity of the laser-treated films and hence the quality of the transparentisation process. 相似文献
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38.
This paper examines the capabilities of cryogenic sample handling to examine composition and structure of hydrogel materials where siloxane components are central to the analysis. XPS analysis of multicomponent polymers with cryogenic sample handling following exposure to aqueous environments has revealed the composition and kinetics of near surface reorganization for siloxane and fluorocarbon containing polymers. In this study we report results from a ToF-SIMS protocol for cryogenic sample handling applied to the analysis of surface changes upon hydration/dehydration of hydrogel polymers. Comparison of results from angle dependent XPS and ToF-SIMS are discussed for a range of commercial soft contact lens materials. Both methods detected changes in surface chemistry between the hydrated (frozen) and dehydrated surfaces. Analysis of the hydrated surfaces detected polymer components indicative of the commercial formulation as well as ice clusters. Analysis of the dehydrated materials detected changes in surface chemistry relative to the hydrated surface in addition to loss of water due to sample dehydration. A quantitative standard additions method for ToF-SIMS data was used to determine submonolayer amounts of PDMS impurities at the surface of the hydrogels. ToF-SIMS analysis of a series of seven poly (allyl methacrylate-g-dimethylsiloxane), AMA-g-DMS, graft copolymers in the hydrated state revealed high mass oligomeric ion distributions for systems with bulk PDMS content greater than 25 wt.%. This marks the first time that detection of high mass oligomeric ion distributions from hydrated (frozen) surfaces has been reported. Analysis of the dehydrated surface detected formation of high mass oligomeric ion distributions for systems with PDMS bulk content greater than 15 wt.%, but only detected these ion distributions in wet (frozen) samples when the bulk concentration was greater than 25 wt.%. 相似文献
39.
The conformation and dimension of SPU polyanion have been studied by viscosity and quasi-elastic light scattering methods. The rigidity of SPU is somewhat similar to CMC and its hydrodynamic radius decreases only slowly with increasing concentration of NaCl. 相似文献
40.
Hans -Peter Deutsch 《Journal of statistical physics》1992,67(5-6):1039-1082
A complete outline is given for how to determine the critical properties of polymer mixtures with extrapolation methods similar to the Ferrenberg-Swendsen techniques recently devised for spin systems. By measuring not only averages but the whole distribution of the quantities of interest, it is possible to extrapolate the data obtained in only a few simulations nearT
c
over the entire critical region, thereby saving at least 90% of the computer time normally needed to locate susceptibility peaks or cumulant intersections and still getting more precise results. A complete picture of the critical properties of polymer mixtures in the thermodynamic limit is then obtained with finite-size scaling functions. Since the amount of information extracted from a simulation in this way is drastically increased as compared to conventional methods, the investigation of mixtures with long chains or built-in asymmetries is now possible. As an example, the critical points, exponents, and amplitudes of dense, symmetric polymer mixtures with chain lengths ranging fromN=16 up toN=256 are determined within the framework of the 3D bond fluctuation model using grand canonical simulation techniques. As an example for an asymmetry, the generalization of the method to asymmetric monomer potentials is briefly discussed. 相似文献