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161.
162.
A poly(vinyl chloride) (PVC) sample was chlorinated in solution in the presence of 2,2′‐azobisisobutyronitrile and by the fluid‐bed method. The aim was to evaluate the scope of the stereoselectivity of the chlorination reaction. The quantitative microstructural analysis of the residual PVC with a degree of chlorination was followed by 13C NMR spectroscopy. From the evolution of the content of isotactic (mm), heterotactic (mr), and syndiotactic (rr) triads and of mmmm, mmmr, and rmmr isotactic pentads in the unchlorinated parts of the polymer, it was unambiguously inferred that the chlorination reaction proceeds by a stereoselective mechanism in that the mr heterotactic triads are the most reactive structures followed by the isotactic triad at mmmr and rmmr pentads. This conclusion was confirmed on the basis of the Fourier transform infrared results. The results provide valuable information regarding the effect of tacticity and related local conformations in the chemical reactions of PVC. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 508–519, 2003  相似文献   
163.
A systematic study of the efficiency of protons, Ni, Pd and Th as chemical modifiers for the determination of cadmium by electrothermal atomic absorption spectrometry (ETAAS) using fast temperature programs was made for platform atomization. A comparison was made in terms of the salt type, absorbance-time profiles and elimination of the sodium chloride interference. The results were adapted to develop a method for the ETAAS determination of cadmium in biological and environmental samples. The highest sensitivity to determine cadmium in biological and environmental samples was obtained using nickel (together with protons) as a chemical modifier. The accuracy of the method was tested by the determination of cadmium in different certified reference materials. The best detection limit and the characteristic mass of Cd were found to be 0.03 ng mL(-1) and 0.35 pg, respectively.  相似文献   
164.
We derive dispersion relations for decay, using the Lehmann-Symanzik-Zimmermann formalism, which allows the analytic continuation of the amplitudes with respect to the momenta of the external particles. No off-shell extrapolation of the field operators is assumed. We obtain generalized Omnès representations, which incorporate the and S-wave phase shifts in the elastic region of the direct and crossed channels, according to the Watson theorem. The contribution of the inelastic final-state and initial-state interactions is parameterized by the technique of conformal mappings. We compare our results with previous dispersive treatments and indicate how the formalism can be combined with lattice calculations to yield physical predictions. Received: 14 October 2002 / Published online: 14 February 2003  相似文献   
165.
A consistent counting scheme is presented that allows to study the reactions NNNNπ within an effective field theory. Within this scheme the chiral expansion is shown to converge contrary to claims in the literature.  相似文献   
166.
The oxidations of diethyl sulfide by potassium dichromate, pyridinium dichromate, quinolinium dichromate, imidazolium dichromate, nicotinium dichromate, isonicotinium dichromate, pyridinium fluorochromate, quinolinium fluorochromate, imidazolium fluorochromate, pyridinium chlorochromate, quinolinium chlorochromate, and pyridinium bromochromate follow identical kinetic orders—first‐order each with respect to the chromium(VI) reagents, sulfide and hydrogen ion, and moderately inhibited by manganese(II) ion. The energy of activation varies linearly with the logarithm of frequency factor and so does the enthalpy of activation with the entropy of activation. Also, the activation free energies do not differ significantly. The dichromates and halochromates of heterocyclic bases oxidize diethyl sulfide via a common mechanism. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 35: 1–8, 2003  相似文献   
167.
Transmission electron microscopy characterizations and XPS analyses have allowed us to show the influence of the microstructure and nanochemistry on the transport properties of Y2O3-(9 mol%)-stabilized zirconia (YSZ) and Gd2O3 (10 mol%)-doped ceria (GDC). The grain boundary electrical conductivity (σgb) and oxygen diffusion coefficient (Do) of conventional YSZ ceramics increase with the grain size, while an opposite behavior was found for GDC samples. This difference was attributed to glassy precipitates present at YSZ grain boundaries. Furthermore, it was shown that kinetic demixing processes take place during cooling, at the end of sintering. This causes important changes in the cationic species distribution at interfaces and plays an important role on the transport properties of these two materials. Paper presented at the 9th EuroConference on Ionics, Ixia, Rhodes, Greece, Sept. 15 – 21, 2002.  相似文献   
168.
The reticulation process of an epoxy resin using an amine as a cure agent was studied at different temperatures and concentrations of the cure agent with dynamic mechanical thermal analysis. The study was performed under both isothermal and nonisothermal conditions, and a temperature–time–transformation diagram was obtained. The measurements from the two modes gave similar results, although the nonisothermal mode required fewer experiments. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1965–1977, 2003  相似文献   
169.
170.
We discuss possible experiments which can exploit recently-developed techniques to accumulate, store, and manipulate low-energy positrons to measure the parameters associated with positron annihilation radiation from media of astrophysical interest. Media discussed include collections of dust grains, partially ionized gases, He, H2, and other molecular gases and gas mixtures, including polycyclic aromatic hydrocarbon (PAH) molecules relevant to the interstellar medium.  相似文献   
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