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111.
R. Zitzumbo F.J. Ornelas-Rodriguez S. Alonso F. Avalos A. Zizumbo 《European Polymer Journal》2006,42(6):1298-1304
The elastic deformation-recovery and mechanical properties of semi-crystalline polymers (HDPE, LDPE and their blends) were investigated. An optoelectronic technique based on a laser beam was used to analyze the behavior of the samples under radial stress. The laser technology showed that the recovery process develops in two stages. The first one is governed by the elastic component and the second and slower one is controlled by the inelastic component of the material. At low deformation, the overall recovery is attributed to the development of structural micro-domains generated when shearing the amorphous segments of the polymer. The radial Young modulus was also determined and compared to unidirectional measurements. At low deformation both techniques provide very similar values; nevertheless, the radial Young modulus departs significantly from the unidirectional one when increasing the number of cycles of deformation-recovery. 相似文献
112.
Solutions of 1-hexanol and 1,2-hexanediol in heptane have been investigated tigated by means of dielectric time domain spectroscopy (TDS). The permittivity spectrum of 1-hexanol in heptane is characterized by a model function containing a sum of three elementary Debye dispersions, while 1,2-hexanediol in heptane is best described by a Cole-Davidson model function. It is shown that dilute solutions of 1-hexanol in heptane have a completely different behavior to that of 1,2-hexanediol. For the diol, the relaxation time levels off at a high value indicating an existence of higher hydrogen bonded complexes. It is possible to quantify the relative amount of monomeric 1-alcohol molecules from the dielectric spectrum. The monomerization rate for 1-hexanol upon dilution with heptane is initially low, but increases rapidly for mole fractions of heptane exceeding 0.4. 相似文献
113.
We consider the relaxation dynamics of two quantum levels coupled to a stochastic bath. We emphasize that even if the matrix elements of the fluctuating Hamiltonian are Gaussian, a second-order cumulant truncation is not exact. For various stochastic models, including the case of a spin-1/2 particle in a fluctuating magnetic field, we calculate 1/T
1, the population relaxation rate, and 1/T
2, the phase relaxation rate, up to fourth order in perturbation theory. We show that unlike the commonly accepted second-order result that 1/T
21/2T
1, when fourth-order terms are included, in some instances 1/T
2<1/2T
1. 相似文献
114.
Martin Macháček 《Journal of statistical physics》1987,47(5-6):949-952
We define mathematically a class of dynamical systems that exhibit relaxation corresponding to that observed in physical systems, and then show that this class is identical with the class ofK-mixing dynamical systems. 相似文献
115.
We extend our method of systematic removal of secular terms in a singular perturbation treatment of the Boltzmann equation with small Knudsen numbers to the initial layer. The requirement that the solution through the initial layer should connect smoothly to the normal solution removes an ambiguity noted in our previous paper. We show that removal of secular terms improves Grad's solution for the initial layer and reintroduces soundlike modes associated with higher moments, first found by Wang Chang and Uhlenbeck. 相似文献
116.
This paper reports the results of a variety of experiments carried out for understanding the solvation behavior of potassium thiocyanate in methanol–water mixtures. Electrical conductivity, speed of sound, viscosity, and FT-Raman spectra of potassium thiocyanate solutions in 5 and 10% methanol–water (w/w) mixtures were measured as functions of concentration and temperature. The conductivity and structural relaxation time suggest the ion–solvent and solvent-separated ion–ion associations increase as the salt concentration increases in the mixtures. The Raman band shifts due to the C–O stretching mode of methanol for the solvent mixtures reveal the formation of methanol–water complexes. The significant changes in the Raman bands for the C–N, C–S and O–H stretching modes indicate the presence of SCN−−solvent interactions through the N-end, “free” SCN− and the solvent-shared ion pairs as potassium thiocyanate is added to the methanol–water mixtures. The relative changes corresponding to H–O–H bending and C–O stretching frequencies indicate that K+ is preferentially solvated by water in these solvent mixtures. The appearance and increase of the intensity of a broad band at ≈940 cm−1 upon salt addition was attributed to the SCN−–H2O–K+ solvent-shared ion pairs. No Raman spectral evidence for K+(H2O)n species was observed. The preferential solvation of K+ and SCN− in the methanol−water mixtures was verified by the application of the Kirkwood−Buff theory of solutions. This theory confirms that K+ is strongly preferentially solvated by water, whereas SCN− is preferentially solvated by the methanol component. 相似文献
117.
The dipole dynamics and α-relaxation behaviour of polyvinyl chloride PVC, poly(ethylene-co-vinyl-acetate) EVA70 and blend of them EVA70/PVC have been investigated by differential scanning calorimetry (DSC) and dielectric relaxation spectroscopy (DRS). The differential scanning calorimetry (DSC) thermograms measured on samples show a single glass transition in the analysed temperature range. These three polymers are wholly amorphous and pure PVC and pure EVA70 are miscible in the ratio 1:1. The glass transition temperature Tg decreases significantly with presence of EVA70. Furthermore, the values of apparent activation energies for molecular motions at the α-relaxation and the values of fragility index have also been determined for each sample using Moynihan expression for DSC results and Vogel-Fulcher-Tammann-Hesse (VFTH) form for DRS results. It is shown a large dependence of all the values of these parameters with the content of EVA70. Comparing these three polymers, we found that the more fragile glass forming liquid is the PVC. Fragility decreases drastically with EVA70 content. EVA70 and EVA70/PVC blend exhibit practically the same behaviour. The effect of inter- and intra-molecular interactions on fragility is discussed to explain these variations. 相似文献
118.
Udo Kaatze 《Journal of solution chemistry》1997,26(11):1049-1112
A tutorial on dielectric (relaxation) spectrometry of liquids is given in this article. Some methods of measuring complex
(electric) permittivity spectra are briefly described. Results for water are presented and related to characteristic properties
of the liquid structure and to models of the molecular dynamics, particularly as resulting from computer simulation studies.
Dielectric spectra for aqueous solutions of low weight electrolytes, polyelectrolytes, small molecules, and polymers are discussed
to illustrate effects of kinetic depolarization, structure saturation, as well as positive, negative, and hydrophobic hydration.
Reference is also made to fluctuations in the hydrogen bond network of mixtures of water with liquids that are completely
miscible with this unique solvent. 相似文献
119.
A comparative quantum-chemical analysis of the electronic structures and spectroscopic parameters of the cycloalkanes C3H6, C4H8, C5H10, and C6H12 and their silicon analogs Si3H6, Si4H8, Si5H10 and Si6H12 was performed in the framework of the SCF MO LCAO method in the INDO approximation. Qualitative interpretation of “abnormal”
ionization potentials and energies of electronic absorption spectra of cyclopolysilanes has been given.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1105–1108, June, 1997. 相似文献
120.
The vertical ionization potentials of bis(-allyl)nickel (see (1) in Fig. 1) are calculated by means of the Green's function approach within a semiempirical INDO extension to the first transition metal series. The computed ionization potentials are in good agreement with an experimentally deduced assignment. In contrast to earlier theoretical and experimental studies, the 7a
u
() level is predicted on top of the levels corresponding to the Ni 3d orbitals. Our approach leads to a complete assignment of the PE spectrum of (1) in the outer valence region. 相似文献