Influence of molecular weight distribution of linear polymers on stress relaxation after steady flow

Stress relaxation after steady flow has been measured with a Weissenberg rheogoniometer for some samples of polystyrene and high-density polyethylene; the same samples have been characterized by column fractionation, gel permeation chromatography, and osmometry.

A method suggested by Menefee and Peticolas has been used to obtain the molecular weight distribution from relaxation data, and the results have been compared with those obtained through the solution measurements. The distributions obtained by the two methods, as represented by the cumulative Z distribution versus the logarithm of molecular weight, are very similar in shape; but, in the case of polyethylenes, the distributions obtained by stress relaxation are found shifted by a factor of 2 toward high molecular weights.     

Molecular relaxation of some rigid polar molecules and their mixtures

The dielectric behavior of benzene solutions of four rigid polar molecules, benzophenone, benzotrichloride, ortho- and meta- dichlorobenzenes and their mixtures has been studied in the microwave region over a range of temperatures. The dielectric data has been used to determine the relaxation times and the thermodynamic parameters for the activated state. The relaxation times for single component solutions agree well at temperatures at which literature values are available. The relaxation times for mixtures are consistent with those of other rigid molecules studied previously. The results have been also compared with the computed values obtained from a relation proposed by us.     

14N核四极共振自旋系统自旋-晶格弛豫时间的测量

¹⁴N核四极共振自旋系统的自旋-晶格弛豫是一种双指数弛豫。本文介绍了¹⁴N核四极共振自旋系统的自旋-晶格弛豫时间的3种测量方法,利用可变多面体方法对实验数据进行拟合,获得了¹⁴N核四极共振自旋系统的自旋-晶格弛豫时间T_1s和T₁₁,对有关文献中关于核四极共振弛豫时间的测量的3个观点提出了质疑。     

Protonation rate constants of proline

The rate constants for protonation reactions of proline positive ion and zwitterion have been measured using a modulated temperature chemical relaxation method. The results are contrasted with those obtained for amino acids.     

Modelling of self-diffusion and relaxation time NMR in multicompartment systems with cylindrical geometry

Multicompartment characteristics of relaxation and diffusion in a model for (plant) cells and tissues have been simulated as a means to test separating the signal into a set of these compartments. A numerical model of restricted diffusion and magnetization relaxation behavior in PFG-CPMG NMR experiments, based on Fick's second law of diffusion, has been extended for two-dimensional diffusion in systems with concentric cylindrical compartments separated by permeable walls. This model is applicable to a wide range of (cellular) systems and allows the exploration of temporal and spatial behavior of the magnetization with and without the influence of gradient pulses. Numerical simulations have been performed to show the correspondence between the obtained results and previously reported studies and to investigate the behavior of the apparent diffusion coefficients for the multicompartment systems with planar and cylindrical geometry. The results clearly demonstrate the importance of modelling two-dimensional diffusion in relation to the effect of restrictions, permeability of the membranes, and the bulk relaxation within the compartments. In addition, the consequences of analysis by multiexponential curve fitting are investigated.     

Dipolar Relaxation Times of Tryptophan and Tyrosine in Glycerol and in Proteins: A Direct Evaluation from Their Fluorescence Decays

The dipolar relaxation process induced around tryptophan, indole and tyrosine in viscous media, as well as in several single tryptophan-containing proteins (staphylococcal nuclease, ribonuclease T1, melittin and albumin), has been studied by dynamic fluorescence measurements. A new theoretical model has been developed, including the relaxation dynamics directly in the fluorescence decay function. The phase shift and demodulation data have been fitted with this new algorithm which allows to resolve the different relaxation times influencing the fluorophore excited state. These parameters are in a good agreement with those measured with the traditional time-resolved emission spectroscopy. The results indicate that indeed a correlation exists between the radiative rate change obtained with the new model and the temporal spectral shift reported in the literature. Finally, this new approach has also been extended to the case of superoxide dismutase and phosphofructokinase, allowing to measure the relaxation time even in proteins lacking a temporal spectral shift during the fluorphore's lifetime.     

Rotational energy relaxation in CH4 and CH4-He,Ar collisions calculated from coherent and stimulated Raman spectroscopy data

Theoretical treatment of the evolution of the methane Q branch contour with pressure is given in the framework of a quantum model of rotational relaxation with allowance for the tetra-hedral symmetry of rotational levels. The results obtained are compared in detail with available experimental data. As a result, rotational energy relaxation cross-sections for methane and its mixtures with helium and argon have been determined.     

A molecular theory of the dielectric permittivity of a nematic liquid crystal

We present a theory of the dielectric permittivity in which the intermolecular dipole-dipole correlations are treated explicitly. The results for the static permittivity agree with those which have previously been obtained by continuum calculations. The frequency dependence of the permittivity is related to two relaxation times which contain the effects of only short range intermolecular correlations. Approximate relationships are derived between these times and independently measurable properties.     

Glass transitions and dynamics in thin polymer films: dielectric relaxation of thin films of polystyrene

The glass transition temperature T(g) and the temperature T(alpha) corresponding to the peak in the dielectric loss due to the alpha process have been simultaneously determined as functions of film thickness d through dielectric measurements for polystyrene thin films supported on glass substrate. The dielectric loss peaks have also been investigated as functions of frequency for a given temperature. A decrease in T(g) was observed with decreasing film thickness, while T(alpha) was found to remain almost constant for d>d(c) and to decrease drastically with decreasing d for d相似文献   

Water absorption kinetics in different wettability conditions studied at pore and sample scales in porous media by NMR with portable single-sided and laboratory imaging devices

NMR relaxation time distributions of water (1)H obtained by a portable single-sided surface device have been compared with MRI internal images obtained with a laboratory imaging apparatus on the same biocalcarenite (Lecce Stone) samples during capillary water uptake. The aim of this work was to check the ability of NMR methods to quantitatively follow the absorption phenomenon under different wettability conditions of the internal pore surfaces. Stone wettability changes were obtained by capillary absorption of a chloroform solution of Paraloid PB72, a hydrophobic acrylic resin frequently used to protect monuments and buildings, through one face of each sample. Both relaxation and imaging data have been found in good quantitative agreement each other and with masses of water determined by weighing the samples. In particular the Washburn model of water capillary rise applied to the imaging data allowed us to quantify the sorptivity in both treated and untreated samples. Combining relaxation and imaging data, a synergetic improvement of our understanding of the water absorption kinetics at both pore and sample scales is obtained. Since relaxation data have been taken over the course of time without interrupting the absorption process, simply by keeping the portable device on the surface opposite to the absorption, the results show that the single-sided NMR technique is a powerful tool for in situ evaluation of water-repellent treatments frequently used for consolidation and/or protection of stone artifacts.     

Effect of dispersion and damping of thermal phonon states on the longitudinal ultrasonic absorption in germanium crystals

A method has been proposed for approximating a phonon spectrum of cubic crystals, which has been obtained from data on inelastic neutron scattering for symmetric directions, over the entire Brillouin zone in the form appropriate for studying relaxation characteristics of phonon systems. The effect of dispersion and damping of thermal phonon states on the longitudinal ultrasonic absorption in anharmonic processes of scattering with the participation of three longitudinal phonons has been investigated for germanium crystals. It has been shown that the inclusion of the dispersion leads to a decrease in the anisotropy of ultrasonic absorption in the LLL relaxation mechanism and makes it possible to fit the results obtained from calculations of the ultrasonic absorption coefficients to the experimental data in the low-temperature range. The temperature dependence and anisotropy of the relaxation rate of longitudinal thermal phonons in germanium crystals have been determined from experimental data on ultrasonic absorption. The performed analysis has refined values of the relaxation parameters obtained from the interpretation of the data on thermal conductivity of germanium crystals with different isotopic compositions in the isotropic-medium model.     

Physical properties of [Formula: see text] polymer electrolytes: nuclear magnetic resonance investigation and comparison with [Formula: see text

The physical properties of the ionic conductor [Formula: see text], obtained by dissolution of lithium trifluoromethanesulphonylimide in poly(propylene oxide), have been investigated for several values of n. The glass transition temperature [Formula: see text] has been established from both DSC and NMR techniques. The diffusion coefficients of [Formula: see text]-containing species have been determined by the pulsed magnetic field gradient technique. The behaviour of the proton relaxation time [Formula: see text] versus temperature and concentration has been correlated to the glass temperature. The behaviour of the proton transverse relaxation function, obtained by the spin-echo technique, has been interpreted using a simple model in which two regimes and consequently two transverse relaxation times coexist and are assigned to the `entangled' and `non-entangled' parts of the high-molecular-weight polymer chains investigated.     

Determination of the Maier-Saupe strength parameter from dielectric relaxation experiments: a molecular dynamics simulation study

Molecular dynamics simulations have been performed to investigate the rotational motion in the nematic and isotropic phases of a model mesogenic system in which the interactions between the molecules are represented by the Gay-Berne potential. First-rank end-over-end rotational relaxation times, analogous to those measured using dielectric relaxation spectroscopy for real mesogens with a longitudinal electric dipole, have been determined as a function of temperature and density. The relaxation times at temperatures throughout the nematic region are found to be larger than the values extrapolated from the isotropic phase to the same temperature. The simulation results are compared with the extended Debye theory for dielectric relaxation in the nematic phase. This relates the reduction in the relaxation rate to the retardation factor which depends on the Maier-Saupe strength parameter, and in turn is defined uniquely by the second-rank orientational order parameter. The simulations indicate that the retardation factor at constant strength parameter is density dependent, a feature neglected in the relaxation theory. We compare the simulation results where possible with experiment.     

Temperature effect on the trapped-charge relaxation in (Ba,Sr)TiO3 films on silicon

The trapped-charge relaxation has been calculated for a two-layer insulator with negligible conductivity in one of the layers the conductivity of the other layer obeying the Pool-Frenkel mechanism. The calculated values are compared with the experimental data on the trapped-charge relaxation in (Ba,Sr)TiO₃ films on silicon substrates. On the basis of this comparison, the depth of location and concentration of Frenkel emission centers are estimated. The results obtained can be used in the analysis of relaxation processes in ferroelectrics, which have strong electric fields in surface layers.     

Conductivity relaxation parameters of some H and K conducting in the polycrystalline compound KDyHP3O10

Polycrystalline samples of KDyHP₃O₁₀ was obtained by heating for 12 hour at 553 K a mixture containing K₂CO₃, Dy₂O₃ and H₃PO₄. Samples were characterized through X-ray diffraction, examined by IR vibrational spectroscopy and impedance and modulus spectroscopy techniques. The conductivity relaxation parameters of some H⁺ and K⁺ conducting in this compound have been determined from an analysis of ac conductivity data measured in a wide temperature range. Transport properties in this material appears as due to H⁺ and K⁺ ions hopping mechanism. The stretched exponential function exp[−(t/τ_σ)^β] has been used to describe the conductivity relaxation. The relaxation parameters have been investigated as a function of the nature of mobile ions. The results obtained are shown to be in good agreement with the predictions of the Ngai coupling model.     

The primary-relaxation process in a supercooled liquid

Summary Dielectric and ultrasonic measurements have been performed in the temperature and in the frequency domain to investigate the α (or primary) relaxation in the supercooled state of a ?fragile? molecular liquid. This relaxation is strictly connected with the phenomenon of the glass transition and therefore an understanding of the former is a prerequisite for the explanation of the latter. The dynamic susceptibilities relative to these probes have been analysed with the Cole-Davidson function employing (where required) a Vogel-Fulcher-Tamman law to relate the main relaxation time to temperature. The results obtained are consistent with the dynamic behaviour of liquids of high fragility. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Relaxation of mechanical stresses in an array of Ge quantum dots obtained in Si

Raman scattering on optical phonons in Si/Ge/Si structures with Ge quantum dots grown by molecular beam epitaxy at low temperatures 200–300°C has been investigated. A pseudomorphic state of an array of Ge quantum dots to a Si matrix with an ideally sharp interface has been obtained. Features associated with the inelastic relaxation of mechanical stresses have been revealed in the Raman spectrum. Two mechanisms of stress relaxation are separated. It has been shown that the spectrum of the electronic states of the array differs significantly from the set of the discrete levels of a single quantum dot, because the relaxation is inhomogeneous.     

环氧树脂高温分子链松弛与玻璃化转变特性

环氧树脂是电力设备中广泛应用的一种绝缘材料, 其介电性能受到分子链运动特性的影响. 本文制备了直径为50 mm、厚度为1 mm的环氧树脂试样, 采用差示扫描量热仪和宽频介电谱仪测试了环氧树脂的玻璃化转变温度和介电特性. 实验结果表明, 环氧树脂的玻璃化转变温度为105 ℃, 在玻璃化转变温度以上, 高频段出现了由分子链段运动造成的松弛过程, 低频段出现了由载流子在材料中迁移造成的直流电导过程. 发现环氧树脂不同尺寸分子链段的松弛时间不同, 其松弛时间分布较宽, 计算得到了分子链段在不同温度下的松弛时间分布特性. 分子链松弛峰频率和直流电导随温度的变化关系服从Vogel-Tammann-Fulcher公式. 拟合实验结果得到分子链松弛峰频率和直流电导的Vogel温度和强度系数. 由Vogel温度计算得到了与差示扫描量热测试结果一致的玻璃化转变温度, 约为102 ℃. 结果表明玻璃化转变温度以上环氧树脂的自由体积增大, 分子链段有足够的空间来响应外电场从而产生分子链松弛极化, 载流子有足够的能量在材料中迁移形成电导.     

Relaxation of the high-frequency shear modulus in bulk metallic glass Zr46(Cu4/5Ag1/5)46Al8

Precision in situ measurements of the shear modulus of bulk metallic glass based on Zr have been performed. The contribution to the shear modulus due to the structural relaxation has been separated. Based on the interstitial theory, the relaxation model explaining the obtained experimental results has been constructed.     

Transient development of backward stimulated Raman and Brillouin scattering on a picosecond time scale measured by subpicosecond thomson diagnostic

The excitation and the relaxation of the plasma waves and ion acoustic waves (IAW), respectively, driven by stimulated Raman (SRS) and Brillouin (SBS) backscatterings have been experimentally investigated with short-pulse lasers. The spectra have been obtained with a 0.3 ps time resolution. It is shown that SRS develops before SBS and suddenly decays around the peak of the pump, as the IAW reaches saturation. On this short time scale, electron kinetic effects play a major role for SRS saturation, contrary to ion dynamics. These results are supported by particle-in-cell simulations.