Cooperative motions in PVC studied by thermally stimulated currents: Comparison with A.C. dielectric derivative analysis

The thermally stimulated current–thermal sampling (TSC–TS) technique was used to study the broadened glass transition in conventional “atactic” poly(vinyl chloride), PVC. The activated parameters obtained from the TSC–TS data, mainly the apparent activation energy (E_a), characterize the breadth of glass transitions in a very sensitive way. These results are compared with those values of E_a obtained from the literature, using a recently proposed method of analyzing a.c. dielectric constants and their derivatives, over the temperature range of −100–130°C. Both techniques detect weak cooperative glass transition-like relaxations well below the main glass transition of ca. 80°C. As is the case with “atactic” PMMA, the data suggest that compositional heterogeneity related to a small fraction of predominantly isotactic sequences contribute to the broad glass transition extending ca. 60°C below the main glass transition in atactic PVC. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 913–918, 1998     

Medium effect on dielectric relaxation behaviors of 4A zeolite bulk dispersion system

Dielectric spectra of 4A zeolite particles bulked in deionized water (4A/W) or cyclohexane (4A/C) were measured respectively under different temperatures, and two dielectric relaxations were found in both of 4A/W and 4A/C. Because of existence of water molecules in pores, both low and high frequency relaxation times (τ_LFR and τ_HFR) of 4A/Wdecreasedmore sharply than 4A/C with increasing temperature. According to the temperature dependence of τ_LFR and τ_HFR, the activation energies of Na⁺ interacting with framework under hydrated and dehydrated environments were calculated respectively, and the original properties of Na⁺ in dehydrated zeolite were obtained by analyzing the dielectric properties of 4A/C. Furthermore, a transient state of Na⁺ motion with temperature was found in 4A/C system.     

Water-protein and ligand-protein interactions as determined by selective NMR relaxation studies

Water-macromolecules and ligand-macromolecules interactions were investigated considering the effects induced by the presence of a macromolecule on both the water and the ligand NMR selective (R₁^SE) and non-selective (R₁^NS) spin-lattice relaxation rates. The results obtained from the solvent studies were used to describe the solvent dynamics at the macromolecule-solvent interface. On the other hand, ligand R₁^SE and (R₁^NS) analysis allowed the definition of the “affinity index”, [A]_L^T, an index related to the extent of the macromolecule-ligand recognition process.     

融合插值点优化的多项式结构宽带波束形成器设计方法

多项式结构设计方法是主瓣指向可调宽带波束形成器设计的一类重要方法。多项式结构的阶数是有限的,导致主瓣实际指向与期望指向之间存在偏差,因而影响了波束形成器的指向性指数。针对这一问题,该文提出了一种基于插值点优化的多项式结构宽带波束形成器设计方法。首先,引入多项式结构插值点处阵列响应的空间导数约束,以减小主瓣指向偏差;进而利用粒子群优化算法对多项式结构中的插值点进行优化,以充分利用插值点位置提供的自由度进一步提升多项式结构宽带波束形成器的性能。优化设计结果表明,与现有设计方法相比,该文提出的方法不仅降低了主瓣的指向偏差,同时也提高了指向性指数,有效改善了多项式结构宽带波束形成器的性能。     

Application of a kinematic hardening viscoplasticity model with thresholds to the residual stress relaxation

The life analysis of engine components needs to take into account the residual stress relaxation induced by cyclic service loads. The paper recalls a new class of constitutive equations for cyclic viscoplasticity, using a series of kinematic hardening models with thresholds. The equations are introduced within a recently enlarged thermodynamic framework. Some attention is focused to the relations with multisurface approaches and to a specific determination procedure of the model parameters. The new model is applied to the calculation of the near surface residual stress relaxation after shot peening, when the structure is submitted to cyclic service loads. The simulated stabilized residual stresses are in good accordance with experimental results obtained on an N18 disk alloy at 650°C. In comparison, the classical model without threshold predicts the complete vanishing of the residual stresses, which is not satisfactory.     

Hypercrosslinked polystyrene: A polymer in a non‐classical physical state

Deformation and relaxation properties of hypercrosslinked polystyrene networks have been studied by thermomechanical method at a uniaxial compression using individual spherical beads of the polymer. The networks examined were prepared by postcrosslinking of highly swollen beads of a styrene‐0.3% DVB copolymer with 0.3–0.75 mole of monochlorodimethyl ether, which results in the introduction of 0.6–1.5 methylene bridges between each two polystyrene phenyl rings. The polymers obtained are shown to belong neither to typical glassy materials, nor to typical elastomers. Though no characteristic plateau of rubberlike elasticity was observed on the deformation curves of the beads, the polymers exhibit two fundamentally important features of the rubberlike state: The deformations are large (up to 30–40% of the initial diameter) and reversible. Relaxation of residual deformations, however, requires prolonged heating of the sample, or a cycle of swelling and drying. The deformation can start in the temperature range from −70 to +150°C depending on pressure applied. The crosslinking degree in the range from 40–100% and higher does not affect noticeably the behavior of the hypercrosslinked polystyrene. Nature of the high mobility of the hypercrosslinked network is discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2324–2333, 1999     

Influence of oxycycloaliphatic groups in the relaxation behavior of acrylic polymers

A comparative study on the mechanical and dielectric relaxation behavior of poly(5‐acryloxymethyl‐5‐methyl‐1,3‐dioxacyclohexane) (PAMMD), poly(5‐acryloxymethyl‐5‐ethyl‐1,3‐dioxacyclohexane) (PAMED), and poly(5‐methacryloxymethyl‐5‐ethyl‐1,3‐dioxacyclohexane) (PMAMED) is reported. The isochrones representing the mechanical and dielectric losses present prominent mechanical and dielectric β relaxations located at nearly the same temperature, approximately −80°C at 1 Hz, followed by ostensible glass–rubber or α relaxations centered in the neighborhood of 27, 30, and 125°C for PAMMD, PAMED, and PMAMED, respectively, at the same frequency. The values of the activation energy of the β dielectric relaxations of these polymers lie in the vicinity of 10 kcal mol⁻¹, ∼ 2 kcal mol⁻¹ lower than those corresponding to the mechanical relaxations. As usual, the temperature dependence of the mean‐relaxation times associated with both the dielectric and mechanical α relaxations is described by the Vogel–Fulcher–Tammann–Hesse (VFTH) equation. The dielectric relaxation spectra of PAMED and PAMMD present in the frequency domain, at temperatures slightly higher than T_g, the α and β relaxations at low and high frequencies, respectively. The high conductive contributions to the α relaxation of PMAMED preclude the possibility of isolating the dipolar component of this relaxation in this polymer. Attempts are made to estimate the temperature at which the α and β absorptions merge together to form the αβ relaxation in PAMMD and PAMED. Molecular Dynamics (MD) results, together with a comparative analysis of the spectra of several polymers, lead to the conclusion that flipping motions of the 1,3‐dioxacyclohexane ring may not be exclusively responsible for the β‐prominent relaxations that polymers containing dioxane and cyclohexane pendant groups in their structure present, as it is often assumed. The diffusion coefficient of ionic species, responsible for the high conductivity exhibited by these polymers in the α relaxation, is semiquantitatively calculated using a theory that assumes that this process arises from MWS effects, taking place in the bulk, combined with Nernst–Planckian electrodynamic effects, due to interfacial polarization in the films. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2486–2498, 1999     

Rouse's dynamics of networks with pendant chains

A model to describe the dynamics of networks with linear pendant chains has been formulated based on the properties of ensembles of micronetworks, using the Rouse model. This development indicates that the terminal relaxation time of pendant chains with relatively large molecular weight scales with the square of the molecular weight of those chains. On the other hand, when the molecular weight of pendant and elastically active chains are comparable, a nearly exponential growth of the terminal relaxation time with the molecular weight is predicted. The main predictions of the model are compared with experimental results of model poly(dimethyl siloxane) (PDMS) networks, with controlled amounts of linear pendant chains of known molecular weight. The terminal relaxation time of these networks was estimated from the values of the loss modulus G″(ω) measured experimentally. An exponential dependence on the molecular weight of pendant chains was derived for the terminal relaxation time. This behavior is in good agreement with the predictions of our model for micronetworks, provided that the friction coefficient scales linearly with the number of entanglements. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1121–1130, 1999     

Pressure‐temperature study of dielectric relaxation of a polyurethane elastomer

The effect of hydrostatic pressure up to 1,361 atms on the dielectric properties of a segmented polyurethane elastomer (Dow 2103‐80AE) is studied at temperatures from 0°C to 80°C. The experimental results show that the relaxation time for both the I–process, associated with the molecular motions in the hard segments, and the α–process, associated with the glass transition, increases with pressure, and this shift is more pronounced for the I–process. Besides the glass transition, it is found that the I–process can be described by the Vogel–Fulcher (V–F) and Williams–Landel–Ferry (WLF) relations. At atmospheric pressure, T_g and T₀ for the I–process are 235.9 K and 4.2 × 10³ K, respectively. Based on the V–F and WLF relations and experimental results, it is found that a parameter, C₁, in the WLF relation is independent of the pressure. Thus, a method is introduced to determine the values of both the characteristic transition temperature (T_g) and activation energy (T₀) for the processes at different pressures. As the pressure increases from atmospheric to 1,361 atms, the increase of T_g for the I–process is about 30°C. The results also show that, for both the I– and the α–processes, T₀ decreases with increasing pressure. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 983–990, 1999