Changes in the dielectric relaxations of water in epoxy resin as a function of the extent of water ingress in carbon fibre composites

Dielectric relaxation measurements are reported over a frequency range from 10⁻¹ to 10⁹ Hz as a function of exposure time for an epoxy resin-carbon fibre composite, ageing at 60 °C in water. Investigation of the nature of the dipole relaxation of the water molecules, indicates the nature of their interaction with the polymer matrix. Analysis of the dielectric relaxation spectra allow identification of processes that can be attributed to ‘free’ and ‘bonded’ water, water in micro-cracking, located in carbon fibre disbonds and plasticizing the polymer matrix. Identification of the various types of location in which water exists was aided by use of the N_g factor from the Kirkwood-Frölich equation, which describes the constraints on free dipole ration nature imposed by the environment in which it is located. These data indicate the power of the dielectric technique for quantitative analysis of water ingress into epoxy composites.     

Local dynamics in epoxy coatings containing iron oxide nanoparticles by dielectric relaxation spectroscopy

Nanocomposites of photocurable epoxy resin and epoxy‐modified iron oxide magnetic nanoparticles were analyzed by dielectric relaxation spectroscopy to study the local dynamics at temperatures well below the glass‐transition temperature. Two secondary processes were detected, β and γ processes, but the second one was just detected at lower temperatures in the high‐frequency part of the spectra and moved out of the frequency range at higher temperatures. Data were fitted to the Havriliak–Negami and Arrhenius models, and the obtained parameters were analyzed. Relaxation times of the β secondary relaxation did not change with the nanoparticle content, but the relaxation strength increased. The increase could not be explained when we took into account the molecular origin of the relaxation. The presence of ferromagnetic nanoparticles enhanced the internal field and increased the relaxation strengths. Transmission electron microscopy images showed that the nanoparticles were well dispersed in the matrix, without magnetic agglomerates. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Changes in the thermomechanical behavior of epoxy glasses under the state of strain aging

Changes in thermomechanical behavior with structural relaxation taking place in epoxy glasses were studied. Differential scanning calorimetry measurements and thermostimulated strain recovery tests were performed for specimens deformed and then aged under fixed strain. In the course of heating, the specimens started to absorb thermal energy, whereas plastic strain was still stable. At higher temperatures, plastic strain started recovery, which was accompanied by exothermic behavior of the specimen. With an increase in the aging duration, the endothermic peak signified and moved to a higher temperature. These results indicated that the longer the aging duration was, the harder the plastic strain and strain energy were frozen in the glassy structure. This freeze‐strain phenomenon was observed for crosslinked epoxy glass, as well as polymeric glasses with linear molecular structures, aged under strain. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Semantic analysis in XTRA,an English — Chinese machine translation system

This paper concerns the resolution of lexical ambiguity in a machine translation environment. We describe the integration of principles of selection restrictions. Preference Semantics, and intelligent relaxation of constraints in handling lexical ambiguity. The approach differs from many previous MT systems in that it is more powerful than brute force systems, while more realistic than systems that assume a large degree of coded encyclopedia information for full understanding.     

Diluent effects on carbonate mobility in bisphenol-A polycarbonate in the solid state

The effect of miscible low molecular weight additives on the mobility of the carbonate group in bisphenol-A polycarbonate (BPAPC) has been studied using n.m.r. and dielectric relaxation experiments in the solid state. Proton-enhanced dipolar-decoupled carbon-13 n.m.r. spectra of BPAPC, isotopically enriched at the carbonate position, are obtained without magic-angle sample spinning. The resolved chemical shift anisotropy allows study of nuclear spin relaxation for the carbonate groups in the polymer that have different orientations relative to the static magnetic field in the laboratory frame. The spin-lattice relaxation time in the rotating frame (T_1?) is measured at a motional-probe frequency of 50 kHz for the undiluted polymer and for BPAPC-diluent blends containing either dibutylphthalate or dinitrobiphenyl. The T_1? exhibits some dependence on orientation in all systems studied. In the blend containing dibutylphthalate (DBP), T_1? is decreased by a factor of two for all orientations of the carbonate group. This implies that DBP substantially increases the spectral density of 50 kHz motions in the carbonate region of the polymer at ambient temperature. In contrast, dinitrobiphenyl does not significantly alter the Fourier component of thermal fluctuations at 50 kHz. Dielectric relaxation measurements at 10 kHz reveal that the primary (T_g) and secondary (β) motional processes in BPAPC are affected by low molecular weight additives. An intermediate relaxation process appears in the temperature interval between the glass transition temperature (T_g) and the sub-T_g β-relaxation (T_β) in the polymer-diluent blends. The n.m.r. spin-lattice relaxation rate in the rotating frame, T^?1_1?, correlates well with the relative magnitude of the dielectric dissipation factor (tan δ_ε) between T_g and T_β.     

Stochastic defect diffusion model for relaxation effects in crystalline polyethylene

It is suggested that some relaxation processes observed in crystalline polyethylene are consequences of the diffusive motion of a particular defect called a point dislocation or twist dispiration loop along the polyethylene stems in lamellar crystals. The motion of the defect, characterized by a diffusion coefficient and a mobility, is described by solutions of the Smoluchowski diffusion equation with boundary conditions that constrain the defect to move along routes that produce experimentally observable results. The fact that passage of the defect causes both a 180° rotation of the chain and moves an extra CH₂ group in the direction of the chain axis is important to the interpretation of the data according to this model. The diffusion coefficient for a defect is estimated to be around 2 × 10^?9 cm² s^?1 at 70°C. This value is shown to be reasonable both from the viewpoint of detailed computer modelling of defect motion and contemporary ideas about scaling.     

Interpretation of quasi-elastic light scattering data for flexible chains: model dependence

The autocorrelation functions and corresponding relaxation times obtained from the forward depolarized quasi-elastic light scattering experiment are exhibited for two quite similar models of flexible polymer chains in solution. A very small change in the chain dynamics is found to be sufficient to change the relaxation time from a relatively short time independent of chain length, with an autocorrelation function suggestive of an unweighted sum of contributions from all the relaxation times in the spectrum of chain motion, to a long time with an autocorrelation function identical with that for the end-to-end vector, strongly dependent upon chain length and dominated by the longest relaxation time in the spectrum. These results raise the question whether widely-used models in which information about short-range chain structure and motion is deliberately omitted can be expected to be appropriate for the interpretation of depolarized scattering experiments.     

Tensile Stress Relaxation of Alumina at High Temperature

The development of a tensile testing methodology for ceramics which enables a stress vs strain-rate response to be measured at high temperature is described. The test involves a carefully controled stress relaxation test at constant total strain using an experimental procedure and phenomenological analysis previously developed for metallic materials. It is demonstrated here with preliminary tests on alumina at 1050° and 1150°C. This offers, with further development, the possibility of establishing design stresses associated with low strain-rate behavior for structural applications. The results demonstrate that data covering four decades of strain rate may be generated in tests lasting a few hours. The inelastic strain consists of substantial anelastic recoverable strain in addition to a permanent creep strain.     

Change of the amorphous state by heat treatment below the glass transition temperature

This study was undertaken to elucidate the state of a polymer in the amorphous state through a change of motion of the molecular chain caused by heat treatment below the glass transition temperature. From dielectric measurements of amorphous poly(ethylene terephthalate) heat-treated below T_g, it was found that the average relaxation time, the distribution of relaxation time and the dielectric strength increase with increase of heat treatment. From these results, it was concluded that the amorphous state becomes more random by heat treatment.