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.     

Evaluation of the characteristics of a viscoelastic material from creep analysis using the universal viscoelastic model. I. Isolation of the elastic component designated as the “Projected Elastic Limit”

In a preceding publication this author introduced a new universal viscoelastic model to describe a definitive relationship between constant strain rate, creep, and stress relaxation analysis for viscoelastic polymeric compounds. One extremely important characteristic of this new model is that it also characterizes secondary creep very well. Because secondary creep is the linear portion of creep after the completion of primary creep, then a straight line with a slope and an intercept can describe secondary creep. To effectively define a straight line in the secondary creep region it was found necessary to obtain averages of the instantaneous slope and the instantaneous intercept strain by averaging over a series of equally spaced data points in the secondary slope region. Most importantly, this average intercept strain was found to be independent of creep stress and creep time. This means that all the secondary creep straight lines must pass through the same intercept creep strain for all creep stresses. The results presented in this study strongly indicate that this secondary creep intercept strain is independent of creep stress and creep time, and appears to increase as the value of the efficiency of yield energy dissipation decreases. Because a decrease in the efficiency of yield energy dissipation, n, appears to correlate with an increase in the elastic solid like character of a material, then it appears that this secondary creep intercept strain should be a direct measure of the strain that the material can survive to retain its full elastic character. Therefore, this secondary creep intercept strain has been designated as the “Projected Elastic Limit” of a given viscoelastic material. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2923–2936, 2003     

Dielectric properties of polyarylate (PAr) around the glass transition

Dielectric characterization of the α-relaxation in polyarylate (PAr) has been carried out by means of a dielectric spectroscopy technique in a frequency range of 10–30 kHz. Complementary thermally stimulated depolarization currents (TSDC) and differential scanning calorimetry d.s.c.) measurements have also been performed. The results are interpreted in terms of the standard Cole-Cole plot and Havriliak-Negami distribution for the dielectric relaxation times. Information about the temperature and frequency dependence of a.c. conductivity is also obtained from the experimental curves. However, the behaviour of the main dielectric relaxation time is deduced from the experimental data in a wide range of temperature around the glass transition. This behaviour results in close agreement with the theoretical predictions of a free-volume approach for the dielectric α-relaxation recently proposed by the authors.     

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.     

Low frequency ac conduction and dielectric relaxation behavior of solution grown and uniaxially stretched poly(vinylidene fluoride) films

The measurements of ac conductivity [σ_m(ω)], dielectric constant [?′(ω)] and loss [?″(ω)] have been performed on solution grown (thickness ∼85 μm) and uniaxially stretched (thickness ∼25, 45 and 80 μm) films of poly(vinylidene fluoride) (PVDF) in the frequency range 0.1 kHz-10 MHz and in the temperature range 77-400 K. The σ_m(ω) can be described by the relation σ(ω) = Aω^s, where s is close to unity and decreases with increase in temperature. Three relaxations, observed in the present investigation, have been designated as the α_c-, the α_a- and the β-relaxations appearing from high temperature side to the low temperature side. The α_c-relaxation could not be observed in the case of uniaxially stretched poly(vinylidene fluoride) films. The α_c- and α_a-relaxations are associated with the molecular motions in the crystalline regions and micro-Brownian motion in the amorphous regions of the main polymer chain, respectively, whereas the β-relaxation is attributed to the rotation of side group dipoles or to the local oscillations of the frozen main polymer chain.     

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.     

多传感器集中式增量卡尔曼滤波融合算法

在单个传感器的状态估计系统中,标准的增量卡尔曼滤波方法可以有效消除量测系统误差。对于多传感器情况,标准算法失效。针对该问题,提出了多传感器集中式增量卡尔曼滤波融合算法,即:增量卡尔曼滤波的扩维融合算法和增量卡尔曼滤波的序贯融合算法。在标准增量卡尔曼滤波算法的基础上,结合扩维融合和序贯融合的思想来实现多传感器数据的融合。实验结果表明,当存在量测系统误差时,提出的集中式融合算法与传统的集中式融合算法相比,提高了滤波精度,并且能够成功地消除量测系统误差。     

原子磁强计检测光闭环稳定系统设计

SERF态原子磁强计已实现人类历史上最高的0.16fT/Hz1/2的灵敏度。其检测方法主要是法拉第调制法。但法拉第调制法中光电流摄动或环境温度变化等干扰导致的检测光强的起伏会造成检测结果的不准确。为抑制检测光强起伏,设计了闭环原子磁强计检测光稳定系统。在法拉第调制法的基础上,增加了光路子系统和控制子系统对检测光强进行闭环稳定控制。通过对随机干扰进行闭环控制仿真与实验,验证本系统可以有效抑制各种干扰引起的光强起伏,使系统抗干扰能力提高1.2%,从而提高原子磁强计的检测精度。     

Comparative study of the physical aging of the epoxy systems BADGE n = 0/m‐XDA and BADGE n = 0/m‐XDA/PEI

The physical aging of the epoxy network consisting of a diglycidyl ether of bisphenol A, m‐xylylenediamine, and polyetherimide was studied by differential scanning calorimetry. The glass transition temperature and the variation of the specific heat capacities have been calculated using the method, based on the intersection of both enthalpy–temperature lines for glassy and liquid states. The apparent activation energy (E_H) was calculated using a single method that involved separate temperature and excess enthalpy dependency. All calorimetric data were compared with those obtained for the epoxy network without thermoplastic. thermoplastic. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3931–3935, 2006