Relaxation times and energy barriers of rubbing-induced birefringence in glass-forming polymers

The relaxations of rubbing-induced birefringence (RIB) in several glass-forming polymers, including polycarbonate and polystyrene (PS) derivatives with various modifications to the phenyl ring side group, are studied. Significant relaxations of RIB are observed at temperatures well below the glass transition temperature T _g . The relaxation times span a wide range from ∼ 10 s to probably geological time scale. Physical aging effects are absent in the RIB relaxations. The model proposed for the interpretation of RIB in PS describes well the RIB relaxations in all the polymers investigated here. The energy barriers are of the order of a few hundred kJ/mol and decrease with decreasing temperature, in opposition to the trend of Vogel-Fulcher form for polymer segmental relaxations above T _g . The relaxation behaviors of different polymers are qualitatively similar but somewhat different in quantitative details, such as in the values of the saturated birefringence, the shape of the initial barrier density distribution functions, the rates of barrier decrease with decreasing temperature, and the dependence of relaxation times on temperature and parameter , etc. The RIB relaxations are different from any of the other relaxations below T _g that have been reported in the literature, such as dielectric relaxations or optical probe relaxations. A microscopic model for the relaxations of RIB is much desired.     

The effects of thermal annealing on the relaxation of rubbing-induced birefringence in polystyrene

We have conducted a systematic study on the effects of post rubbing annealing on the relaxation of rubbing-induced birefringence of polystyrene. It is found that annealing at T₀ only affects the relaxation up to T₀ + T_Lag, where T_Lag is proportional to the logarithm of the annealing time t_A. A theoretical model based on the distribution of relaxation times due to the individual birefringence elements is proposed. To remove its contribution to the net birefringence each element must overcome an energy barrier E = (317 + 1.17ξ)×10³ J/mol, and therefore must have a characteristic relaxation time τ which depends on temperature T and a barrier height which ranges from 340.4 kJ/mol to 445.7 kJ/mol. The relaxation of birefringence is expressed by the equation NB(T, t) = N(ξ)e^-t/τ(T,ξ)dξ, in which both the relaxation time τ(T,ξ) and the distribution function N(ξ) can be extracted from experimental data. The predictions of the model agree well with all the experimental results presented in this work. The differences and similarities of the relaxation of birefringence with respect to the physical aging of quenched PS are discussed. In particular, similarities in terms of the general temperature lag phenomena are noted.     

The absence of physical-aging effects on the surface relaxations of rubbed polystyrene

Extensive experimental results are presented to reveal the relaxations of polystyrene surface deformed by rubbing with a velvet cloth. We found that surface topographic features, such as ditches and ridges created by rubbing, relax at temperatures at about 20^° C below the bulk glass transition temperature of the polystyrene for a molecular weight of 442 kg/mol, even though we estimate the Laplace Pressure driving the relaxation to be 1/500 of the yield limit. The relaxation is independent of the thermal history before the rubbing process, and post rubbing thermal history below 55^° C . In other words, physical-aging processes at 23^° C for up to 7 days and at 50^° C for 2 days, which would have drastic effects on the relaxations of bulk polymers, have little effects on the relaxations of rubbed surfaces. This is consistent with the mobility enhancement in the surface layer previously reported in the literature.     

Do deviations from reptation scaling of entangled polymer melts result from single- or many-chain effects?

By studying the relaxation of small amounts of short entangled "probe" chains in a high molecular weight matrix, we show that the deviations from reptation scaling of the longest relaxation time are not as much dominated by single-chain effects (usually referred to as contour length fluctuations or CLF) as assumed by current mesoscopic models but also originate to a very significant extent from mutual chain relaxation effects. This result is in fact consistent with literature data on tracer and self-diffusion. Moreover, tube theories also overpredict the influence of CLF on the plateau modulus. Improved theories, simulations, and careful experiments are urgently needed to resolve this important question.     

Nucleation-and-growth problem in model lipid membranes undergoing subgel phase transitions is a problem of time scale

In this Rapid Note, we show that the problem of growth of molecular superlattice in a fully hydrated dipalmitoylphosphatidylcholine (DPPC) membrane during the gel-to-subgel phase transformation process is a problem of time scale. There are, in fact, two time scales. The first is an “integrated” or, in some sense, stagnant time scale, that reflects the well-known isotropic growth effect in the d-dimensional space, but assigns the problem to be still in a category of Debye relaxation kinetics. The fraction of old (parent) phase does not suit the Paley-Wiener criterion for relaxation functions, and the time behavior is exclusively due to the geometrical characteristics of the kinetic process. The second (multi-instantaneous) time scale, in turn, is recognised to be a “broken” (fractional time derivative) or memory-feeling (dynamic) scale, which carries some very essential physics of the phenomenon under study, and classifies the problem to be of non-Debye (viz., stretched exponential) nature. It may, in principle, contain all the important effects, like small scale coexistence, presence of collisions between domains, with possible annihilation and creation of domain boundaries, and/or a headgroup packing, hydration against lipid mobility behavior, and finally, a multitude of quasi-crystalline states. It turns out, that within the range of validity of the dynamic scale approximation proposed, the criterion for relaxation functions is very well fulfilled. Received 30 November 1998     

Near-Field Birefringence Response of Liquid Crystal Molecules in Thickness Direction of Liquid Crystal Thin Film Orientated by Shear Force

Information of molecular orientation in nematic liquid crystal （LC） is attractive and important for applications in the field of display devices. We demonstrate a novel method using a birefringence scanning near-field optical microscope （Bi-SNOM） with a probe which is inserted into the LC thin film to detect the molecular orientation from its birefringence responses in the thickness direction of the LC thin film. The probe is laterally vibrated when going forward into the LC thin film, and the retardation and azimuth angle are recorded as the probe going down. Firstly, the thickness of the LC thin film is measured by the shear force detection. Since the shear force acts as a stimulation to reorientate the LC molecules above the substrate surface, we can detect the molecular orientation caused by a polyimide alignment substrate and the effect to molecular orientation caused by vibration of fibre probe. As a result, the orientation profiling of the LC film in depth direction is obtained in both the cases that the direction of probe vibrating is vertical/parallel to the rubbing direction of the alignment film. Furthermore, the thickness of completely orientated layers just above the substrate surface can also be obtained by either vibrating probe or no-vibrating probe. Ultimately, the LC thin film can be modelled in thickness direction from all the results using this method.     

Inverse Relaxation of Photoinduced Birefringence in a Liquid-Crystalline Azobenzene Side-Chain Polymer

Photoinduced birefringence in a liquid-crystalline azobenzene side-chain polymer is investigated. It is observed that the birefringence does not show any decay but increases after switching off the pump light at room temperature. The magnitude of the birefringence relaxation is found to depend on the exposure dose of the pump light. A discussion about the mechanism of the inverse relaxation of birefringence is presented.     

Tightly Focusing of Circularly Polarized Vortex Beams through a Uniaxial Birefringent Crystal

Under the approximation of small birefringence, the properties of circularly polarized vortex beams tightly focused through a uniaxial birefringent crystal are studied. With the proper combination of the topological charge and the birefringence, the small focus, the small bottle beam and the inverse c-shaped intensity profile can be obtained. The effects of the focal shift and the Strehl ratio on the birefringence are analysed. A relation between angular momentum （included spin and orbital） and topological Pancharatnam charge is also presented.     

On the response of infrared absorption spectra of polymers to large inelastic deformations

It is well known that the refractive index of a material and its coefficient of absorption are coupled quantities. Within the theory of light propagation they appear as a single complex eigenvalue. Thus, birefringence and in particular induced birefringence as the physical base of stress optics, have their counterpart in the absorption spectrum. This phenomenon is called dichroism or induced dichroism. Dichroism is recording absorption spectra using light with two different planes of polarisation (generally, the orientation of the planes is perpendicular to each other) resulting in two different absorption spectra of the same specimen at the same amount of stretch. It can be shown that the dependence of absorption spectra on the orientation of the polarisation plane of the light comes out of two roots. A (small) detuning off the resonance frequency of the molecular oscillators of the material and a (dramatic) change of absorption, the latter being a consequence of change of orientation of the molecular polarisation vectors. Both, the detuning and the orientation effects, can be related to the macrodeformation of the specimen. Some possible applications of these effects in experimental mechanic are discussed.     

Dipolar interaction and incoherent quantum tunneling: a Monte Carlo study of magnetic relaxation

We study the magnetic relaxation of a system of localized spins interacting through weak dipole interactions, at a temperature large with respect to the ordering temperature but low with respect to the crystal field level splitting. The relaxation results from quantum spin tunneling but is only allowed on sites where the dipole field is very small. At low times, the magnetization decrease is proportional to as predicted by Prokofiev and Stamp, and at long times the relaxation can be described as an extension of a relaxed zone. The results can be directly compared with very recent experimental data on Fe₈ molecular clusters. Received 9 February 1999     

Magneto-optically induced retardation and relaxation study in a mixed system of magnetic fluid and cationic micelles

Stable colloidal systems composed of a double surfactant water-based magnetic fluid mixed with a cationic isotropic micellar solution of cetyletrymethyleammonium bromide (CTABr) are prepared for different concentrations of magnetic fluid. The structural integrity between nanomagnetic particles of magnetic fluids and soft micelles is investigated using the magneto-optical techniques like magnetic birefringence, transmission and relaxation measurements. Magneto-optically induced retardation and relaxation measurement indicates the existence of magnetically induced interactions in this mixed system. Similar behaviour is also observed in small angle neutron scattering experiments.     

Soliton Propagation in Optical Fibers with Random Polarization Dispersion

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Generalized Einstein Relation in an aging colloidal glass

We present an experimental investigation of the Generalized Einstein Relation (GER), a particular form of a fluctuation-dissipation relation, in an out-of-equilibrium visco-elastic fluid. Micrometer beads, used as thermometers, are immersed in an aging colloidal glass to provide both fluctuation and dissipation measurements. The deviations from the Generalized Einstein Relation are derived as a function of frequency and aging time. The observed deviations are interpreted as directly related to the change in the glass relaxation times with aging time. In our scenario, deviations are observed in the regime where the observation timescale is of the order of a characteristic relaxation time of the glass.     

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.     

Huge (but finite) time scales in slow relaxations: beyond simple aging

Experiments performed in the last years demonstrated slow relaxations and aging in the conductance of a large variety of materials. Here, we present experimental and theoretical results for conductance relaxation and aging for the case-study example of porous silicon. The relaxations are experimentally observed even at room temperature over time scales of hours, and when a strong electric field is applied for a time tw, the ensuing relaxation depends on tw. We derive a theoretical curve and show that all experimental data collapse onto it with a single time scale as a fitting parameter. This time scale is found to be of the order of thousands of seconds at room temperature. The generic theory suggested is not fine-tuned to porous silicon, and thus we believe the results should be universal, and the presented method should be applicable for many other systems manifesting memory and other glassy effects.     

Electric birefringence study of an amyloid fibril system: The short end of the length distribution

In this article, a system of amyloid fibrils, based on the protein β-lactoglobulin, is studied by transient electric birefringence. Single pulses of an electric field were applied to the solution, and the initial rise and subsequent decay of birefringence analysed. The decay takes place on a range of relaxation times, and therefore contains information about the length distribution of fibrils in the system. The information can be extracted using theories of the electric polarisability of polyelectrolyte rods, since the fibrils are an example of these. Despite the long-standing complications of such theories, useful quantitative information about the system can still be obtained. Using the Fixman model of polyelectrolyte polarisability, we obtain a measurement of the short end of the length distribution which shows the fibril concentration as a function of length rising linearly from 0.02-2 μm. The short end of the length distribution was unobtainable in our previous study using rheo-optics (S.S. Rogers et al., Macromolecules 38, 2948 (2005)), but reasonable agreement between the two techniques shows they are complementary.     

Specific heat of super carbon nanotube and its chirality independence

The specific heat of the super carbon nanotube (ST) was investigated by the molecular structure mechanics method. At given temperature, it was found that the specific heat of the ST is a fixed value and is almost independent both of the length, diameter and of chirality of the ST. By comparing the influences of the chirality of the ST on its mechanical properties, electronic properties and thermal properties as well, we find that the chirality effects on the physical properties of STs can be neglected. This result may be regarded as a universal law for the physical properties of STs.     

Influence of the polarization mode dispersion on the propagation of ultrashort optical pulses in single-mode fiber lightguides with very weak linear birefringence and random inhomogeneities

We consider the influence of the polarization mode dispersion, which is stipulated by the presence of random inhomogeneities in single-mode fiber lightguides, on the propagation of ultrashort optical pulses in the fiber communication lines with very weak linear birefringence. Evolution of the envelope of ultrashort optical pulses and their spectra as functions of the length of a single-mode fiber lightguide with very weak linear birefringence and random inhomogeneities are obtained by the method of mathematical simulation. An increase in the pulse duration is shown to be proportional to the square root of the length of a single-mode fiber lightguide. The numerical-simulation results are compared with the results of experimental measurements of the polarization mode dispersion.     

Applied electric field effect on light-scattering birefringence of dye-doped liquid crystal molecule and consistent neural network empirical physical formula construction for scattering intensities

In this paper, we realized two objectives. Firstly, birefringence of azo and anthraquinone dye-doped nematic liquid crystal (NLC) molecules was investigated by applied electric field dependent laser scattering intensities. The birefringence was essentially calculated from ordinary and extraordinary ray phase difference, which is determined from the measured intensities corresponding to parallel and perpendicular orientations of analyzer to polarizer. The birefringence was found to be dependent on both applied voltage and the kind of the doping dye. As the second objective, by nonlinear universal function approximator layered feedforward neural network (LFNN), we constructed explicit form of empirical physical formulas (EPFs) for experimentally measured dye-doped NLC nonlinear scattering intensities. Excellent LFNN test set predictions over yet-to-be measured experimental data proved that the constructed LFNN-EPFs estimated the measured intensities consistently. The correlation coefficients assessing the goodness of predictions were about r = 0.998for all cases. The LFNN-EPFs also extracted the intensity dependency on the kind of dye used. When theoretical and LFNN-EPFs intensities are compared, we conclude that given certain experimental conditions, theoretical and LFNN-EPFs predictions are in excellent agreement. In this sense, we can say that the physical laws embedded in the birefringence scattering data can be consistently extracted by LFNN. Therefore, judging from the consistent extraction of the molecular dependencies of pure and doped NLC intensities, we predict that the LFNN-EPFs can help to identify unknown molecular structural parameters in liquid crystal extracts. More concretely, by suitable mathematical operations such as differentiation, integration, minimization on these intensity LFNN-EPFs, some useful information into the charge distributions of the LC molecules can be gained.     

Distributions of switching times of single-domain particles using a time quantified Monte Carlo method

Using a time quantified Monte Carlo scheme we performed simulations of the switching time distribution of single mono-domain particles in the Stoner–Wohlfarth approximation. We considered uniaxial anisotropy and different conditions for the external applied field. The results obtained show the switching time distribution can be well described by two relaxation times, either when the applied field is parallel to the easy axis or for an oblique external field and a larger damping constant. We found that in the low barrier limit these relaxation times are in very good agreement with analytical results obtained from solutions of the Fokker–Planck equation related to this problem. When the damping is small and the applied field is oblique the shape of the distribution curves shows several peaks and resonance effects.