Dynamic light scattering as a probe of orientational dynamics in confined liquid crystals

The eigenmodes of director orientational fluctuations in nematic liquid crystals in confined geometries were studied both theoretically and experimentally by dynamic light-scattering tehnique. The fundamental mode of the orientational fluctuations shows a crossover from bulk behavior, dominated by bulk elastic constant K, to surface dominated one, in which the relaxation rate is determined by the ratio of surface anchoring strength W and viscosity eta. The contribution of surface viscosity zeta is also significant when its characteristic length zeta/eta becomes comparable to the size of the confined system. It was measured in nematic liquid crystal in cylindrical pores of polycarbonate (Nuclepore) membranes to be of the order of 10 nm.     

An interstitialcy theory of structural relaxation and related viscous flow of glasses

A theory of isothermal structural relaxation and creep of glasses below the glass transition temperature is given. According to the interstitialcy theory, the supercooled liquid state does not exist below a Kauzmann "pseudocritical" temperature T(k), which lies above the temperature T(K), commonly called the "Kauzmann temperature." Structural relaxation is simply a reduction with time of the interstitialcy concentration to the crystalline state for TT(k). The predicted viscosity eta is universal, given by eta=eta(0) + eta(T)t, in agreement with experiment. eta is continuous in T, with eta discontinuous at T(k) but linear in 1/T above and below T(k). The dependence of eta on the shear modulus directly connects kinetic and thermodynamic properties of glasses and liquids.     

大块金属玻璃Zr41Ti14Cu12.5Ni10Be22.5的流变行为研究

采用静态拉伸方法在连续升温条件下动态地测量了大块金属玻璃Zr41Ti14Cu12.5Ni10Be22.5（Vit1）的黏度随温度的变化关系.在应变速率与温度的关系曲线中，观测到了与玻璃转变和晶化过程相联系的多个应变速率峰.在玻璃转变温度Tg以上，大块金属玻璃Zr41Ti14Cu12.5Ni10Be22.5的过冷液体呈现Newton流体特征，其黏度与温度的关系符合Vogel Fulcher-Tammann (VFT)关系式，拟合得到脆度D*＝36，VFT温度T0＝319K，脆度参数m＝30，这说明Zr41T 关键词： 大块金属玻璃 应变速率 剪切黏度 自由体积     

Coexistence of glass and ferroelectric order in deuterated betaine phosphate0.05 betaine phosphite0.95 crystals

The dielectric spectra of ferroelectric hydrogen bonded betaine phosphate_0.05 betaine phosphite_0.95 (DBP_0.05DBPI_0.95) was investigated in the very wide temperature (300–20 K) and frequency (20–35 GHz) regions. The dielectric dispersion was analyzed in terms of distribution of relaxation times, using Tichonov regularization method. Strongly asymmetric and broad distribution of relaxation times below ferroelectric phase transition temperature T _c?≈?253 K clearly differs from the one that is usually observed in ferroelectrics. The observed disorder in deuterons system close to ferroelectric phase transition temperature is an embryo of coexistence ferroelectric order and dipolar glass disorder observed at low temperatures.     

Dielectric and conductivity relaxation in mixtures of glycerol with LiCl

We report a thorough dielectric characterization of the α relaxation of glass-forming glycerol with varying additions of LiCl. Nine salt concentrations from 0.1 to 20mol% are investigated in a frequency range of 20Hz-3GHz and analyzed in the dielectric loss and modulus representation. Information on the dc conductivity, the dielectric relaxation time (from the loss) and the conductivity relaxation time (from the modulus) is provided. Overall, with increasing ion concentration, a transition from reorientationally to translationally dominated behavior is observed and the translational ion dynamics and the dipolar reorientational dynamics become successively coupled. This gives rise to the prospect that, by adding ions to dipolar glass formers, dielectric spectroscopy may directly couple to the translational degrees of freedom determining the glass transition, even in frequency regimes where usually strong decoupling is observed.     

Dynamical studies of highly deuterated betaine phosphate near the antiferroelectric phase transition

The dielectric response and the Raman spectra of single crystals of deuterated betaine phosphate are studied around the antiferroelectric phase transition. The dielectric data between 10 MHz and 11 GHz can be explained on the basis of a simple Debye-relaxation with a critical slowing-down of the relaxation rate on approachingT _C . Using the Cole-Davidson form of the dielectric function we succeeded in fitting the data in the whole frequency range from 10 MHz to 11 GHz and from 64–400 GHz over a temperature range from 145–280 K. Raman spectra clearly indicate that the doubling of the unit cell does not take place at the antiferroelectric transition temperature, but some degrees below.     

On the dynamics of liquids in their viscous regime approaching the glass transition

Recently, Mallamace et al. (Eur. Phys. J. E 34, 94 (2011)) proposed a crossover temperature, T(×), and claimed that the dynamics of many supercooled liquids follow an Arrhenius-type temperature dependence between T(×) and the glass transition temperature T(g). The opposite, namely super-Arrhenius behavior in this viscous regime, has been demonstrated repeatedly for molecular glass-former, for polymers, and for the majority of the exhaustively studied inorganic glasses of technological interest. Therefore, we subject the molecular systems of the Mallamace et al. study to a "residuals" analysis and include not only viscosity data but also the more precise data available from dielectric relaxation experiments over the same temperature range. Although many viscosity data sets are inconclusive due to their noise level, we find that Arrhenius behavior is not a general feature of viscosity in the T(g) to T(×) range. Moreover, the residuals of dielectric relaxation times with respect to an Arrhenius law clearly reveal systematic curvature consistent with super-Arrhenius behavior being an endemic feature of transport properties in this viscous regime. We also observe a common pattern of how dielectric relaxation times decouple slightly from viscosity.     

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   

偏氟乙烯/三氟乙烯铁电共聚物的非晶介电弛豫

用溶液成膜、液氮淬火、熔融慢冷和热处理4种方法制得不同结晶度的VDF/TrFE共聚物试样。在已改进的介电弛豫谱仪(精度由原来的1％提高到2‰)上测得复数介电常数。从结晶度为20％的淬火试样室温以下的介电频率谱中发现了非晶介电弛豫,并由此得到了玻璃化温度与共聚物组分含量的关系。 关键词：     

Glass transition and relaxation processes in supercooled water

Many of water's peculiar physical properties are still not well understood, and one of the most important unresolved questions is its glass transition related dynamics. The consensus has been to accept a glass transition temperature (T(g)) around 136 K, but this value has been questioned and reassigned to about 165 K. We find evidence that the dielectric relaxation process of confined water that has been associated with the long accepted T(g) of water (130-140 K) must be a local process which is not related to the actual glass transition. Rather, our data indicate a glass transition at 160-165 K for bulk water and about 175 K for confined water (depending on the confining system).     

How we can interpret the T1 dispersion of MC, HPMC and HPC polymers above glass temperature?

The chain dynamics in methyl cellulose (MC), hydroxypropylmethyl cellulose (HPMC) and hydroxypropyl cellulose (HPC) were studied with the aid of field-cycling NMR relaxometry technique in the temperature range from 300 to 480 K that is above the glass transition, but below thermal degradation. The frequency dependence of proton spin-lattice relaxation time was determined between 24 kHz and 40 MHz for selected temperatures. The experimental spin-lattice relaxation dispersion data were fitted with the power law relations of T(1) proportional variant omega(gamma) predicted by the tube/reptation model. The exponent's values found from the fitting procedure for MC, HPMC and HPC almost exactly match the ones predicted in tube/reptation model for limit II (gamma=0.75) and in MC also for limit III (gamma=0.50). Remarkably, this finding concerns the polymers in networks formed of the same polymer species.     

Thermally stimulated currents in poly(vinyl chloride): Tacticity and molecular weight influence

Thermally stimulated currents (TSC) have been measured in several samples of poly(vinyl chloride) differing in tacticity and molecular weight as a result of polymerizing them at different temperatures. This has allowed us to characterize the relaxation behavior of PVC. No dielectric relaxation can be observed by this experimental technique at temperatures between liquid helium and liquid nitrogen. The β relaxation is observed around 173°K, with similar parameters in all samples studied. Around the glass transition the relaxation times isolated in the α peak follow a compensation law. Molecular weight and tacticity have a strong influence on the temperature of the maximum and the intensity of this relaxation, respectively.     

Microscopic theory of heterogeneity and nonexponential relaxations in supercooled liquids.

Recent experiments show that supercooled liquids around the glass transition temperature are "dynamically heterogeneous" [H. Sillescu, J. Non-Cryst. Solids 243, 81 (1999)]. Such heterogeneity is expected from the random first order transition theory of the glass transition. Using a microscopic approach based on this theory, we derive a relation between the departure from Debye relaxation as characterized by the beta value of a stretched exponential response function, phi(t) = e(-(t/tau(KWW))beta), and the fragility of the liquid. The beta value is also predicted to depend on temperature and to vanish as the ideal glass transition is approached at the Kauzmann temperature.     

Thermostimulated creep in amorphous polyolefins. II

The thermostimulated creep of three amorphous polyolefins having the repeating unit ─(CH₂)_mC(CH₃)(C₂ H₅)─, where m = 1, 2, and 3, was investigated from 77° K to 350° K. A broad relaxation process is observed around the glass transition temperature in each polyolefin. The corresponding TSC peaks have been resolved into elementary components with a relaxation time τ obeying a compensation law τ = τ_c exp {(ΔH/k)[1/T) —(1/T_c)], where T_c and T_c are characteristic of the polyolefin. From the TSC data, we have calculated, the mechanical loss peaks associated with the glass transition and we have compared them with the dielectric loss peaks.     

Brillouin scattering in liquid sulfur dioxide: relaxational behaviour

The frequency dependence of hypersonic absorption and the dispersion of hypersonic speed in liquid sulfur dioxide (SO₂) were determined at (293.75±0.30) K and at (284.65±0.30) K by Brillouin spectroscopy. The results are used to experimentally establish the second relaxation step in the double vibrational relaxation of these quantities in the liquid phase, which was first conjectured by R. Bass and J. Lamb, Proc. R. Soc. Ser. A (1958) 243, 94. This second relaxation takes place at approximately 1.5 GHz for both temperatures within experimental error, whereas the first relaxation step, previously determined by ultrasonic spectroscopy, takes place at approximately 23 MHz. In the course of this investigation, some evidence was found that for the temperatures considered the shear viscosity relaxes in the hypersonic frequency range.     

Structure and properties of confined sodium nitrite

The temperature evolution of the structure of NaNO(2) nanocomposite ferroelectric material in a porous glass with 7 nm pores was studied by neutron diffraction in temperature region from room temperature up to the melting, i.e. in the ferro- and paraelectric phases. It is demonstrated that in the ferroelectric phase the structure is consistent with the structure of the bulk, but above the ferroelectric phase transition (and up to approximately 513 K) a volume premelted state is formed, manifesting itself in a growth of amplitudes of ion thermal vibrations, a steep increase of elementary cell volume and "softening" of lattice. For the first time the temperature dependence of order parameter eta for confined sodium nitrite is determined. eta (T) follows a power law with T(C)=425.6+/- 2.1 K and beta= 0.31+/- 0.04, which is essentially different from that for bulk NaNO(2). Our obtained data are in a good agreement with the results of earlier dielectric and neutron diffraction measurements.     

Structural relaxation and viscous flow in amorphous ZrAlCu

The ternary metallic glass Zr₆₅Al_7.5Cu_27.5 offers a wide temperature range between glass transition temperature and crystallization temperature and is therefore well suited for investigation of the glass transition and the state of the super cooled liquid. The non-linear viscosity change caused by structural relaxation has been measured caused by structural relaxation has been measured using tensile creep experiments on as quenched samples. The increase of viscosity can be described by bimolecular annihilation kinetics of flow defects. The Arrhenius plot of equilibrium viscosity shows a kink at a temperature which seems to be the glass transition temperature. The activation energies of viscous flow below and above that glass transition temperature differ by nearly a factor two. Different microscopic processes responsible for viscous flow in the two regimes of temperature are therefore conceivable. This view is also encouraged by Dynamic-Mechanical-Analysis on relaxed samples, a method to examine the viscoelastic behaviour of glassy materials on different time scales and by recent diffusion measurements on a different system.     

Intrinsic aging and effective viscosity in the slow dynamics of a soft glass with tunable elasticity

We investigate by rheology and light scattering the influence of the elastic modulus, G0, on the slow dynamics and the aging of a soft glass. We show that the slow dynamics and the aging can be entirely described by the evolution of an effective viscosity, eta(eff), defined as the characteristic time measured in a stress relaxation experiment times G0. At all times, eta(eff) is found to be independent of G0, of elastic perturbations, and of the rate at which the sample is quenched in the glassy phase. We propose a simple model that links eta(eff) to the internal stress built up at the fluid-to-solid transition.     

From a simple liquid to a polymer melt: NMR relaxometry study of polybutadiene

We utilize NMR field cycling relaxometry to study the crossover from glassy dynamics (t approximately > tau alpha) through Rouse to reptation behavior in a series of monodisperse polybutadienes with molecular weights M=355 to 817,000 g/mol. We separate characteristic polymer dynamics from the total spectrum dominated by glassy dynamics. The polymer dynamics show typical Rouse relaxation features that grow with M and saturate at high M. Comparing to Rouse theory, we determine the Rouse unit size MR approximately = 500 and entanglement weight Me approximately = 2000; the Rouse spectrum saturates at Mmax approximately = 4000. The local order parameter S approximately 0.11 is relatively large, indicating noticeable local packing already in the Rouse regime. The M dependence of the glass transition temperature Tg, obtained from dielectric relaxation spectra, shows distinctive kinks at MR and Me.