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1.
Dielectric relaxation measurements of 5 mole % 4-n-hexyloxycyanobenzene (I) dissolved in 4-n-pentyloxyphenyl-trans-4-n-octylcyclohexylcarboxylate (II) were carried out from 1 kHz to 10 MHz in the nematic, smectic A and smectic B phases. The relaxation frequency of I parallel to the director is about 05 MHz in the SBphase and increases rapidly at the transition from SB to SA.  相似文献   

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The molecular dynamics of amorphous and liquid-crystalline (LC) side-chain polycarbonates was studied by dielectric spectroscopy at frequencies from 10−2 to 106 Hz and at temperatures from −160 to 180°C. ‘Model’ compounds containing no mesogenic side-groups showed two relaxations, which originate from the carbonate group (α, βm-relaxation). By contrast, in LC-polycarbonates bearing a mesogenic nitrostilbene side group around and above the glass transition temperature Tg up to three relaxation modes were distinguished (α-, λ1-, λ2-process); below Tg four secondary relaxations (γ-, βm-, βs-, βsc-relaxation) were observed. The γ-relaxation was found only in compounds possessing an aliphatic spacer linked to the backbone by an ether bond. Apart from βm-, two additional β-processes were identified as relaxations associated with the mesogenic unit in the glassy (βs) or in the crystalline state (βsc).  相似文献   

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The Laplace transform of the electric polarization with respect to time for a molecule having two equivalent interacting rotational groups has been expressed in terms of an infinite continued fraction. This modifies the Debye equation by considering the intramolecular interaction.  相似文献   

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Dielectric measurements on two mixtures of a low and high molecular liquid crystal and the pure components have been carried out in the frequency range from 1 Hz to 100 kHz. In the SA and supercooled SA phase two absorption ranges were observed. The low frequency absorption belongs to the low molecular weight liquid crystal. The shift in the relaxation frequency of both compounds indicates complete miscibility. The strong difference of the absorption intensity of the polymer on heating and cooling can be associated with the formation of mixed crystals at smaller concentrations of the low molecular weight compound.  相似文献   

6.
The relaxation of electric field-induced polar orientation in a side-chain-bearing liquid-crystalline polysiloxane was measured by means of thermally stimulated depolarization currents. Different relaxation mechanisms were identified and characterized: the glass transition cooperative relaxation exhibits compensation behaviour. On the other hand, lowerT g and upperT g discharges were observed and their molecular nature is discussed.  相似文献   

7.
The dielectric properties of a hydrogen-bonded side-chain liquid-crystalline polysiloxane have been examined over wide ranges of frequency and temperature. This polymer has a side-chain mesogenic moiety consisting of a benzoic acid and a stilbazole. The observed dielectric loss curves contain a component from dipole reorientation of the hydrogen-bonded mesogenic group. It has been found to be possible that, using electrical and thermal treatments, such a polymer built through hydrogen bonding can align homeotropically.  相似文献   

8.
Six binary liquid-crystalline mixtures have been studied by means of dielectric, microscopic and refractometric measurements. Induced smectic phases appear for four of them. The effective values of the components p and p of the dipole moment per one molecule of the mixtures have been calculated from values of e and e. It has been established that the heterocomplexes formed in the mixtures are weak so that they do not cause any changes in the distribution of molecular charges. The observed deviations from linearity of the dielectric constants of the mixtures are caused either by dissociation of the cyanomesogen dimers or by a non-additive behaviour of the mixture density.  相似文献   

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Dielectric studies were performed on crystallized and amorphous polydimethylsiloxane which had been characterized by differential thermal analysis and polarized light microscopy. The crystallized specimen displayed one relaxation near 160 K at 1 kHz while the amorphous specimen showed absorption peaks at 155 and 165 K. For the latter material the high-temperature peak was not due to a true relaxation but resulted from crystal nucleation at 160 K and the subsequent growth of spherulites. The low-temperature peak at 155 K resulted from the relaxation associated with the glass transition. A sharp decrease of dielectric constant was observed for both specimens at the melting point (235 K). For the dielectric relaxation associated with the glass transition in crystallized specimens, the values of the dispersion amplitude, the apparent activation energy at 160 K, and the half-width of the absorption curve are 0.43 and 29 kcal/mole, and 5.6 decades, respectively, which are in marked contrast to the corresponding values of 0.82, 18, and 2.2 for amorphous specimens.  相似文献   

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The crosslinking of ferroelectric liquid-crystalline (LC) polysiloxanes — performed within the region of microphase separation — allows the preparation of LC-elastomers which combine macroscopic form stability (insolubility) with nearly unchanged switching time (compared to the uncrosslinked polymers).  相似文献   

14.
A method for obtaining elastic moduli and frictional properties of gel chains, diagonal and off-diagonal elements of a friction tensor, from a tensile force relaxation of cylindrical gel that is stretched in a good solvent is presented. The theory to describe the relaxation is developed on the assumption that an off-diagonal element of the friction tensor is nonzero and compared with experimental results obtained for the poly(acrylamide) gel in water. The experiments revealed that the tensile force relaxation, F(t) at a long t, was described by a function: F(t)=A(Fi-FS) x exp(-t/tau)+FS, where Fi, FS, and A, respectively, were tensile forces at the initiation and the steady state, and a constant. The tau was found to be proportional to a square of radius of the gel. The experiments also revealed that the elastic force relaxation was synchronized with a change of the gel diameter. The theory well elucidates the experimental results to reveal the bulk and shear moduli, and the diagonal and off-diagonal elements of friction tensor.  相似文献   

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The temperature dependence of the dielectric relaxation time of amorphous polymers can be described quite satisfactorily by an expression derived from the theory of the relaxation time for local conformational transitions in a polymer chain. This theory was recently developed using the Kramers theory of the rate constant together with the free-volume theory.  相似文献   

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The dielectric constant ?′ and loss factor ?″ of poly(butyl acrylate), poly(butyl methacrylate), and poly(isobutyl methacrylate) solutions are reported in the frequency region of 1 kHz to 24.42 GHz at four different temperatures of 27, 40, 50, and 60°C. Cole–Cole plots are plotted to obtain the distribution parameter and relaxation time. The activation energies are evaluated assuming dielectric relaxation to be a rate process in these solutions. A possible relaxation mechanism is discussed.  相似文献   

17.
The present study aims at the detailed elaboration of the dielectric relaxation behavior in PVDF composites using broadband dielectric spectroscopy and the Havriliak – Negami method. The composites with multi-wall nanotube carbon and zirconium dioxide in PVDF is fabricated using a simple melt mixing method. The polarization behavior in PVDF composites are investigated on the different frequency region with various temperature. The complex dielectric constants are calculated with the aid of the Havriliak – Negami equation. The characteristic parameters in Havriliak – Negami equation were in excellent agreement with the experimental complex dielectric constants. The results of utilizing these calculated parameters to analyze the origination of the polarization relaxation are given. The purposes of this work expect to give a deeper insight into the impact of different fillers on the dielectric relaxation behavior, and it could provide the technique for the discrepancy with the dipolar for interfacial polarization and the filler effect on the dielectric relaxation.  相似文献   

18.
Relaxation processes in glass-fiber-reinforced composites with a polymer matrix based on blends of thermosetting and thermoplastic polyimides are studied via dielectric-relaxation spectroscopy. For all investigated blends, two relaxation processes related to the β relaxation of different fragments of the polymer chain are found. Linear flexiblechain polyimide incorporated into the polymer matrix serves as a plasticizer.  相似文献   

19.
The relative permittivity at frequencies of 10kHz and 10GHz and the refractive indices have been measured for dilute solutions of (a) nitroethane, (b) 1-nitropropane, (c) 2-nitropropane, and (d) 1-nitrobutane in cyclohexane at 10°, 20°, 30° and 40°C. Materials (b) and (c) together with (e)2-nitro 1-propanol and (f) 2-nitro-l-butanol, have also been studied in different nonpolar solvents. The electric dipole moments, the dielectric relaxation times, and the molar activation energy parameters have been calculated. The results for nitroalcohols show the existence of internal hydrogen bonding between the hydroxyl group and an oxygen atom of the nitro group. The plots of log τ versus log η for materials (b) and (c) are linear for the solvents n-heptane, cyclohexane and decalin. The possibility of interaction of these materials with p-xylene, carbon tetrachloride and p-dioxane are discussed. Activation enthalpy (ΔHε) of these materials is observed to be higher in dilute solutions than in pure liquids, and also ΔHε for nitrobutane is significantly lower than for the other materials.  相似文献   

20.
Rod-like molecules with a strong dipole in the long axis were mixed with synthetic polyisoprene (IR305) in low concentrations (0.1–5 wt%) and measured dielectrically in the frequency range 10–2–106 Hz and the temperature range –60°–0°C (glass relaxation range). The measurements showed an additional symmetrical relaxation process slower than the glass process by a factor ranging from 10 to 100 times, depending on the length and structure of the label. The label relaxation process was characterized by a narrow distribution of relaxation times and its strong coupling with the segmental motion. For the labels with only a longitudinal dipole moment, no relevant part of the label relaxation was observed in the relaxation frequencies of the glass process; this may be attributed to the parallelism and compactness of the polyisoprene chains. In contrast, the labels with an additional vertical dipole component showed an additional relaxation process superimposed on the glass relaxation with also almost the same distribution of relaxation times. The slow label relaxation could be attributed to a diffusion or rotational diffusion relaxation process through a multistep relaxation mechanism determined by the segmental motion of the matrix.  相似文献   

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