Dielectric relaxation of a short molecule in a liquid-crystalline solvent

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 S_Bphase and increases rapidly at the transition from S_B to S_A.     

Dielectric relaxation spectroscopy of amorphous and liquid-crystalline side-chain polycarbonates

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, β_m-relaxation). By contrast, in LC-polycarbonates bearing a mesogenic nitrostilbene side group around and above the glass transition temperature T_g up to three relaxation modes were distinguished (α-, λ₁-, λ₂-process); below T_g four secondary relaxations (γ-, β_m-, β_s-, β_sc-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 β_m-, two additional β-processes were identified as relaxations associated with the mesogenic unit in the glassy (β_s) or in the crystalline state (β_sc).     

Dielectric relaxation of a flexible molecule with an intramolecular interaction

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.     

Dielectric relaxation in a mixture of a side chain liquid-crystalline polymer and a low molecular liquid crystal

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 S_A and supercooled S_A 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.     

Dielectric behaviour of a side-chain-bearing liquid-crystalline polysiloxane

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.     

Dielectric properties of a hydrogen-bonded liquid-crystalline side-chain polymer

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.     

Dielectric studies of binary liquid-crystalline mixtures

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.     

Dielectric relaxation of polydimethylsiloxane

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.     

Stress relaxation of deformed gel in a good solvent

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.     

Ferroelectric liquid-crystalline elastomers with short switching times

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).     

Dielectric relaxation time of polymers

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.     

Dielectric relaxation in some polyacrylate solutions

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.     

Dielectric relaxation in a thermosetting polyimide modified with a thermoplastic polyimide

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.     

Dielectric relaxation of ball-like labels in polyisoprene

Ball-like molecules with strong dipoles (labels) were mixed with synthetic polyisoprene (IR305) in low concentrations (<1%) and measured dielectrically in the frequency range 10^–2–10⁷ Hz and the temperature range –70–0°C (glass relaxation region). Calorimetric measurements showed that this type of label has a plasticizing effect on the polymeric matrix. The dielectric measurements showed that these ball-like molecules relax through cooperative rotations with the polymeric segments and at the same relaxation frequency. In addition, the label molecules showed a high-frequency local relaxation process. The relaxation strength ratio of the local process (X _local) to the total relaxation strength of the label was found to be dependent on the volume as well as on the shape of the label. A comparison between the relaxation behaviors of the ball-and rod-like molecules, having the same volume, showed that the length of the label is also an important parameter for the determination of the local contribution as well as of the cooperative relaxation mechanism of the label. The label relaxation process is discussed in relation to the molecular packing of the host polymer.     

Dielectric relaxation of electrolyte solutions in acetonitrile

Complex permittivity spectra in the frequency range 0.95v (GHz)89 for acetonitrile and its solutions of LiBr, NaI, NaClO₄, and Bu₄NBr at 25°C show one Debye equation for the neat solvent whereas the superposition of a Debye process for the solute and a Cole-Cole distribution for the solvent is necessary to account for the dielectric relaxation behavior of the solutions. The reorientation of bulk acetonitrile is diffusive and only weakly coupled to viscosity. The number of solvent molecules irrotationally bound to the electrolyte is in good agreement with conventional solvation numbers for all electrolytes, when kinetic depolarization is assumed to be negligible. The solute relaxation process is dominated by the formation kinetics and reorientation of contact ion pairs. There is evidence for solvent-shared ion pairs in dilute NaClO₄ solutions.