Dielectric properties of novel poly(aryl prehnitimide)s

Six different variants of a new type of polyimide, poly(aryl prehnitimide)s, containing various moisture contents have been studied using dielectric relaxation spectroscopy. Dielectric loss measurements show the presence of a double peak near 200 K (depending on frequency) due to water relaxation. The two peaks have been designated γ₁ and γ₂. The γ₂ peak appears as a shoulder on the γ₁ peak at lower temperatures and is very sensitive to moisture content. The γ₁ peak is less sensitive to moisture content and is associated with isolated water molecules coupled to the polymer chains. Both of the γ-relaxation peaks were studied in detail to obtain the associated activation energies. © 1996 John Wiley & Sons, Inc.     

Transport of water in polyvinyl alcohol films: Effect of thermal treatment and chemical crosslinking

Data on sorption and transport of water in polyvinyl alcohol films, modified by thermal treatment above T_g, or by chemical crosslinking with glutaraldehyde at different crosslinking degrees, are presented. Equilibrium swelling is constrained by both treatments, except for low degrees of crosslinking where the said reduction is counterbalanced by the partial loss of crystallinity. Analysis of the resulting water uptake kinetics indicates that viscous relaxation effects are, at least partly, responsible for the observed non-Fickian kinetic behavior. Thermodynamic diffusion coefficients of water, D_W, and relaxation frequencies of the swelling polymer, β_W, are determined by application of a theoretical model accounting for relaxation-dependent sorption kinetics in glassy polymers. The results indicate that the effect of both heat-treatment and chemical crosslinking is more intense on the macromolecular relaxation process than on the diffusion coefficient of water. Comparison of the release kinetics of a model drug from as-prepared, non-crosslinked and from crosslinked matrices indicate that the retardation of macromolecular relaxations process induced by crosslinking results in a more uniform release rate.     

Water and polymer dynamics in poly(hydroxyl ethyl acrylate-co-ethyl acrylate) copolymer hydrogels

Water and polymer dynamics in hydrogels based on random copolymers of hydrophilic poly(hydroxyl ethyl acrylate) (PHEA) and hydrophobic poly(ethyl acrylate) (PEA), in wide ranges of composition, were investigated by means of two dielectric techniques, thermally stimulated depolarization currents (TSDC) and, mainly, broadband dielectric relaxation spectroscopy (DRS) at several levels of relative humidity/water content. Water sorption of the hydrogels was studied by equilibrium sorption isotherms (ESI). Two secondary relaxations (γ and β_sw) and the primary (segmental) α relaxation associated with the glass transition of the copolymer matrix were followed and analyzed against copolymer composition and water content. The results show that the copolymers are homogeneous at nm scale, except at very high PEA content. Correlations were observed between results on the organization of water in the hydrogels and on water effects on polymer dynamics. Distinct changes in the dielectric response, in particular in the time scale and the dielectric strength of the β_sw relaxation, at the water content of the completion of the first hydration layer indicate that water molecules themselves contribute to the dielectric response at higher water contents. Proton conductivity of the hydrogels at various levels of water content was also studied and correlation to segmental dynamics (decoupling) was analyzed.     

Interval kinetic gravimetric sorption of acetone in random copolymers of poly(ethylene terephthalate) and poly(ethylene 2,6-naphthalate)

Interval sorption kinetics of acetone in solvent cast films of random poly(ethylene terephthalate)-co-(ethylene 2,6-naphthalate) (PET-co-PEN) are reported at 35°C and at acetone pressures ranging from 0 to 7.3 cm Hg. Polymer composition is varied systematically from 0% to 50% poly(ethylene 2,6-naphthalate). Equilibrium sorption is well described by the dual-mode sorption model. Interval sorption kinetics are described using a two-stage model that incorporates both Fickian diffusion and protracted polymer structural relaxation. The incorporation of low levels of PEN into PET significantly reduces the excess free volume associated with the glassy state and, for these interval acetone sorption experiments in ∼ 5 μm-thick films, decreases the fraction of acetone uptake controlled by penetrant-induced polymer structural relaxation. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2973–2984, 1999     

NMR studies of water in polyimide films

Commercial polyimide films containing up to ～ 3 wt % water have been studied by proton, deuteron, and oxygen-17 nuclear magnetic resonance (NMR). Comparisons between NMR results and previous dielectric relaxation (DR) results for a variety of Kapton films show that there is a one-to-one correspondence between specific dielectric loss peaks and features of the ²H or ¹⁷O NMR spectra. It is concluded that water molecules, which interact only weakly with the polymer, reside in the polyimide matrix in two configurations, randomly oriented single molecules and chains of water molecules oriented perpendicular to the plane of the film. The correspondence between NMR and DR observed in water in Kapton extends to water in Upilex and to methanol and acetic acid in Kapton. © 1995 John Wiley & Sons, Inc.     

Sorption and diffusion of organic vapors in amorphous Teflon AF2400

Vapor sorption in amorphous Teflon AF2400 of various organic solutes was studied in a wide range of activity at 25 °C by means of the gravimetric technique. The sorption isotherms of hexane, toluene, and chloroform were shown to be concave to the pressure axis and are consistent with the dual mode sorption model (DMS). The parameters of the DMS model k_D and b reveal a linear correlation with squared critical temperature of solutes T. The third model parameter, the Langmuir sorption capacity C′_H decreases when the size of solutes (critical volume) increases. Sorption isotherms of methanol and ethanol were shown to be convex to the pressure axis and are consistent with cluster formation in this strongly hydrophobic polymer. Concentration‐dependent diffusion coefficients D were determined using a linear implicit difference scheme in analysis of sorption kinetics. It was shown that D values increase exponentially with concentration for all the solutes, except alcohols for which exponential reduction of D(C) was observed. The partitioning of the thermodynamic and mobility contributions in D indicated that the reduction of D values of alcohols is consistent with clustering phenomena in AF2400. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 832–844, 2006     

Kinetics and equilibria associated with the absorption and desorption of water and lithium chloride in an ethylene—vinyl alcohol copolymer

Sorption and desorption equilibria and kinetics for LiCl and H₂O in an ethylene—vinyl alcohol copolymer film containing 70 mole percent vinyl alcohol were investigated at 25°C. The swelling behavior of water in the polymer was characterized by vapor and liquid sorption experiments over a range of water activities. p]The effects of LiCl content on the water sorption kinetics and equilibria in the films are presented and discussed. The kinetics and mechanism of LiCl sorption have also been studied. The amount of salt sorbed into the polymeric films increases linearly with the salt concentration in the external aqueous solutions. Both the rate and the amount of sorbed water increase significantly as the LiCl content increases. p]The desorption of LiCl, previously sorbed into the polymer, was characterized for different salt loadings. The rate of fractional salt release is independent of LiCl concentration in the film. Initially, the salt release is controlled by the nearly constant-rate absorption of water. The salt release, at long times, lags behind the swelling-controlled water uptake, indicating that the salt release is not completely controlled by the water sorption and that diffusion in the swollen polymer matrix contributes significantly to the long term elution of LiCl. Independent thermal analysis experiments suggest the formation of a metal salt—poly(ethylene—vinyl alcohol) complex.     

Sorption of small molecules in various polycarbonates and Kapton-H

Pressure-composition isotherms were determined at 20°C for CO₂ in Kapton and various substituted polycarbonates and for H₂O, Ar, N₂, CH₄, and acetone in bisphenol-A-polycarbonate. The isotherms are described by two parameters an average free energy of sorption and a width of a Gaussian distribution of free sorption energies. Within the framework of a recent model these parameters can be calculated assuming an elastic distortion of the polymer caused by the incorporation of solute atoms in preexisting holes. By comparing experimental values with predictions of the model the experimental width of the free energy distribution is only 30% smaller than the theoretical one. Functional relationships are obeyed between the sorption parameters on the one hand and glass transition temperature, average hole volume, and molecular volume of the solute on the other hand. Deviations occur for larger molecules like acetone and ethylene which are attributed to a viscoelastic distortion of the polymer. Comparing free energies of solution for the rubbery and glassy state of the polymer reveals more negative values for the glassy polymers despite their extra elastic distortion energy. This discrepancy is overcome by taking into account that the occupied volume has to be re-formed in the case of the rubbery or liquid polymer. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 483–494, 1998     

The origin of DC electrical conduction and dielectric relaxation in pristine and doped poly(3‐hexylthiophene) films

We present here the evidence for the origin of dc electrical conduction and dielectric relaxation in pristine and doped poly(3‐hexylthiophene) (P3HT) films. P3HT has been synthesized and purified to obtain pristine P3HT polymer films. P3HT films are chemically doped to make conducting P3HT films with different conductivity level. Temperature (77–350 K) dependent dc conductivity (σ_dc) and dielectric constant (ε′(ω)) measurements on pristine and doped P3HT films have been conducted to evaluate dc and ac electrical conduction parameters. The relaxation frequency (f_R) and static dielectric constant (ε₀) have been estimated from dielectric constant measurements. A correlation between dc electrical conduction and dielectric relaxation data indicates that both dc and ac electrical conductions originate from the same hopping process in this system. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1047–1053, 2010     

Role and effect of dopant ion on sorption-induced motion of polypyrrole films

The sorption-induced bending and recovery motion of PPy films containing different dopant ions have been investigated, and the interaction between water vapor and PPy was studied from sorption isotherms and kinetics. It was found that the PPy/BF₄ film exhibited the most rapid motion, and the initial speeds of bending and recovery motion were 7.9 and 5.9 mm s⁻¹, respectively. The linear expansion coefficient of the film increased in order of PPy/DBS, PPy/TsO, PPy/ClO₄, and PPy/BF₄, which is consistent with the packing density of the PPy chains (ϕ_PPy). The dual-mode sorption model applied to the isothermal sorption of water vapor to the PPy demonstrated that the Langmuir's capacity constant increased in the same order with the ϕ_PPy, while the Henry's law constant was nearly constant. The sorption kinetics obeyed Fickian despite the dimensional change of the films, and the PPy/BF₄ film had the largest diffusion coefficient of 3.13 × 10⁻⁸ cm² s⁻¹. The experimental results indicated that the kind of dopant ion was crucial to the thermodynamics and kinetics of sorption, and the quick and intensive bending motion of PPy/BF₄ films was attributed to the fast diffusion of water vapor, which caused the large dimensional change of the film.© 1998 John Wiley & Sons, Inc. J. Polym. Sci. B Polym. Phys. 36: 2635–2642, 1998     

Conductivity and dielectric relaxation in various polyvinyl alcohol/ammonium salt composites

We studied electrical conductivity and dielectric relaxation in polyvinyl alcohol/ammonium chloride and polyvinyl alcohol/ammonium acetate composite films. Infrared absorbance showed the presence of H-bonding interaction between the salt and the polymer. X-ray diffraction showed the reduction of the grain size of ordered regions in the polymer matrix after adding salt. Thermo gravimetric analysis (TGA) showed water wt% content between 4.2 and 5.8%. Differential Scanning Calorimetry (DSC) showed the decrease of the glass transition due to retained water indicating its plasticizer effect. The ac conductivity studied in the frequency range from 10^?1 Hz to 1 MHz and the temperature range from 10 to 150°C is described by the universal law of Jonsher characterizing the charge transport in disordered materials. With NH₄Cl inclusion, the dc conductivity showed a higher value in the vicinity of 4% but with NH₄CH₃CO₂ the dc conductivity decreases monotonically by increasing the salt amount. By using the dielectric permittivity and dielectric modulus we detected three relaxation processes which we attributed to electrode/sample polarization, alpha relaxation and conductivity relaxation respectively.     

Dielectric relaxation of polymer networks built from macromolecules with dipole moment directed along the end-to-end chain vector

The dielectric relaxation properties are considered for polymer networks built from polar macromolecules with the dipole moment directed along the end-to-end chain vector. The viscoeleastic cubic model of a regular network is used. The fixed average volume of a polymer network is ensured by the effective internal pressure. The dynamic models of polymer networks with external and interchain friction are studied. Two cases are considered: (1) polar chains cross-linked in a network at their ends, and (2) a densely cross-linked network with many network junctions per polar chain. The expressions for the autocorrelation functions of the total dipole moment of a network, which determine the dielectric susceptibility, are calculated. The relaxation spectrum of the autocorrelation function consists of two regions: the high-frequency relaxation spectrum of a chain fragment between two neighbouring junctions (intrachain relaxation spectrum) and the lowfrequency interchain relaxation spectrum. The interchain relaxation spectrum is determined by cooperative motions of chains which form a network. The characteristic time of this spectrum for networks of type (1) is the relaxation time of a chain between junctions τ_min. For networks of type (2) a second time scale τ₁ exists, which corresponds to motions inside the volume occupied by a single long polar chain included in a network. It leads to different time behaviour of the autocorrelation functions for both network models. The existence of only interchain friction in the network model leads to a cut-off of the relaxation spectrum at the time τ_max depending on the volume of viscous interchain interactions.     

Aqueous process to limit hydration of thin-film inorganic oxides

Aqueous-processed aluminum oxide phosphate (AlPO) dielectric films were studied to determine how water desorbs and absorbs on heating and cooling, respectively. In-situ Fourier transform infrared spectroscopy showed a distinct, reversible mono- to bidentate phosphate structural change associated with water loss and uptake. Temperature programmed desorption measurements on a 1-μm thick AlPO film revealed water sorption was inhibited by an aqueous-processed HfO₂ capping film only 11-nm thick. The HfO₂ capping film prevents water resorption, thereby preserving the exceptional performance of AlPO as a thin-film dielectric.     

Measurement of the dielectric relaxation property of water-ion loose complex in aqueous solutions of salt at low concentrations

Electrolytes and their dissociated ions are thought to form positive or negative hydration layers around them. In this study, we have developed a method to determine the volume and the dielectric relaxation property (relaxation frequency f c, dispersion intensity delta) of the water hydrating ions in salt solutions. The method consists of four steps: (1) By use of a high-resolution microwave dielectric spectroscopy technique, the dielectric spectra of sample salt solution and bulk water are measured in pair. (2) The dielectric spectrum of solutes (ions) with water layers for a given volume fraction varphi is then calculated from each pair of dielectric spectra of a sample salt solution and reference water according to the Hanai mixture theory. (3) Each spectrum of solutes with water layers at a given varphi is decomposed into a few Debye relaxation functions and the bulk water component. (4) The volume fraction varphi is operationally decreased from 0.5, and steps (2) and (3) are repeated at each varphi until the bulk water component vanished. Then the volume fraction of the hydrated solutes (ions) in solution is determined. The method was applied to NaF and NaCl solutions. As a result the different spectral intensity was nearly proportional to the salt concentration below 0.2 M in the frequency range of 3-26 GHz. The hydration number N h and the dielectric relaxation property of the hydration layer for each salt solution was successfully determined as ( f c1, delta 1, N h)= (18.7, 44.9, 27.9) for NaCl and ( f c1, delta 1, f c2, delta 2, N h) = (26.0, 6.70, 5.64, 19.2) for NaF.     

Effect of penetrant-induced isothermal glass transition on sorption,dilation, and diffusion behavior of polybenzylmethacrylate/CO2

The effect of a penetrant-induced isothermal glass transition on sorption, dilation, and diffusion behavior was studied in a single experimental run for CO₂ in cast polybenzylmethacrylate films. The dual-mode type sorption isotherms below the glass transition temperature of the polymer changed to linear ones above a certain concentration. Meanwhile, partial molar volume of CO₂ determined from the dilation of the films above the concentration gave a value very close to the one reported for rubbery polymers, and diffusion coefficients became less concentration-dependent. The results were conformable to the concept of unrelaxed volume in glassy polymers. © 1996 John Wiley & Sons, Inc.     

A molecular dynamics study of the dielectric properties of aqueous solutions of alanine and alanine dipeptide

Molecular dynamics simulations were used to compute the frequency-dependent dielectric susceptibility of aqueous solutions of alanine and alanine dipeptide. We studied four alanine solutions, ranging in concentration from 0.13-0.55 mol/liter, and two solutions of alanine dipeptide (0.13 and 0.27 mol/liter). In accord with experiment we find a strong dielectric increment for both solutes, whose molecular origin is shown to be the zwitterionic nature of the solutes. The dynamic properties were analyzed based on a dielectric component analysis into solute, a first hydration shell, and all remaining (bulk) waters. The results of this three component decomposition were interpreted directly, as well as by uniting the solute and hydration shell component to a "suprasolute" component. In both approaches three contributions to the frequency-dependent dielectric properties can be discerned. The quantitatively largest and fastest component arises from bulk water [i.e., water not influenced by the solute(s)]. The interaction between waters surrounding the solute(s) (the hydration shell) and bulk water molecules leads to a relaxation process occurring on an intermediate time scale. The slowest relaxation process originates from the solute(s) and the interaction of the solute(s) with the first hydration shell and bulk water. The primary importance of the hydration shell is the exchange of shell and bulk waters; the self-contribution from bound water molecules is comparatively small. While in the alanine solutions the solute-water cross-terms are more important than the solute self-term, the solute contribution is larger in the dipeptide solutions. In the latter systems a much clearer separation of time scales between water and alanine dipeptide related properties is observed. The similarities and differences of the dielectric properties of the amino acid/peptide solutions studied in this work and of solutions of mono- and disaccharides and of the protein ubiquitin are discussed.     

Induction and measurement of glassy-state relaxations by vapor sorption techniques

Recent gravimetric studies of the sorption of organic vapors by poly(vinyl chloride) and polystyrene powders have demonstrated several features which promise to be generally useful in studying the structure and properties of the glassy state. The uptake of vapor can be significantly altered by prior thermal or vapor treatment of the polymer, apparently reflecting changes in the microvoid content or free volume of the polymer. Fickian sorption in sufficiently fine powders proceeds to equilibrium in a few minutes. Upon exposure of a polymer powder to an appreciable pressure of vapor, both a rapid Fickian sorption and a slower, relaxation-controlled sorption are observed. Superposition of these processes leads to widely varied sorption kinetics; a model comprising Fickian diffusion and first-order relaxation terms accurately describes the data and allows estimation of equilibrium and rate constants for both processes. After prolonged exposure, removal of a swelling vapor induces a slow reconsolidation of the polymer structure; this deswelling relaxation can be monitored by the decreasing amounts of vapor sorbed in repeated brief exposures to low vapor pressures, and can also be described by a first-order relaxation model. In this regard, the penetrant vapor serves as a molecular probe, monitoring glassy-state relaxation occurring in the absence of penetrant. The same, presumably true equilibrium is ultimately reached both by swelling from a low free-volume state and by consolidation from a preswollen state of high free volume. The rates of both swelling and consolidation relaxations appear to be retarded by the presence of low concentrations of vapor in the polymer, suggesting that vapor molecules may preempt some of the free volume required for relaxation.     

Thermal transitions and dynamics in nanocomposite hydrogels

Hydrogels based on nanocomposites of statistical poly(hydroxyethyl acrylate-co-ethyl acrylate) and silica, prepared by simultaneous copolymerization and generation of silica nanoparticles by sol?Cgel process at various copolymer compositions and silica contents, characterized by a fine dispersion of filler, were investigated with respect to glass transition and polymer dynamics by dielectric techniques. These include thermally stimulated depolarization currents and dielectric relaxation spectroscopy, covering together broad ranges of frequency and temperature. In addition, equilibrium water sorption isotherms were recorded at room temperature (25?°C). Special attention was paid to the investigation of effects of silica on glass transition, polymer dynamics (secondary ?? and ?? _sw relaxations and segmental ?? relaxation), and electrical conductivity in the dry systems (xerogels) and in the hydrogels at various levels of relative humidity/water content. An overall reduction of molecular mobility is observed in the nanocomposite xerogels, in particular at high silica contents. Analysis of the results and comparison with previous work on similar systems enable to discuss this reduction of molecular mobility in terms of constraints to polymeric motion imposed by interfacial polymer?Cfiller interactions and by the formation of a continuous silica network interpenetrated with the polymer network at filler contents higher than about 15?wt%.     

Gas permeability and hydrocarbon solubility of poly[1‐phenyl‐2‐[p‐(triisopropylsilyl)phenyl]acetylene]

The effects of film thickness, physical aging, and methanol conditioning on the solubility and transport properties of glassy poly[1‐phenyl‐2‐[p‐(triisopropylsilyl) phenyl]acetylene] are reported at 35 °C. In general, the gas permeability coefficients are very high, and this polymer is more permeable to larger hydrocarbons (e.g., C₃H₈ and C₄H₁₀) than to light gases such as H₂. The gas permeability and solubility coefficients are higher in as‐cast, unaged films than in as‐cast films aged at ambient conditions and increase to a maximum in both unaged and aged as‐cast films after methanol conditioning. For example, the oxygen permeability of a 20‐μm‐thick as‐cast film is initially 100 barrer and decreases to 40 barrer after aging for 1 week at ambient conditions. After methanol treatment, the oxygen permeabilities of unaged and aged films increase to 430 and 460 barrer, respectively. Thicker as‐cast films have higher gas permeabilities than thinner as‐cast films. Propane and n‐butane sorption isotherms suggest significant changes in the nonequilibrium excess free volume in these glassy polymer films due to processing history. For example, the nonequilibrium excess free volume estimated from the sorption data is similar for as‐cast, unaged samples and methanol‐conditioned samples; it is 100% higher in methanol‐conditioned films than in aged, as‐cast films. The sensitivity of permeability to processing history may be due in large measure to the influence of processing history on nonequilibrium excess free volume and free volume distribution. The propane and n‐butane diffusion coefficients are also sensitive to film processing history, presumably because of the dependence of diffusivity on free volume and free volume distribution. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1474–1484, 2000     

Dielectric properties of propylene carbonate and propylene carbonate solutions

Permittivity data at frequencies from 0.9 to 12 GHz for propylene carbonate and for the solutions of NaI, NaClO₄, Bu₄NI, Bu₄NClO₄, ZnBr₂, and Ca(ClO₄)₂ in propylene carbonate at 25°C are reported and discussed. The contaminating influence of water on the dielectric spectra is shown. Measurements were executed by the method of travelling waves with equipment known to produce data of high precision. Evaluation of the data is performed on the basis of models presupposing one or more relaxation regions. The dielectric spectra of all salts with the exception of ZnBr₂ yield relaxation time distributions with a single critical relaxation time or can be analyzed by assuming two critical relaxation times for the solvent. ZnBr₂ solutions show a supplementary relaxation region at low frequencies which is attributed to the solute. The variation of permittivities at zero frequency with the salt concentration is discussed in the framework of kinetic depolarization. Solvation numbers are estimated.