Broadband dielectric spectroscopy on a discotic liquid crystalline polymer

Broadband dielectric spectroscopy is employed for the first time to study the molecular dynamics in discotic liquid crystalline polymers. One dielectric relaxation process is found which is strongly broadened and asymmetric. It is assigned a local hindered rotation of the ester groups attaching the spacer to the discotic mesogen. This assignment is supported by NMR measurements on the identical substance.Dedicated to Prof. E. W. Fischer on the occasion of his 60th birthday.     

In situ vibrational spectroscopy of conducting polymer electrodes

The application of in situ Fourier transform infrared spectroscopy for the study of electrochemical redox reactions of conducting polymers is described. The experimental setup of two different methods, external reflection absorption spectroscopy and attenuated total reflection spectroscopy, is shown. The results of spectroelectrochemical investigations of the reactions of polyaniline in different electrolyte solutions are discussed.     

Local dielectric spectroscopy of near-surface glassy polymer dynamics

A noncontact scanning probe microscopy method was used to probe local near-surface dielectric susceptibility and dielectric relaxation in polyvinyl acetate near the glass transition. Dielectric spectra were measured from 10(-4) to 10(2) Hz as a function of temperature. The measurements probed a 20 nm thick layer below the free surface of a bulk film. A significant change in the fragility index and moderate narrowing of the distribution of relaxation times were found in the near-surface layer. In contrast to results for ultrathin films confined on or between metallic electrodes, no reduction in the dielectric strength was found, inconsistent with the immobilization of slower modes.     

Studies of polymer solvation by dielectric relaxation spectroscopy II: Polyethylene glycol in methyl pyrrolidone

Frequency domain dielectric spectroscopy (30 MHz to 72 GHz) is utilized to study solvation in polyethylene glycol (PEG) — methyl pyrrolidone (MPy) mixtures over the whole mixture range at 20 °C, in particular with PEG 200. Further pure PEGs (200 to 400) and butyl glycol (in the pure state and in benzene and n-hexane solution) are considered for comparison to facilitate the assessment of PEG relaxational behavior. It turns out that the PEG-MPy mixtures can be described in terms of a simple solvation model which takes into account only the bulk and the solvating solvent state. The solvation number per repeat unit is about 0.85 in the dilute solution limit. It decreases gradually with increasing PEG concentration in accordance with a solvation equilibrium model.     

Molecular dynamics of amorphous/crystalline polymer blends studied by broadband dielectric spectroscopy

The molecular dynamics of poly(vinyl acetate), PVAc, and poly(hydroxy butyrate), PHB, as an amorphous/crystalline polymer blend has been investigated using broadband dielectric spectroscopy over wide ranges of frequency (10⁻² to 10⁵ Hz), temperature, and blend composition. Two dielectric relaxation processes were detected for pure PHB at high and low frequency ranges at a given constant temperature above the T_g. These two relaxation peaks are related to the α and α′ of the amorphous and rigid amorphous regions in the sample, respectively. The α′-relaxation process was found to be temperature and composition dependent and related to the constrained amorphous region located between adjacent lamellae inside the lamellar stacks. In addition, the α′-relaxation process behaves as a typical glass relaxation process, i.e., originated from the micro-Brownian cooperative reorientation of highly constraints polymeric segments. The α-relaxation process is related to the amorphous regions located between the lamellar crystals stacks. In the PHB/PVAc blends, only one α-relaxation process has been observed for all measured blends located in the temperature ranges between the T_g’s of the pure components. This last finding suggested that the relaxation processes of the two components are coupled together due to the small difference in the T_g’s (ΔT_g = 35 °C) and the favorable thermodynamics interaction between the two polymer components and consequently less dynamic heterogeneity in the blends. The T_g’s of the blends measured by DSC were followed a linear behavior with composition indicating that the two components are miscible over the entire range of composition. The α′-relaxation process was also observed in the blends of rich PHB content up to 30 wt% PHB. The molecular dynamics of α and α′-relaxation processes were found to be greatly influenced by blending, i.e., the dielectric strength, the peak broadness, and the dielectric loss peak maximum were found to be composition dependent. The dielectric measurements also confirmed the slowing down of the crystallization process of PHB in the blends.     

Effect of curing on the broadband dielectric spectroscopy of powder coating

The effect of curing process of thermosetting powder coating consists of carboxylated polyester resin cured with triglycidyl isocyanurate has been investigated using broadband dielectric relaxation spectroscopy over a wide range of frequency (10⁻¹-10⁶ Hz) and temperature (70-105 °C) for different constant curing times. The molecular dynamics of the glass relaxation process (α-process) was investigated as a function of curing time, frequency, and temperature. It has been found that, only one common α-relaxation process has been observed for all measured samples of different degree of curing stages, its dynamics and broadness were found to be curing time dependent. In addition, the curing time dependence of the dielectric relaxation strength, Δε, has also been examined for the α and β-relaxation processes. The Δε for the two relaxation processes decreased strongly at the beginning of curing process and then became almost constant at longer curing times. This finding implied that the numbers of reoriented dipoles decrease with curing time as a result of the formation of three-dimensional polymer network. Furthermore, the dislocation energy, ε_s, calculated from the Meander model was found to be increased with increasing the curing time, i.e. the formation of a three-dimensional polymer network produces many structural defects or dislocation points. In addition, the activation energy of the curing process was calculated from the analysis of the calorimetric exothermic peaks of the curing process at different heating rates.     

Dynamics of water in partially crystallized polymer/water mixtures studied by dielectric spectroscopy

The dielectric relaxation process of water was investigated for polymer/water mixtures containing poly(vinyl methyl ether), poly(ethyleneimine), poly(vinyl alcohol), and poly(vinylpyrrolidone) with a polymer concentration of up to 40 wt % at frequencies between 10 MHz and 10 GHz in subzero temperatures down to -55 degrees C. These polymer/water mixtures have a crystallization temperature TC of water at -10 to -2 degrees C. Below TC, part of the water crystallized and another part of the water, uncrystallized water (UCW), remained in a liquid state with the polymer in an uncrystallized phase. The dielectric relaxation process of UCW was observed, and reliable dielectric relaxation parameters of UCW were obtained at temperatures of -26 to -2 degrees C. At TC, the relaxation strength, relaxation time, and relaxation time distribution change abruptly, and their subsequent changes with decreasing temperature are larger than those above TC. The relaxation strength of UCW decreases, and the relaxation time and dynamic heterogeneity (distribution of relaxation time) increase with decreasing temperature. These large temperature dependences below TC can be explained by the increase in polymer concentration in the uncrystallized phase C(p,UCP) with decreasing temperature. C(p,UCP) is independent of the initial polymer concentration. In contrast to the relaxation times above TC, which vary with the chemical structure of the polymer and its concentration, the relaxation times of UCW are independent of both of them. This indicates that the factor determining whether the water forms ice crystals or stays as UCW is the mobility of the water molecules.     

Non-linear dielectric response of a ferroelectric liquid crystal

Dielectric spectroscopy is a very useful method for investigation of the structure and dynamics of liquid crystals. However, with few exceptions, most investigations have been only in the linear regime. In this note we present a simple method for extraction of the non-linear contributions to the dielectric constant and as an example give the results obtained for a ferroelectric liquid crystal.     

Silicone-enriched surface of immersed polyurethane-POSS antifouling coating

Abstract

A series of waterborne polyurethane-polyhedral oligomeric silsesquioxane (WBPU-POSS) dispersions were synthesized. Different POSS contents were used to evaluate the effect of POSS content on silicone enrichment under both nonimmersed and immersed conditions. The impact of silicone enrichment under immersed conditions on antifouling properties was also evaluated. The structure of the WBPU-POSS coating was identified by FT-IR and ²⁹Si-NMR. X-ray photoelectron spectroscopy (XPS) analysis confirmed a silicone-enriched surface with a certain composition of the WBPU-POSS coating under both nonimmersed and immersed conditions. The mechanical properties, hydrophilicity and hydrolytic degradation of the coating all varied with POSS content. The long-term antifouling performance of immersed coatings depends on surface silicone enrichment, which was found to be above 0.0021?mole POSS content in WBPU-POSS coatings.     

Adsorption kinetics of ultrathin polymer films in the melt probed by dielectric spectroscopy and second-harmonic generation

We studied the adsorption kinetics of supported ultrathin films of dye-labeled polystyrene (l-PS) by combining dielectric spectroscopy (DS) and the interface-specific nonlinear optical second harmonic generation (SHG) technique. While DS is sensitive to the fraction of mobile dye moieties (chromophores), the SHG signal probes their anisotropic orientation. Time-resolved measurements were performed above the glass transition temperature on two different sample geometries. In one configuration, the l-PS layer is placed in contact with the aluminum surface, while in the other one, the deposition is done on a strongly adsorbed layer of neat PS. From the time dependence of the dielectric strength and SHG signal of the l-PS layer in contact with the metal, we detected two different kinetics regimes. We interpret these regimes in terms of the interplay between adsorption and orientation of the adsorbing labeling moieties. At early times, dye moieties get adsorbed adopting an orientation parallel to the surface. When adsorption proceeds to completeness, the kinetics slows down and the dye moieties progressively orient normal to the surface. Conversely, when the layer of l-PS layer is deposited on the strongly adsorbed layer of neat PS, both the dielectric strength and the SHG signal do not show any variation with time. This means that no adsorption takes place.     

Electrocatalytic and antifouling properties of CeO2-glassy carbon electrodes

Journal of Solid State Electrochemistry - Binary metal oxides with different degrees of covalent/ionic character of the oxygen-metal bond are tested as a partial coating of glassy carbon electrode...     

Soft mode and related behaviour in the SmA and SmC* phases of a ferroelectric liquid crystalline polymer by dielectric spectroscopy

Anomalous dielectric relaxation behaviour is observed in the ferroelectric liquid crystalline polymer (viz. ferroelectric copolysiloxane (R)-COPS 11-10) around the ferroelectric SmC* to paraelectric SmA phase transition. Measurements have been performed on sample of thickness ~10 mum in indium-tin-oxide coated cell in the frequency range 10 Hz to 13 MHz. With increase of temperature, a gradual shift of the soft mode frequency towards the higher frequency side was observed, while a decrease in the relaxation strength was seen with the corresponding increase in temperature. The shifts of the soft modes in the SmC* and SmA phase are considered to be due to change in the viscosity of the polymer, as an increase in viscosity increases fluctuations of the coupling between the dipoles in the network even far from the paraelectric-ferroelectric phase transition. Application of a bias field causes a shift of the critical frequency towards the higher frequency side, while the dielectric strength ( Δε) decreases under the bias field. The Cole-Cole fitting parameters obtained from the best fit of the dielectric constant data are found to be consistent with other similar materials. Another relaxation mode (molecular mode) was also observed which comes into play in both the smectic phases (SmC* and SmA) and contributes to the dielectric permittivity.     

Soft mode and related behaviour in the SmA and SmC* phases of a ferroelectric liquid crystalline polymer by dielectric spectroscopy

Anomalous dielectric relaxation behaviour is observed in the ferroelectric liquid crystalline polymer (viz. ferroelectric copolysiloxane (R)-COPS 11-10) around the ferroelectric SmC* to paraelectric SmA phase transition. Measurements have been performed on sample of thickness ～10 μm in indium-tin-oxide coated cell in the frequency range 10 Hz to 13 MHz. With increase of temperature, a gradual shift of the soft mode frequency towards the higher frequency side was observed, while a decrease in the relaxation strength was seen with the corresponding increase in temperature. The shifts of the soft modes in the SmC* and SmA phase are considered to be due to change in the viscosity of the polymer, as an increase in viscosity increases fluctuations of the coupling between the dipoles in the network even far from the paraelectric-ferroelectric phase transition. Application of a bias field causes a shift of the critical frequency towards the higher frequency side, while the dielectric strength (δε) decreases under the bias field. The Cole-Cole fitting parameters obtained from the best fit of the dielectric constant data are found to be consistent with other similar materials. Another relaxation mode (molecular mode) was also observed which comes into play in both the smectic phases (SmC% and SmA) and contributes to the dielectric permittivity.     

Molecular dynamics of oligofluorenes: a dielectric spectroscopy investigation

The molecular dynamics were investigated in a series of "defect-free" oligofluorenes up to the polymer by dielectric spectroscopy (DS). The method is very sensitive to the presence of keto "defects" that when incorporated on the backbone give rise to poor optical and electronic properties. Two dielectrically active processes were found (beta and alpha process). The latter process (alpha) displays strongly temperature dependent relaxation times and temperature- and molecular weight-dependent spectral broadening associated with intramolecular correlations. The glass temperature (Tg) obeys the Fox-Flory equation and the polymer Tg is obtained by DS at 332 K. The effective dipole moment associated with the alpha process is 0.27 +/- 0.03 D.     

A novel technique to measure the surface electrical potential of polymer films by using dielectric spectroscopy

A novel method that allows the determination of the electrical potential of a polymer surface has been applied for polypropylene film treated by N₂ + H₂ cold plasma. The plasma treatment results in formation on the film surface of NH₂ groups, which then gets transformed to NH₃⁺ in contact with an electrolyte and leads to the formation of an electrical double layer. The method consists of theoretical calculation of electrical model potential, using the measurement of the electrical capacitance of the film in contact with an electrolyte by dielectric spectroscopy. Comparison with the results obtained by theoretical model shows similar dependencies of the electrical potential as a function of amino‐groups density and electrolyte concentration, but systematic differences of absolute values are observed. Copyright © 2005 John Wiley & Sons, Ltd.     

Modeling electrode polarization in dielectric spectroscopy: Ion mobility and mobile ion concentration of single-ion polymer electrolytes

A novel method is presented whereby the parameters quantifying the conductivity of an ionomer can be extracted from the phenomenon of electrode polarization in the dielectric loss and tan delta planes. Mobile ion concentrations and ion mobilities were determined for a poly(ethylene oxide)-based sulfonated ionomer with Li(+), Na(+), and Cs(+) cations. The validity of the model was confirmed by examining the effects of sample thickness and temperature. The Vogel-Fulcher-Tammann (VFT)-type temperature dependence of conductivity was found to arise from the Arrhenius dependence of ion concentration and VFT behavior of mobility. The ion concentration activation energy was found to be 25.2, 23.4, and 22.3+/-0.5 kJmol for ionomers containing Li(+), Na(+), and Cs(+), respectively. The theoretical binding energies were also calculated and found to be approximately 5 kJmol larger than the experimental activation energies, due to stabilization by coordination with polyethylene glycol segments. Surprisingly, the fraction of mobile ions was found to be very small, <0.004% of the cations in the Li(+) ionomer at 20 degrees C.     

Studies of polymer solvation by dielectric relaxation spectroscopy I: polyvinyl pyrrolidone in propylene carbonate,dimethyl sulfoxide and tetramethyl urea

The dielectric relaxation behavior of the title solutions of PVP 40000 is measured in the frequency domain (50 MHz to 36 GHz) at 20 °C. The polymer content of the solutions (up to 0.25 mole fraction of monomer units) is such that it does not yet contribute significantly to dielectric loss. The solvent relaxation shows in all cases a bulk and a slowed down contribution, both characterized by concentration-independent relaxation times. The slow contribution is ascribed to the solvate. Solvation numbers for dilute solutions roughly range between 2 and 4 per PVP repeat unit.     

Dynamics of a supercooled ionic liquid studied by optical and dielectric spectroscopy

We have measured the dynamics of solvation of a triplet state probe, quinoxaline, in the glass-forming ionic liquid dibutylammonium formate near its glass transition temperature Tg=153 K. The Stokes-shift correlation function displays a relaxation time dispersion of considerable magnitude and the optical line width changes systematically along the solvation coordinate. The solvent dynamics in the viscous regime is compared with the rotational behavior of the solute and with the dielectric relaxation of the ionic liquid. Among the different quantities derived from the dielectric experiments, the relaxation of the macroscopic electric field, i.e., the modulus Mt, matches best the solvent response Ct regarding time scale and stretching exponent. Many other properties are reminiscent of the behavior of polar molecular liquids which lack the ionic character.     

The photooxidative degradation and stabilisation of water-borne acrylic coating systems

The influence of manufacturing and processing parameters on the photooxidative stability of aqueous acrylic based latices is examined by FTIR and hydroperoxide analysis. These are based on emulsion polymerised formulations of methyl methacrylate and butyl acrylate. Here acrylic latices based on different formulations are chosen as homo-polymers and copolymers. The nature of impurities and oxidation products generated during their manufacture are characterised and inter-related to their influence on subsequent photooxidative degradation. This involves the use of reflectance FT-IR spectroscopy to show functional group changes together with colourmetric U.V. analysis to determine the photochemical generation of hydroperoxides. The early chemical changes and their subsequent influence on the physical and chemical properties of the latices during the later stages of photooxidation are found to exhibit a close inter-relationship. To date the nature of the surfactant and the composition of the latex in terms of end group modification are important parameters. De-esterification and hydroperoxide formation are found to be important processes during latex photooxidation while the addition of low levels of co-monomer to the emulsion give latices with improved photostability. While co-reactive hindered piperidine stabilisers are found to be effective the incorporation of simple terminal dialkyl acrylamide/methacrylamide groups are equally as effective. Oxygen scavenging via the formation of alkylamino radicals is disussed.