Evolution of morphology,segmental dynamics,and conductivity in ionic liquid swollen short side chain perfluorosulfonate ionomer membranes

We investigate the morphology, segmental dynamics, and conductivity of 1‐ethyl‐3‐methylimidazolium trifluoromethanesulfonate (EMI‐Tf) swollen short side chain perfluorosulfonate ionomer (Aquivion) over a broad uptake range using small angle X‐ray scattering (SAXS), dielectric relaxation spectroscopy, and transient current measurement. The SAXS data indicate that the absorbed EMI‐Tf is mainly bounded in the ionic region of Aquivion. At low uptakes, EMI‐Tf acts as an effective plasticizer lowering the cluster T_g and markedly shifting the segmental relaxation to a high frequency; however, at high uptakes, the additional EMI‐Tf acts like a filler instead. A time–domain model was employed to quantify the conductivity of these membranes containing two mobile ion species, that is, cations and anions. The conductivity of both neat EMI‐Tf and EMI‐Tf swollen membranes exhibits Vogel‐Fulcher‐Tamman relation, revealing different activation parameters for ionic conduction. Furthermore, membranes containing different EMI‐Tf uptakes have similar conductivity over the reduced T_g/T axis and also follow Debye‐Stokes‐Einstein relation. Therefore, despite the abrupt change in conductivity near the critical uptake (29 wt %), both cluster T_g and segmental motion remain the key factors for the ionic conduction in these EMI‐Tf swollen membranes. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1273–1280     

Unusual relaxation process in polybutadiene: Resolving the controversy

We report the observation of an unusual relaxation process in depolarized light scattering spectra of polybutadiene (PBD) with two different vinyl contents. The process showed up in the gigahertz frequency range with relatively mild temperature dependence and was similar to a secondary relaxation process. The most surprising observation was that the process exists even at high temperatures and does not merge with the segmental relaxation up to a temperature of 400 K (T > 2T_g). Possible mechanisms of this particular relaxation in PBD are discussed. The process is compared to the so‐called E process, double‐bond hopping process, and dielectric β process. We emphasize that this process differs from the dielectric β process, is unique for 1,4‐PBD, and has not been observed in other polymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 994–999, 2004     

Molecular relaxation of isotactic polystyrene: Real‐time dielectric spectroscopy and X‐ray scattering studies*

The molecular relaxation processes and structure of isotactic polystyrene (iPS) films were investigated with real‐time dielectric spectroscopy and simultaneous wide‐ and small‐angle X‐ray scattering. The purpose of this work was to explore the restrictions imposed on molecular mobility in the vicinity of the α relaxation (glass transition) for crystallized iPS. Isothermal cold crystallization at temperatures of T_c = 140 or 170 °C resulted in a sigmoidal increase of crystallinity with crystallization time. The glass‐transition temperature (T_g), determined calorimetrically, exhibited almost no increase during the first stage of crystal growth before impingement of spherulites. After impingement, the calorimetric T_g increased, suggesting that confinement effects occur in the latter stages of crystallization. For well‐crystallized samples, the radius of the cooperativity region decreased substantially as compared with the purely amorphous sample but was always smaller than the layer thickness of the mobile amorphous fraction. Dielectric experiments directly probed changes in the amorphous dipole mobility. The real‐time dielectric data were fitted to a Havriliak–Negami model, and the time dependence of the parameters describing the distribution of relaxation times and dielectric strength was obtained. The central dipolar relaxation time showed little variation before spherulite impingement but increased sharply during the second stage of crystal growth as confinement occurred. Vogel–Fulcher–Tammann analysis demonstrated that the dielectric reference temperature, corresponding to the onset of calorimetric T_g, did not vary for well‐crystallized samples. This observation agreed with a model in which constraints affect primarily the modes having longer relaxation times and thus broaden the glass‐transition relaxation process on the higher temperature side. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 777–789, 2004     

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     

Synthesis and characterization of a series of wholly aromatic copolyesters containing 2‐(α‐phenylisopropyl)hydroquinone moiety

Two series of new wholly aromatic thermotropic copolyesters containing the 2‐(α‐phenylisopropyl)hydroquinone (PIHQ) moiety have been synthesized and their basic properties such as glass transition temperature (T_g), melting temperature (T_m), thermal stability, crystallinity, and liquid crystallinity were studied by differential scanning calorimetry (DSC), thermogravimetry (TG), and wide‐angle X‐ray diffractometry (WAXD) and on a polarizing microscope. The first series was prepared from acetylated PIHQ, terephthalic acid (TPA), and 2,6‐naphthalenedicarboxylic acid (NDA), and the second series from acetylated PIHQ, TPA, and 1,1′‐biphenyl‐4,4′‐dicarboxylic acid (BDA). The T_g values (152–168°C) of the two series are not much different, although the values for the first series appear slightly higher. The T_m values (287–378°C) and the degree of crystallinity of the first series are appreciably greater than those of the second series. Such differences can be explained by the geometric structure of NDA and BDA moieties. All of the present polyesters are thermotropic and nematic. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 881–889, 1999     

Effects of different composition ratio on the dielectric relaxation and dynamic mechanical properties of poly(ω‐dodecalactam‐co‐ε‐caprolactam‐co‐propylene oxide) copolymers

The molecular dynamics of new poly (ω‐dodecalactam‐co‐ε‐caprolactam‐co‐propylene oxide) copolymers (DL/CL/PAC) has been investigated by using dynamic mechanical thermal analysis (DMTA) and dielectric relaxation spectroscopy (DRS) measurements. The copolymers were synthesized via anionic polymerization of relevant lactams activated with carbamoyl derivatives of telechelic hydroxyl terminated polypropylene oxide with isophorone diisocyanate (PAC). The calorimetric, X‐ray diffraction, and DMTA measurements were performed to recognize the influence of the composition ratio and the type of PAC on the physical, thermal, and mechanical properties of the synthesized copolymers. The DRS was used to study the frequency dependence of the dielectric permittivity of some isotherms from ?110 to 145 °C. Copolymerization of ε‐caprolactam with about 10 wt % ω‐dodecalactam results in a copolymer that has lower water absorption, a melting point close to that of polyamide 6 and has a high enough degree of crystallinity in respect to high storage modulus. Five dielectric relaxations have been observed in the dielectric spectra, three at lower temperature and two at higher temperature. The copolymers have two glass transition temperatures for polyamide segments and polyether blocks, indicating microphase separation in the copolymers. Other studies directed toward molecular dynamics of polyamide DL/CL/PAC copolymers have not been reported. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010     

Segmental and secondary dynamics in hydrogen‐bonded poly(4‐vinylphenol)/poly(methyl methacrylate) blends

Broadband dielectric spectroscopy was used to study the segmental (α) and secondary (β) relaxations in hydrogen‐bonded poly(4‐vinylphenol)/poly(methyl methacrylate) (PVPh/PMMA) blends with PVPh concentrations of 20–80% and at temperatures from ?30 to approximately glass‐transition temperature (T_g) + 80 °C. Miscible blends were obtained by solution casting from methyl ethyl ketone solution, as confirmed by single differential scanning calorimetry T_g and single segmental relaxation process for each blend. The β relaxation of PMMA maintains similar characteristics in blends with PVPh, compared with neat PMMA. Its relaxation time and activation energy are nearly the same in all blends. Furthermore, the dielectric relaxation strength of PMMA β process in the blends is proportional to the concentration of PMMA, suggesting that blending and intermolecular hydrogen bonding do not modify the local intramolecular motion. The α process, however, represents the segmental motions of both components and becomes slower with increasing PVPh concentration because of the higher T_g. This leads to well‐defined α and β relaxations in the blends above the corresponding T_g, which cannot be reliably resolved in neat PMMA without ambiguous curve deconvolution. The PMMA β process still follows an Arrhenius temperature dependence above T_g, but with an activation energy larger than that observed below T_g because of increased relaxation amplitude. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3405–3415, 2004     

Vibrational spectroscopy analysis of ion conduction mechanism in dispersed phase polymer nanocomposites

A novel combination of dispersed phase polymer nanocomposite electrolyte based on PEO₈‐LiClO₄+ x wt % nano‐CeO₂ has been investigated. A model for ion transport mechanism has been proposed to account for substantial enhancement of its electrical conductivity by ～ 2 orders of magnitude at low volume fraction of the filler reinforcement in the polymer nanocomposite films. The strength of the proposed model is based on unambiguous evidences from FTIR, TEM, and conductivity analysis. The FTIR results provide clear role of nanofiller concentration on ion–ion interaction quantified in terms of the fraction of free anion and ion‐pairs present in the nanocomposite films and its excellent correlation with conductivity versus filler concentration. The presence of asymmetry in the ν₄(ClO₄^?) band observed at 625 cm^?1 is attributed to its resolved degeneracy suggesting the presence of both uncoordinated and cation‐coordinated ClO₄^? anion in the matrix due to ion–ion and ion–filler interactions assisted by Lewis acid–base interaction. The enhancement in conductivity at low concentration is possibly due to direct interaction of nano‐CeO₂ with both polymer host and anions resulting in the release of ionic charges. Drastic conductivity reduction at higher concentration is related to charge immobilization because of ion/ion‐pair entrapment by local clusters of filler as evidenced in TEM. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 60–71, 2009     

Dynamics in disordered block copolymers and miscible blends composed of poly(vinyl ethylene) and polyisoprene

We investigated the segmental and terminal relaxation dynamics of a well‐characterized disordered diblock copolymer, poly(isoprene‐b‐vinyl ethylene) (PI‐PVE), and miscible blends of polyisoprene (PI)/poly(vinyl ethylene) (PVE), using dielectric and viscoelastic spectroscopies. Generally, the concentration fluctuation (CF) amplitude of a disordered diblock copolymer is smaller than that of the miscible blend, especially in a length scale longer than the size of the whole block chain. To test whether the difference in the CF amplitudes causes the difference in the segmental relaxation spectra, we compared the shape of the dielectric loss curves between PI‐PVE and PI/PVE with the same composition (PI/PVE ratio = 17:83). However, no appreciable difference was observed, indicating that the CF amplitudes in PI‐PVE and PI/PVE are not so different in the length scale of the segmental motions. We also examined the effect of distinct friction coefficients of the PI and PVE chains on the terminal relaxation dynamics by comparisons of the viscoelastic and dielectric normal mode relaxations in PI‐PVE. The former probes the whole chain motion and the latter probes motions of the PI block. Shift factors (a_T) for the viscoelastic and dielectric relaxations were compared. The dielectric normal mode a_T was found to have weaker temperature dependence than the viscoelastic a_T, which indicates that the friction for the PI block chain is lower than the average friction for the PI‐PVE chain. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4084–4094, 2004     

Dielectric relaxation of poly(phenylene sulfide) containing a fraction of rigid amorphous phase

The dielectric relaxation behavior of poly(phenylene sulfide), PPS, has been investigated from room temperature to 180°C. This study was undertaken to examine the mobility of the amorphous phase through the glass transition region, to determine the contribution that rigid amorphous phase material makes to the relaxation process. Semicrystalline samples contain a fraction of the rigid amorphous phase, which was determined from the heat capacity increment at the glass transition, using degree of crystallinity determined from x-ray scattering. In the dielectric experiment, we measured the temperature and frequency dependence of the real and imaginary parts of the dielectric function. ε″ vs. ε′ was used to determine the dielectric relaxation intensity, δε = ε_s–ε∞, at temperatures above the glass transition. For amorphous PPS, δε decreases as temperature increases, while for all semicrystalline PPS, δε increases with temperature. The ratio of semicrystalline intensity to amorphous intensity determines the total fraction of dipoles which are already relaxed at a given temperature. Results indicate that more and more rigid amorphous phase material relaxes as the temperature is increased. This provides the first evidence that rigid amorphous phase material in PPS contains chains that possess different levels of molecular mobility. Finally, to the temperature of the loss peak maximum, at a given frequency, we assign the value of the dielectric T_g. For both melt and cold crystallization, the dielectric T_g systematically decreases as the crystallization temperature increases, and as the fraction of rigid amorphous phase decreases.     

Relaxor type perovskites: Primary candidates of nano-polar regions

Relaxor properties of 0.7Pb(Mg_1/3Nb_2/3)O₃-0.3PbTiO₃ (PMN-PT) and non-lead perovskite thin films have been analysed in terms of large frequency dispersion of dielectric response at low temperatures. A wide spectrum of dielectric relaxation was observed in the frequency-dependent response of the imaginary part of the dielectric permittivity. Transformation from normal ferroelectric to relaxor behaviour has been observed in the case of the Ca substituting the BaTiO₃ thin films. A number of techniques were exploited to investigate the wide spectrum of relaxation times in pulsed laser ablated thin films.ac anddc electric field induced complex dielectric properties of 0.7Pb(Mg_1/3Nb_2/3)O₃-0.3PbTiO₃ (PMN-PT) thin films were studied as function of frequencies at different temperatures. Nonlinear behaviour of dielectric susceptibility with respect to the amplitude of theac drive was observed at lower temperatures. The frequency dependence of transition temperatureT _m (temperature of the maximum of dielectric constant) was studied using the Vogel-Fulcher relation. Dedicated to Professor C N R Rao on his 70th birthday     

Rheological properties of ferrite nanocomposites based on nylon‐66

Effects of ferrite nanoparticles (0.1–20 wt %) on the rheological and other physical properties of nylon‐66 were investigated. The presence of ferrite nanoparticles less than 1 wt % increased the crystallization temperature (T_c) by 4.2 °C with ferrite content, but further addition decreased T_c. The onset temperature of degradation was increased by 7.3 °C at only 0.1 wt % loading of ferrite, after which the thermal stability of nylon‐66 was decreased with ferrite content. The incorporation of ferrite nanoparticles more than 5 wt % increased the dynamic viscosity (η′) with the loading level. Further, it produced notably shear thickening behavior in the low frequency, after which high degree of shear thinning was followed with ferrite content. In the Cole–Cole plot, the nanocomposites with ferrite lower than 5 wt % presented a single master curve, while further addition gave rise to a deviation from the curve. The relaxation time (λ) was increased with ferrite content and the difference of λ between nylon‐66 and its nanocomposite was greater at lower frequency. The tensile strength was a little increased up to 1 wt % loading, after which it was decreased with increasing the loading level. In addition, the introduction of the nanoparticles increased tensile modulus and decreased the ductility with ferrite content. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 371–377, 2006     

Dielectric relaxations of chitosan: The effect of water on the α‐relaxation and the glass transition temperature

In this work thermal relaxations of chitosan are reported by using a novel methodology that includes subtraction of the dc conductivity contribution, the exclusion of contact and interfacial polarization effects, and obtaining a condition of minimum moisture content. When all these aspects are taken into account, two relaxations are clearly revealed in the low frequency side of the impedance data. We focus on the molecular motions in neutralized and non‐neutralized chitosan analyzed by dielectric spectroscopy in the temperature range from 25 to 250 °C. Low and high frequency relaxations were fitted with the Havriliak and Negami model in the 10^?1 to 108 Hz frequency range. For the first time, the low frequency α‐relaxation associated with the glass‐rubber transition has been detected by this technique in both chitosan forms for moisture contents in the range 0.05 to 3 wt % (ca. 18–62 °C). A strong plasticizing effect of water on this primary α‐relaxation is observed by dielectric spectroscopy and is supported by dynamic mechanical analysis measurements. In the absence of water (<0.05 wt %) the α‐relaxation is obscured in the 20–70 °C temperature range by a superposition of two low frequency relaxation processes. The activation energy for the σ‐relaxation is about 80.0–89.0 kJ/mol and for β‐relaxation is about 46.0–48.5 kJ/mol and those values are in agreement with that previously reported by other authors. The non‐neutralized chitosan possess higher ion mobility than the neutralized one as determined by the frequency location of the σ‐relaxation. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 2259–2271, 2009     

Double‐helical network in amylose as seen by slow calorimetry and FTIR

The phase content and crystallinity of initially amorphous amylose–water mixtures (70/30 W/W) have been changed by slow cycles of dissolution and recrystallization from T_max with 50 °C < T_max < 120 °C. Analysis of the treatment‐induced changes is made by X‐ray diffraction, FTIR, fast T‐ramp DSC and slow calorimetry. Our interest was to follow the relaxation of the network phase and its consequence on the growth of crystallinity. The DSC technique, which gives the temperature of disappearance of long‐range order, is unable to quantitatively follow the growth of crystallinity achieved by treating the samples. In highly interactive polymer–solvent systems, order is unmeltable in a fast T‐ramp due to strain developed during the ramp. In a 6 K/h T‐ramp, the order becomes meltable and grows from 21 J/g to 147 J/g when T_max increases. The other conclusion is that strain‐melting and the network phase, characterized first in polyolefins has a more prominent role in the characterization of H‐bonded polysaccharide–water mixtures. Correlation is achieved between the concentration of bands in the C O stretching region, the fraction of single and double helices, and the three endotherms found on the slow T‐ramp dissolution traces. FTIR spectra show that chains in the network cannot be disentangled by quenching but can be organized during a slow cooling. The B and V crystalline modifications are observed in the treated samples. Quenched treated amylose and enzyme‐resistant amylose seem to contain a comparable amount of double‐helical/strainable fraction. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1662–1677, 2000     

Dielectric properties of sols of silver nanoparticles capped by alkyl carboxylate ligands

Sols of silver nanoparticles in toluene were studied by broadband dielectric spectroscopy (10⁻³–10⁵ Hz). The frequency dependences of the specific alternating current (ac) conductivity and the complex electric modulus were used to estimate the temperature/frequency intervals of long- and short-range charge transfer occurs, respectively. A considerable increase (by more than 30 °C) in the Vogel temperature T ₀ and the glass transition temperature T _g in sols compared with the pure solvent was found. It can be hypothesized that these cooperative effects reflect the initial stage of the superlattice formation. Although the dielectric characteristics of sols are generally controlled by the conductivity relaxation, the dielectric response was observed in the high-frequency range (1–10³ Hz) at low temperatures (from −50 to +10 °C). This response results from the presence of nanoparticles in solution. It is supposed that the relaxation is caused by the motion of ion impurities on the Ag nanoparticle surface within the carboxylate ligands shell. The dielectric properties of films strongly depend on both the characteristics of nanoparticles and the conditions of the film preparation. Like in sols, the direct current (dc) conductivity and the dielectric response of Ag nanoparticles in films are due to ion impurities.     

35Cl NQR studies of 1‐chloro‐2,4‐dinitrobenzene and 1,2‐dichloro‐3‐nitrobenzene as a function of pressure and temperature

The temperature and pressure dependences of ³⁵Cl nuclear quadrupole resonance (NQR) frequency and spin–lattice relaxation time (T₁) were investigated for 1‐chloro‐2,4‐dinitrobenzene and 1,2‐dichloro‐3‐nitrobenzene. T₁ was measured in the temperature range 77–300 K. Furthermore, the NQR frequency (ν) and T₁ for these compounds were measured as a function of pressure up to 5.1 kbar at 300 K. Relaxation was found to be due to the torsional motion of the molecule and the reorientation motion of the nitro group. By analysing the temperature dependence of T₁, the activation energy for the reorientation motion of the nitro group was obtained. The temperature dependence of the average torsional lifetimes of the molecules and the transition probabilities W₁ and W₂ for the Δm = ±1 and Δm = ±2 transitions, were also obtained. Both compounds showed a non‐linear variation of NQR frequency with pressure. The pressure coefficients were observed to be positive. A thermodynamic analysis of the data was carried out to determine the constant‐volume temperature coefficients of the NQR frequency. The spin–lattice relaxation time T₁ for both the compounds was found to be weakly dependent on pressure, showing that the relaxation is mainly due to the torsional motions. Copyright © 2002 John Wiley & Sons, Ltd.     

Temperature‐dependent fluorescence from pyrenyl‐modified polyethylene films. A comparison of attachment methods and morphology changes by irradiation with eV‐range photons and bombardment with MeV‐range positive ions

1‐Pyrenyl groups were attached covalently to three polyethylene ( Py–PE ) films with different crystallinities by irradiating (eV‐range photons–UV‐photons) or by bombarding (MeV‐range ions–protons and alpha particles) pyrene‐doped PE films ( Py/PE ). Onset temperatures of relaxation processes (T_x) of the Py–PE were approximated from (1) Arrhenius‐type plots of the normalized integrated intensities of the films and (2) the temperature dependence of the full‐width half‐maximum (FWHM) films and the position of the 0–0 fluorescence band. DSC thermograms of the native and irradiated or bombarded films were also compared to independently assess the morphological changes. The onset temperatures T_x in lower crystallinity Py–PE films were more difficult to locate when prepared by bombardment with high doses than with low doses of photons or ions or by irradiation. The ease of locating the T_x in higher crystallinity Py–PE films was independent of dose, suggesting little change in the mobility in the vicinity of pyrenyl probes. Fluorescence from Py–PE bombarded with alpha particles indicated the presence of both singly‐ and doubly‐attached pyrenyl groups. The singly‐attached pyrenyl groups were less sensitive than the doubly attached to the T_x. Py–PE films were more sensitive luminescence reporters of T_γ segmental motions than were 9‐anthryl groups covalently attached to the same polymers. We also discuss possible reasons why the values of the activation energies for the relaxation processes, as calculated from the Arrhenius plots, were much smaller than those based on the dynamic mechanical methods. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2957–2970, 2004     

Correlation between dipolar TSDC and AC dielectric spectroscopy at the PVDF glass transition

The α_a-mode (associated to the dynamic glass transition) in PVDF-α has been studied by Thermally Stimulated Depolarization Currents (TSDC) and Dielectric Spectroscopy (DS) techniques. The distribution of relaxation parameters, reorientation energies, characteristic temperature, and preexponential factors of the Vogel–Tammann–Fulcher relaxation times have been precisely determined by using the Simulated Annealing Direct Signal Analysis applied to a partially discharged TSDC α_a peak. This distribution has been used to predict the variation of the dielectric loss, ε″(ω, T), in the temperature and frequency range where the DS measurements were made on the same material. The simulated ε′(T, ω) for various ω, are compared to the experimental values. The width of the peak is always too low, due to the restricted distribution used for the generation of the curves. A relaxation map including the TSDC results is used to determine the relaxation time variation. In the limited frequency range where the AC DS experiments are performed (10² ≤ f ≤ 10⁵ Hz) a master curve is drawn and the exponents of the frequency dependence are found at low and high frequency; also, a fitting to the Havriliak–Negami distribution is successfully performed. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 2483–2493, 1997