The nearly constant loss,Johari‐Goldstein β‐relaxation,and α‐relaxation of 1,4‐polybutadiene

From high‐resolution dielectric spectroscopy measurements on 1,4‐polybutadiene (1,4‐PB), we show that in addition to the structural α‐relaxation and higher frequency secondary relaxations in the spectra, a nearly constant loss (NCL) is observed at shorter times/lower temperatures. The properties of this NCL are compared to those of another chemically similar polymer, 1,4‐polyisoprene. The secondary relaxations in 1,4‐PB include the well‐known Johari‐Goldstein (JG) β‐relaxation and two other higher‐frequency peaks. One of these, referred to as the γ‐relaxation, falls between the JG‐relaxation and the NCL. Seen previously by others, this γ‐relaxation in 1,4‐PB is not the JG‐process and bears no relation to the glass transition. At very low temperatures (<15 K), we confirm the existence of a very fast secondary relaxation, having a weak dielectric strength and an almost temperature‐invariant relaxation time. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 342–348, 2007     

Relaxations in chitin: Evidence for a glass transition

Relaxations in chitin have been investigated in the temperature range 298–523 K using impedance spectroscopy in the frequency range 10⁻¹–10⁸ Hz. The objective was to detect a glass‐transition temperature for this naturally occurring, semicrystalline polysaccharide. The impedance study was complemented with X‐ray diffraction, thermogravimetric, and differential scanning calorimetry measurements. Preliminary impedance data treatment includes the subtraction of the dc conductivity contribution, the exclusion of contact and interfacial polarization effects, and obtaining a condition of minimum moisture content for further analysis. When all these aspects are taken into account, two relaxations are clearly revealed in the impedance data. For the first time, evidence is presented for a relaxation process, which exhibits a non‐Arrhenius temperature dependence, in dry α‐chitin (∼0.1% moisture content), and likely represents the primary α‐relaxation. This evidence suggests a glass transition temperature for chitin of 335 ± 10 K estimated on the basis of the temperature dependence of the conductivity and of the relaxation time. A second relaxation in dry α‐chitin, not previously reported in the literature, is observed from 353 K to the onset of thermal degradation (∼483 K) and is identified as the σ‐relaxation often associated with proton mobility. It exhibits a normal Arrhenius‐type temperature dependence with activation energy of 113 ± 3 kJ/mol. The latter has not been previously reported in the literature. A high frequency secondary β‐relaxation is also observed with Arrhenius activation energy of 45 ± 1 kJ/mol. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 932–943, 2009     

Influence of oxycycloaliphatic groups in the relaxation behavior of acrylic polymers

A comparative study on the mechanical and dielectric relaxation behavior of poly(5‐acryloxymethyl‐5‐methyl‐1,3‐dioxacyclohexane) (PAMMD), poly(5‐acryloxymethyl‐5‐ethyl‐1,3‐dioxacyclohexane) (PAMED), and poly(5‐methacryloxymethyl‐5‐ethyl‐1,3‐dioxacyclohexane) (PMAMED) is reported. The isochrones representing the mechanical and dielectric losses present prominent mechanical and dielectric β relaxations located at nearly the same temperature, approximately −80°C at 1 Hz, followed by ostensible glass–rubber or α relaxations centered in the neighborhood of 27, 30, and 125°C for PAMMD, PAMED, and PMAMED, respectively, at the same frequency. The values of the activation energy of the β dielectric relaxations of these polymers lie in the vicinity of 10 kcal mol⁻¹, ∼ 2 kcal mol⁻¹ lower than those corresponding to the mechanical relaxations. As usual, the temperature dependence of the mean‐relaxation times associated with both the dielectric and mechanical α relaxations is described by the Vogel–Fulcher–Tammann–Hesse (VFTH) equation. The dielectric relaxation spectra of PAMED and PAMMD present in the frequency domain, at temperatures slightly higher than T_g, the α and β relaxations at low and high frequencies, respectively. The high conductive contributions to the α relaxation of PMAMED preclude the possibility of isolating the dipolar component of this relaxation in this polymer. Attempts are made to estimate the temperature at which the α and β absorptions merge together to form the αβ relaxation in PAMMD and PAMED. Molecular Dynamics (MD) results, together with a comparative analysis of the spectra of several polymers, lead to the conclusion that flipping motions of the 1,3‐dioxacyclohexane ring may not be exclusively responsible for the β‐prominent relaxations that polymers containing dioxane and cyclohexane pendant groups in their structure present, as it is often assumed. The diffusion coefficient of ionic species, responsible for the high conductivity exhibited by these polymers in the α relaxation, is semiquantitatively calculated using a theory that assumes that this process arises from MWS effects, taking place in the bulk, combined with Nernst–Planckian electrodynamic effects, due to interfacial polarization in the films. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2486–2498, 1999     

Interpretation of the TSDC fractional polarization experiments on the α‐relaxation of polymers

We report on the interpretation of the thermally stimulated depolarization current (TSDC) experiments, with partial polarization methods, on the dielectric α‐relaxation. The results obtained on polyvinyl acetate are rationalized on the basis of the Boltzmann superposition principle in combination with a Kohlrausch–Williams–Watts (KWW) time decay of the polarization (with the β exponent essentially temperature independent and equal to the value determined by conventional dielectric methods at T_g). From this analysis of the global TSDC spectrum we found a complex temperature dependence of the KWW relaxation time, which is Arrhenius‐like at the lowest temperatures but crosses over to the Vogel–Fulcher behavior observed above T_g in the temperature range of the TSDC peak. On the basis of these results, we found the way of predicting the TSDC spectra measured after partial polarization procedures. We found that, the distribution of activation energies and compensation behavior deduced by following the standard way of analysis are associated to the assumption of an Arrhenius‐like temperature dependence of the α‐relaxation time in the temperature range explored by TSDC. Therefore we conclude that both the distribution of activation energies and compensation behavior obtained by following the standard way of analysis do not give a proper physical picture of the α‐relaxation of glassy polymers around the glass‐transition temperature. Our results also show that the partial polarization TSDC methods are not able to give insight about the actual existence or not of a distribution of relaxation times at the origin of the nonexponentiality of the α‐relaxation of polymers. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2105–2113, 2000     

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     

Dielectric relaxation processes in epoxy resin—ZnO composites

Polymer matrix‐ZnO microcomposites were prepared in different filler concentrations. The electrical relaxation dynamics of all samples was examined by means of broadband dielectric spectroscopy (BDS) over a wide temperature range. Two relaxation modes (namely β and γ), observed in the low temperature region, are attributed to the reorientation of small polar groups of the polymer matrix. Glass‐rubber transition (α‐mode) of the polymeric matrix and interfacial polarization phenomena are considered as responsible for the recorded relaxation processes in the high temperature region. An additional relaxation mode, named intermediate dipolar effect (IDE), is recorded at temperatures higher than ?30 °C in all composites. Its occurrence and dynamics are related to the presence and concentration of the filler. IDE and α‐relaxation are observed in the same frequency and temperature range, leading to a mutual superposition. The two processes were distinguished following a simulation procedure employing the simultaneous fitting of two Havrilliak‐Negami terms and a third term describing the contribution of DC conductivity to dielectric losses. The temperature dependence of relaxation times for α‐mode follows the Vogel‐Tamann‐Fulcher equation, whereas IDE relaxation times follow unusual temperature dependence. The latter is discussed under the assumption of intrinsic interfacial polarization phenomena within ZnO crystal domains. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 445–454, 2009     

Segmental‐ and normal‐mode dielectric relaxation of poly(propylene glycol) under pressure

Dielectric measurements were obtained on poly(propylene glycol) (molecular weight: 4000 Da) at pressures in excess of 1.2 GPa. The segmental (α process) and normal‐mode (α′ process) relaxations exhibited different pressure sensitivities of their relaxation strengths, as well as their relaxation times. Such results are contrary to previous reports, and (at least for the dielectric strength) can be ascribed to the capacity for intermolecular hydrogen‐bond formation in this material. With equation‐of‐state measurements, the relative contributions of volume and thermal energy to the α‐relaxation times were quantified. Similar to other H‐bonded liquids, temperature is the more dominant control variable, although the effect of volume is not negligible. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 3047–3052, 2003     

Dipolar motions and phase transitions in a side‐chain polysiloxane liquid crystal. A study by thermally stimulated depolarization currents

The relaxation mechanisms present in a side‐chain liquid crystalline polymer have been studied by Thermally Stimulated Depolarization Currents (t.s.d.c.), in a wide temperature range covering the glassy state, the glass transition region, and the liquid crystalline phase. The thermal sampling procedure was used to decompose the complex relaxations into its narrowly distributed components. Three relaxation mechanisms were observed in this polymer: a relaxation below the glass transition temperature that is broad and extends from −150°C up to −110°C, the glass transition relaxation whose maximum intensity appears at ∼20°C, and a relaxation above the glass transition temperature, in the liquid crystalline phase. The attribution of these relaxations at the molecular level is discussed. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 227–235, 1999     

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     

Relaxations during the postcure of unsaturated polyester networks by ultrasonic wave propagation,dynamic mechanical analysis,and dielectric analysis

Ultrasonic wave propagation, dynamic mechanical analysis, and dielectric analysis were used to monitor relaxation phenomena during the nonisothermal postcure of unsaturated polyester networks. The measurements covered 6 decades of frequency. As a result, the residual reactive groups, immobilized in the glassy state by vitrification during an isothermal cure step, gained molecular mobility, which promoted the formation of additional crosslinks. After the postcure, the reaction was complete, and the maximum achievable glass‐transition temperature was reached. Moreover, the frequency and temperature dependence of the two relaxations, one related to the glass‐transition temperature of the partially cured sample and the other to the glass transition of the fully cured sample, was evaluated. The Williams–Landel–Ferry equation was used to model the frequency dependence of the main α‐relaxation data obtained with the different techniques. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 596–602, 2005     

Evidence for the γ‐relaxation in the light scattering spectra of poly (n‐hexyl methacrylate) near the glass transition

The full range of relaxation processes present in optically pure poly‐(n‐hexyl methacrylate) (PHMA) was studied using Rayleigh–Brillouin and photon correlation spectroscopy (PCS). Brillouin shifts, linewidths, and Landau–Placzek ratios (LPR) were measured over the temperature range from ?11 to 21 °C. The Brillouin splitting and linewidth were consistent with previous studies of PHMA, but the LPR was much lower, indicating that the scattered light primarily comes from intrinsic density fluctuations. Relaxation functions of the same PHMA sample were measured using PCS over the temperature range 0.5–52.5 °C. The average relaxation times calculated from a Williams–Watts fit follow a VFT temperature dependence, with the stretching parameter β decreasing with decreasing temperature. The distribution of relaxation times reveals a merging of the α and β‐relaxations over this temperature range, and the temperature dependent width confirms that there are at least two processes with separate temperature dependences. Furthermore, there appears a process at short times in the correlation function window at low temperatures. This upturn at the fastest relaxation times is attributed to the γ‐relaxation present in higher order methacrylate polymers. The effect of the γ‐relaxation is discussed in terms of the dynamic behavior over 12 decades in time. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1504–1519, 2005     

Dynamic mechanical and dielectrical properties of poly(vinyl alcohol) and poly(vinyl alcohol)‐based nanocomposites

In this article we report on the investigation of the dynamics of poly(vinyl alcohol) (PVA) and PVA‐based composite films by means of dielectric spectroscopy and dynamic mechanical thermal analysis. Once the characterization of pure PVA was done, we studied the effect of a nanostructured magnetic filler (nanosized CoFe₂O₄ particles homogeneously dispersed within a sulfonated polystyrene matrix) on the dynamics of PVA. Our results suggest that the α‐relaxation process, corresponding to the glass transition of PVA, is affected by the filler. The glass‐transition temperature of PVA increases with filler content up to compositions of around 10 wt %, probably as a result of polymer–filler interactions that reduce the polymer chain mobility. For filler contents higher than 10 wt %, the glass‐transition temperature of PVA decreases as a result of the absorption of water that causes a plasticizing effect. The β‐ and γ‐relaxation processes of PVA are not affected by the filler as stated from both dynamic mechanical thermal analysis and dielectric spectroscopy. Nevertheless, both relaxation processes are greatly affected by the moisture content. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 1968–1975, 2001     

Molecular motion and relaxation studies of aliphatic polyureas by thermal windowing thermally stimulated depolarization current technique

Molecular motion and relaxation studies using a thermal windowing thermally stimulated depolarization current (TW‐TSDC) were performed for aliphatic polyureas 7 and 9. Global thermally stimulated depolarization current gave three characteristic major peaks corresponding to the α, β, and γ relaxation modes at 78.5, −44, and −136°C for polyurea 7 and at 80, −50, and −134°C for polyurea 9, respectively. The α relaxation is related to the large‐scale molecular motion due to micro‐Brownian motion of long‐range segments. This relaxation is significantly related to the glass‐transition temperature. The β relaxation is caused by the local thermal motion of long‐chain segments. The γ relaxation is caused by the limited local motion of hydrocarbon sections. Temperature dependence of relaxation times was expressed well using Vogel–Tammann–Fulcher (VTF) expression. 3‐D simulation of dielectric constants of dielectric strength and loss factor were performed in the frequency range from 10⁻⁶ to 10⁴ Hz and temperature range from −150 to 250°C, using the relaxation parameters obtained from the TW‐TSDC method. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 88–94, 2000     

Dielectric and thermal characterization of low density ethylene/10‐undecen‐1‐ol copolymers prepared with nickel catalysts

Ethylene and 10‐undecen‐1‐ol copolymers, prepared using a nickel complex as catalyst, were studied using differential scanning calorimetry (DSC), X‐ray diffraction, and dielectric relaxation spectroscopy. The behavior exhibited by copolymers containing incorporated 10‐undecen‐1‐ol amounts within 0.5 and 4.6 mol % was compared with neat polyethylene. DSC revealed that a new crystalline region with lower thickness lamellae emerges in copolymers due to the side‐chains crystallization. Nevertheless, the global crystallization degree decreases due to the loss of crystallinity that occurs in a greater extent in PE‐like regions. Dielectric relaxation spectroscopy detected two processes, a low activation energy process below ?20 °C related with localized mobility increasing in intensity and deviating to higher temperatures with the increase in 10‐undecen‐1‐ol amount, and a high activation energy process ascribed to the glass transition, located at higher temperatures for the different copolymers relatively to neat polyethylene. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2802–2812, 2007     

Relaxation behavior of acrylate and methacrylate polymers containing dioxacyclopentane rings in the side chains

The synthesis of poly[(2,2‐dimethyl‐1,3‐dioxolan‐4‐yl) methyl acrylate)] (PACGA) and poly[(2,2‐dimethyl‐1,3‐dioxolan‐4‐yl) methyl methacrylate] (PMCGA) is reported. Both polymers present dielectric and mechanical β subglass absorptions at −128 and −115 °C, respectively, at 1 Hz, followed by ostensible glass–rubber or α relaxations centered in the vicinity of 0 and 67 °C, respectively, at the same frequency. The values of the activation energy of both the mechanical and dielectric β absorptions lie in the vicinity of 10 kcal mol⁻¹. The critical interpretation of the relaxation behavior of PMCGA suggests that dipolar intramolecular correlations play a dominant role in the response of the polymer to an electric field. The subglass relaxations of PACGA and PMCGA are further compared with the relaxation behavior of poly(1,3‐dioxane acrylate), poly(1,3‐dioxane methacrylate), and other polymers in the glassy state. The strong conductive processes observed in PMCGA at low frequencies and high temperatures were studied under the assumption that that these processes arise from Maxwell–Wagner–Sillars effects occurring in the bulk combined with Nernst–Planckian electrodynamic effects caused by interfacial polarization in the films. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 39: 286–299, 2001     

Molecular and collective relaxations of ferroelectric side chain liquid crystalline polysiloxanes

The influences of mesogenic group chemical structures on dielectric relaxation behavior were investigated for ferroelectric side chain liquid crystalline polymers (FLCPs). The relaxation time and activation energies of the Goldstone mode, α‐, and β‐relaxations decrease with increasing spacer length because of the plasticizer effect of the spacer. Moreover, the relaxation intensity increases with increasing spacer length for FLCPs. An FLCP with a longer spacer length exhibits a higher mesogenic group mobility, and subsequently leads to easier reorientation toward the alternating electrical field. An increase in mesogenic core rigidity results in an increase in the relaxation time and activation energies, and a decrease in the relaxation intensities for the Goldstone mode, α‐, and β‐relaxations. Moreover, the β‐relaxation is suppressed and cannot be observed in the glassy state for FLCPs containing naphthyl biphenylcarboxylate as the mesogenic group. Shorter relaxation time, smaller activation energies, and higher intensity of the α‐, and β‐relaxations were obtained for FLCPs containing chiral moiety with a flexible heptyl alkyl chain. However, the relaxation intensity of the Goldstone mode for FLCPs containing this chiral moiety was smaller than that for FLCPs containing the chiral moiety with a butyl alkyl chain. For FLCPs containing a chiral moiety with two asymmetrical centers, their Goldstone mode relaxation showed larger amplitude. The α‐ and β‐relaxations are suppressed for these FLCPs because of the dense packing and memory effect of the smectic phase. The relationship between the chemical structure of the mesogenic group and dielectric relaxations is discussed in great detail. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2035–2049, 2006     

Relaxation behavior of aliphatic-aromatic poly(ether amide)s as revealed by dynamic mechanical and dielectric methods

The mechanical and dielectric relaxation of a set of aromatic-aliphatic polyamides containing ether linkages have been examined as a function of temperature (−140 to 190°C) and frequency (3 to 10⁶ Hz). The polymers differ in the orientation (meta and para) of the aromatic rings, in the length of the aliphatic chain, and in the number of ether linkages per repeating unit. Dynamic mechanical experiments showed three main relaxation peaks related to the glass transition temperature of the polymers (α relaxation), the subglass relaxations associated to the absorbed water molecules (β) and to the motion of the aliphatic moieties (γ). Dielectric experiments showed two subglass relaxation processes (β and γ) that correlates with the mechanical β and γ relaxations, and a conduction process (σ) above 50°C that masks the relaxation associated to the glass transition. A molecular interpretation is attempted to explain the position and intensity of the relaxation, studying the influence of the proportion of para- or meta- oriented phenylene rings, the presence of ether linkages and the length of the aliphatic chain. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys, 35: 457–468, 1997     

Micromechanical fast quasi‐static detection of α and β relaxations with nanograms of polymer

Micromechanical string resonators are used as a highly sensitive tool for the detection of glass transition (T_g or α relaxation) and sub‐T_g (β relaxation) temperatures of polystyrene (PS) and poly (methyl methacrylate) (PMMA). The characterization technique allows for a fast detection of mechanical relaxations of polymers with only few nanograms of sample in a quasi‐static condition. The polymers are spray coated on one side of silicon nitride (SiN) microstrings. These are pre‐stressed suspended structures clamped on both ends to a silicon frame. The resonance frequency of the microstrings is then monitored as a function of increasing temperature. α and β relaxations in the polymer affect the net static tensile stress of the microstring and result in measureable local frequency slope maxima. T_g of PS and PMMA is detected at 91 ±2°C and 114 ±2°C, respectively. The results match well with the glass transition values of 93.6°C and 114.5°C obtained from differential scanning calorimetry of PS and PMMA, respectively. The β relaxation temperatures are detected at 30 ± 2°C and 33 ± 2°C for PS and PMMA which is in accordance with values reported in literature. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1035–1039     

Probing the dielectric response of polyurethane/alumina nanocomposites

The dielectric properties of polyurethane (PUR) latex–boehmite alumina nanocomposites were investigated by means of broadband dielectric spectroscopy in the temperature range ?100 °C to 70 °C. The concentration of the filler (alumina) was kept constant at 10 phr for all specimens, whereas the mean particle diameter (namely 220, 90, and 25 nm) of the incorporated nanoparticles varied accordingly. For reasons of comparison, pure PUR was also examined. Four distinct relaxation modes were recorded in the spectra of all systems. They were attributed to interfacial polarization, glass transition (α‐relaxation), local motions of polar side groups, and chain segments (β‐relaxation and γ‐relaxation). All four relaxation processes exhibit a symmetric distribution of relaxation times, which in the case of interfacial polarization, becomes narrower. The intensity of interfacial polarization increases with the reduction of the mean particle diameter indicating enhanced interfacial area. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2010