Thermoluminescence and thermally stimulated conductivity in polymers

Thermoluminescence (TL) and thermally stimulated conductivity (TSC) glow curves in poly(vinyl chloride), polyethylene, polystyrene, polytetrafluoroethylene, and polyimide have been compared, and many similarities have been observed. Comparison with available NMR, dynamic mechanical loss, and dielectric loss, molecular mobility data shows that most TL and TSC peaks occur at temperatures similar to those assigned to the onset of specific molecular motions, suggesting that the peaks are due to the liberation of electrons from traps formed by the polymer chains themselves, e.g., potential wells or cavities due to chain entanglement in amorphous regions, or main-chain branching points. Peaks for which correlation with molecular motion is not apparent are tentatively assigned to liberation of electrons from traps centered on impurities. The TSC peak temperatures in PVC were not affected in any consistent fashion by the application of high-strength electric fields during the warming process, indicating that the electron traps are electrically neutral when empty and charged when filled; the direction of the TSC currents appears to be determined by temperature gradients existing within the samples. The TL glow-curves are generally in good agreement with the results of other workers. The dark dc conductivity of PVC not exposed to ionizing radiation rises sharply in the temperature region assigned to the β-relaxation process, suggesting that the electron mobility in that polymer is dominated by molecular chain motion, i.e., the interchain charge transport process is probably best described in terms of a hopping process.     

A thermally stimulated discharge currents study of the molecular motions in two polysiloxane side-chain liquid crystalline polymers

The technique of thermally stimulated depolarization currents was used to study the dipolar relaxation mechanisms in two side-chain liquid-crystalline polysiloxanes. The studied polymers have the same mesogenic side-group, but they differ in the number (or density) of side groups attached to the main chain. In both cases three different relaxations were observed: one in the vitreous state, one in the liquid crystalline phase, and the glass transition relaxation. The features of those thermally stimulated discharges are discussed and some suggestions are made concerning the attribution of those discharges at the molecular level. © 1995 John Wiley & Sons, Inc.     

Chemical origin of thermally stimulated discharge currents in polyacrylonitrile

Thermally stimulated discharge has been used in the past to diagnose and estimate the magnitude of electrical polarization in polymers. Nevertheless, molecular characterization of operative phenomena by this technique alone is often a difficult task. In the present work, infrared attenuated total reflection spectroscopy has been used to investigate the origin of thermally stimulated discharge currents near 200°C in externally unpolarized films of polyacrylonitrile (PAN). Spectroscopic analysis of thermally degraded films reveals some unsaturation of the PAN backbone and possibly the generation of cyanide ions. Opposite surfaces in a solvent-cast film give different spectra, indicating a gradient in chemical degradation products across the film thickness. Data suggest that nonuniform generation of charged species and unsaturated bonds gives rise to internal potentials in PAN. The origin of thermally stimulated currents in PAN near 200°C is thus believed to be associated with the onset of chemical degradation.     

Molecular mobility in polymers studied with thermally stimulated recovery

Thermally stimulated recovery, TSR, like as thermally stimulated depolarisation currents, is a suitable technique that allows for the study of conformational mobility in polymeric systems. Due to its relatively low equivalent frequency and transient nature, the viscoelastic data obtained from this technique are complementary to conventional dynamic mechanical analysis (DMA). In this work TSR-like experiments, including TSR, thermally stimulated creep and thermal sampling (TS) experiments were carried out in the same commercial DMA equipment, allowing for the direct comparison of the data. Some advises for running TSR experiments are presented, such as the need of performing blank experiments and temperature calibrations. The analysis of the data to obtain the thermokinetic parameters of TS experiments is revised. In particular, from the direct fitting of the data, it is reported a tendency for a linear relationship between the pairs of values of (E _a, log τ₀) that best adjust any TS single experiment. It is concluded that the usual equation for describing TS experiments possesses an intrinsic compensation between these two thermokinetic parameters. This revised version was published online in August 2006 with corrections to the Cover Date.     

Characterization of polymers using the thermally stimulated current technique

Thermally Stimulated Current (TSC) technique is a relaxation technique, such as DMA, but works at very low equivalent frequency (10^?3–10^?4Hz) and thus clearly resolves the peaks related to the molecular mobility. The effect of orientation on Polypropylene fibers, the relaxation of internal stresses on Polycarbonate disks, and the effect of aging on acrylic airplane windows have been investigated using the TSC method.     

General properties of secondary relaxations in polymers as determined by the thermally stimulated current method

The method of thermally stimulated current (TSC) has been used to study the low-temperature dielectric β relaxations of several polymers including especially poly(vinyl chloride), poly(vinyl acetate), polyamide 6, 6,6,poly(t-butyl acrylate), poly(methyl methacrylate), poly(ethyl methacrylate), poly(phenyl methacrylate), and poly(t-butyl methacrylate). The distribution characteristics of the relaxation processes have been determined from the corresponding TSC peaks by a fractional polarization technique which consists of applying the electric field in several discrete steps during a slow cooling. Several common features have been found in all the polymers investigated: the β peaks are characterized by a distribution of relaxation times resulting from a distribution in activation energy and this distribution is quasisymmetrical and continuous. These facts are in agreement with the hypothesis of a relaxation involving local motions of small polar groups undergoing various interactions with the environment. Some discrepancy remains, however, between our calculated values of the mean activation energy and those obtained from the dielectric loss.     

Comparison of head-to-head and head-to-tail polystyrenes by thermally stimulated discharge

Thermally stimulated depolarization (TSD) experiments were carried out on several polystyrene samples. They included normal head-to-tail polystyrene (atactic) obtained by anionic polymerization of styrene, amorphous and substantially crystalline isotactic polystyrene, and the newly available head-to-head polystyrene. By TSD, six maxima of current intensity occurred at specific temperatures. Their features are compared for the various samples. Only three peaks could be identified with transitions which had been found by other techniques. Peak 5, located near T_g, is the primary relaxation. Maximum 6 could be the transition found above the T_g by torsional braid analysis and called T₁₁ for polystyrene samples. Maximum 1 seems to correspond to what is sometimes referred to as the γ transition.     

Scope of electron transport studies by thermally stimulated discharge current measurement

A logical approach to electron transport studies for barrier conduction in layered structures was adopted by thermally stimulated discharge current (TSDC) measurement. The scope and applicability of this technique to the evaluation of the thermoelectric parameters of relaxation time, detrapping energy and depolarization rates are demonstrated here. These are characterized by the controlling factors of layer resistance and the resultant thermal and voltage gradients which apply to the drift of electrons arising from both dipolar and interfacial charges. The methodologies used in this study are suitable for parametric evaluation of structured electronic devices. This revised version was published online in July 2006 with corrections to the Cover Date.     

Analysis of ice water by the thermally stimulated depolarized current (TSDC) method.

The thermally stimulated depolarized current and temperature profiles (TSDC analysis) on iced water was proved to be an effective tool for the qualitative evaluation of various water samples, each having an independent relaxation process, brought about by a pure dipolar orientation. The method proved to be applicable to different kinds of water samples used in the experiment and tap-water samples from different suppliers. Five main peaks (A to E, in the order of increasing temperature) were observed, of which two peaks (B and D) were found for the first time. The appearance of multiple peaks suggested the existence of multi-states of the hydrogen bond, cleaved by the TSDC process. The TSDC profiles were quite reproducible when the water samples contained practically no cations. A separate addition of each cation at a low concentration level revealed that a cation with a smaller ionic radius shifted peak A to a higher temperature. For ice of tap water, which contained relatively higher amount of cations, the TSDC profiles were quite different in shape compared with the standard ice-water samples (shift of peaks A - D to higher temperature, and a strong increase in the current strength of peaks B - E). However, it was still possible to tell from which districts the water samples were supplied.     

Effect of catalysts on thermally stimulated current in poly(ethylene terephthalate)

The effect of catalysts on relaxation phenomena in poly(ethylene terephthalate) (PET) was studied by thermally stimulated current (TSC). Resins Sb-PET and Ge-PET were produced by the antimony and germanium main catalyst systems, respectively. Spontaneous, global and thermal sampling of TSC were compared in both PETs. The lower TSC peaks are observed in Ge-PET than those in Sb-PET for equivalent treatment. The compensation parameters were determined from the variation polarization temperatures (Tp) data. These parameters were used to calculate degree of disorder (DOD). The DOD of Sb-PET and Ge-PET were 36.14 and 66.23, respectively. The relaxation time at the maximum current and the dipolar relaxation strength in the Sb-PET has the higher values and wider distribution than that in Ge-PET. Furthermore, Sb-PET exhibited electrically softer. These results are attributed to the stiffening amorphous parts by the entanglement network in Ge-PET. This revised version was published online in July 2006 with corrections to the Cover Date.     

Study of multiple relaxations in styrene-acrylonitrile copolymer using thermally stimulated current method

The dielectric behaviour and the electrical polarization in as-cast and polarized films of styrene-acrylonitrile (SAN) copolymer have been investigated using the Thermally Stimulated Current (TSC) technique. Films were polarized with various field strengths in the range 20 to 80 kV cm^?1. The TSC spectrum showed four peaks (at ～ 70, 105, 130 and ～ 180°); their origins are explained in terms of the relaxation of the nitrile side-groups, glass-transition of the copolymer and the space-charge displacement. Thermal peak-cleaning and partial-heating techniques were applied in order to determine the exact positions of the peaks and the activation energies associated with the processes.     

Influence of photogeneration centers on the intensity of a thermally stimulated current transport peak. Application to poly(N-vinylcarbazole)

The influence of coulomb centers (coulomb traps and photogeneration centers) on the intensity of a thermally stimulated current (TSC) transport peak is examined. We apply these concepts to account for the field dependent transport charge associated to the area under the TSC traces resulting from poly(N-vinylcarbazole).Dedicated to Professor Dr. F. H. Müller.     

Correction to: Study of human blood under influence of magnetic field by AC dielectric and thermally stimulated discharge current methods

Journal of Thermal Analysis and Calorimetry - In the original publication of the article, Tables 1 and 2 were swapped. The correct versions are given below. The original article has been...     

Investigations on electric properties of polymers—II. Dielectric relaxation in atactic polystyrene determined by thermally stimulated depolarization currents

The thermally stimulated depolarization currents (TSDC) from atactic polystyrene and d.c. conductivity of the same material have been studied over the temperature ranges 200–395 K and 363–393 K respectively. TSDC spectra are complex and consist of four peaks, β₁, β₂, β₃ (β₃ of reduced intensity) and α in order of increasing temperature. The first three peaks appeared below the glass transition temperature T_g of the polymer. The β₁ peak seems to arise from a single dipolar relaxation process. The β₂ peak and probably β₃ arise from a distribution in activation energy of dipolar relaxation processes. On the basis of the molecular origin of the β relaxation process, it was suggested that β₁, β₂ and β₃ peaks involve motions of backbone chain fragments of various lengths. The last peak α appeared at T_g and could be considered as a result of dipole relaxation and electric conductivity. TSDC peaks and d.c. conductivity have been related to the second order transition in the polymer.     

Study of human blood under influence of magnetic field by AC dielectric and thermally stimulated discharge current methods

Journal of Thermal Analysis and Calorimetry - The aim of the present work is to study the effect of magnetic field on thermally stimulated discharge current (TSDC) characteristics and dielectric...     

A thermoreversible conformational change in two poly(zwitterions) evidenced by thermally stimulated depolarization currents

A thermally induced conformational change of zwitterionic groups of two polymers has been observed by thermally stimulated depolarization currents. Different dipole moments of the two conformations is a prerequisite. The appearance of peaks of opposite sign confirms the process. Giant dielectric constants can be obtained at room temperature using high-temperature poling and rapid cooling.     

Retardation and relaxation behaviour of poly (ether-block-amide)s (PEBA) copolymers by thermally stimulated creep (TSCr) and current (TSCu)

The retardation and relaxation behaviour of poly(ether-block-amide)s PEBA copolymers was investigated as a function of hard polyamide sequence length by using thermally stimulated creep (TSCr) and Current (TSCu). Two primary TSCr and TSCu peaks, called ß_PE and ß_PA were observed in the temperature range 150–300 K. The “low temperature” peak ß_PE was characterized by a peak position T ß_PE which depends poorly upon hard segment content as the corresponding DSC glass transition temperature Tg_PE. The peak position Tß_PA of the “high temperature” relaxation showed a progressive shift towards higher temperatures as the hard segment average length was increased as it is observed in series of pure polyamide oligomers. So, complex spectra suggest that an amorphous phase separation occurs in PEBA copolymers. The TSCr ß_PE and ß_PA modes were analysed by thermal sampling method (TS). The elementary TSCr processes isolated in the ß_PE and ß_PA distributed retardation modes were characterized by retardation times following a compensation law. The comparison of activation and compensation parameters confirmed the existence of a biphasic amorphous phase in PEBA. In TSCr spectra, an additional peak, noted α, is observed at a temperature close to the DSC melting point T_mPE of the poly(tetramethylene glycol) segments.     

New approach to filled polymers

Mechanopolymerization of pentabromobenzyl (mono)acrylate (PBB-MA) on the surface of inorganic fillers Mg(OH)₂ and CaCO₃ was studied. The role of activated surface of fillers was investigated using DSC and FTIR. The influence of milling time and of the filler chemical content on polymerization starting temperature and polymerization enthalpy was studied using DSC. It was shown that an increase of the filler concentration leads to a higher maximum conversion degree. The correlation between conversion kinetics and polymerization enthalpy of the material notpolymerized during milling was shown. This paper was presented on the Second Conference of The Israel Group of Mechanochemistry.