Do theories of the glass transition, in which the structural relaxation time does not define the dispersion of the structural relaxation, need revision?

Upon decreasing temperature or increasing pressure, a noncrystallizing liquid will vitrify; that is, the structural relaxation time, taualpha, becomes so long that the system cannot attain an equilibrium configuration in the available time. Theories, including the well-known free volume and configurational entropy models, explain the glass transition by invoking a single quantity that governs the structural relaxation time. The dispersion of the structural relaxation (i.e., the structural relaxation function) is either not addressed or is derived as a parallel consequence (or afterthought) and thus is independent of taualpha. In these models the time dependence of the relaxation bears no fundamental relationship to the value of taualpha or other dynamic properties. Such approaches appear to be incompatible with a general experimental fact recently discovered in glass-formers: for a given material at a fixed value of taualpha, the dispersion is constant, independent of thermodynamic conditions (T and P); that is, the shape of the alpha-relaxation function depends only on the relaxation time. If derived independently of taualpha, it is an unlikely result that the dispersion of the structural relaxation would be uniquely defined by taualpha.     

The influence of gamma radiation on the dielectric relaxation behaviour of isotactic polypropylene: The α relaxation

The high-temperature α relaxation in gamma irradiated isotactic polypropylene (iPP) was studied over the temperature (298-406 K), frequency (10³-10⁶ Hz) and absorbed dose (0-700 kGy) ranges by means of dielectric spectroscopy. The multiple α relaxation was resolved from the β relaxation by curve fitting and its parameters were determined. Its position, intensity and activation energy were found to be strongly dependent on the changes in the structural and morphological parameters attributed to the exposure of the samples to radiation. Wide angle X-ray diffraction (WAXD) was used to investigate radiation-induced changes in the crystalline structure and degree of crystallinity, since this relaxation is connected with the crystal phase. Infrared (IR) spectroscopy and gel measurements were used to determine the changes in the oxidative degradation and the degree of network formation, respectively; the polar (carbonyl and/or hydroperoxide) groups that were introduced by irradiation were considered as tracer groups. Conclusions derived according to different methods were compared. The results reveal uncommon α relaxation behaviour with gamma radiation and confirm the multiple nature of this process, together with high dielectric and/or relaxation sensitivity of iPP to the radiation-induced changes.     

Dielectric γ relaxation in NaSCN salt complexed PEO

Real and imaginary dielectric spectra of pure, and sodium thiocyanate (NaSCN) salt complexed polyethylene oxide (PEO) have been measured as a function of temperature in the region of the relaxation peak. The results support previous assumptions; the concentration of the amorphous phase and the conductivity depend on the salt content. In this temperature range the dielectric loss is apparently the sum of a pure Gaussian relaxation (always present in amorphous polymers) and an additional component which linearly increases with temperature. The microscopic origin of the additional loss needs to be clarified.     

Dielectric relaxation in OH—O bond complexes

Abstract

The dielectric absorption of the mixtures of Phenol with Acetone and Ethyl methyl ketone having different concentration ratios (3:1, 2:1, 1:1, 1:2 and 1:3) has been determined at microwave frequency 9.8 GHz, at 33°C. The dielectric data have been analyzed, to yield relaxation times and dipole moments, using Higasi method and Higasi, Koga and Nakamura method. All the mixtures yielded high values of the distribution parameter indicating the flexible nature of the OH-O type hydrogen bonding. The high values of the relaxation times and dipole moments give confirmative results for the association of the phenol with these electron donar molecules in all mixtures investigated.     

Enthalpic relaxation of silica–polyvinyl acetate nanocomposites

Although the effects of filler nanoparticles size and surface treatment on the glass transition temperature of the matrix phase have received well-deserved attention, nanofiller effects on other physical parameters associated with the glass transition have received less interest. To better understand how the incorporation of nanofillers affects the enthalpic relaxations associated with the glass transition, differential scanning calorimeter measurements were carried out on silica–polyvinyl acetate nanocomposites with respect to filler content, annealing temperature, and annealing period. As expected, longer annealing periods below the glass transition temperature resulted in an increase of the subsequent enthalpic relaxations. However, the presence of filler substantially reduces the enthalpic relaxation relative to that of the neat polymer at longer annealing periods only. The underlying enthalpic relaxations and the effects suppressed by the fillers are specific to the annealing temperature. These results suggest a significant alteration in the physical state of the matrix because of the presence of the filler particles. However, this does not imply the existence of a glassy layer or layers with a glass transition gradient near the filler surface. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 2733–2740, 2008     

Strain-induced large fluctuations during stress relaxation in polymer melts observed by small-angle neutron scattering. “Lozenges”, “butterflies”, and related theory

We discuss the neutron scattering features of melts containing a fraction of labeled chains, and of rubbers containing a fraction of deuterated paths along several successive elementary chains. Both types of material are studied during relaxation after a fast deformation in very similar conditions. An unusual feature is the shape of the anisotropic scattering as visualized on a bidimensional detector: the isointensity lines have the shape of lozenges. A detailed review of various cases makes this appear as a general feature in SANS scattering from melts and rubbers in a state of partially relaxed deformation. We then describe results for mixtures of small labeled chains inside matrices of large entangled chains or crosslinked matrices: we find another unusual shape of the isointensity levels, called butterfly. We propose the lozenges to be a combination of the classical elliptical scattering with a butterfly scattering, which has a main axis orthogonal to the main axis of the ellipses. We discuss in more details the origin of the butterfly effect, by following two tracks: the first is several theories about demixing under strain, including influence of the strain on the enthalpic, elastic, and conformational terms of the free energy of mixing. The second track is the influence of heterogeneities in crosslinked materials. An explanation which would be common to the case of crosslinked and uncrosslinked material remains to be established.     

Dielectric relaxation study of formamide–propylene glycol using time domain reflectometry

Using picoseconds time domain reflectometry, dielectric relaxation studies have been carried out for formamide (FMD)–propylene glycol (PLG) mixtures over the frequency range from 10?MHz to 20?GHz at various temperatures. The dielectric parameters, i.e. static dielectric constant (ε ₀) and relaxation time (τ), have been obtained by Fourier transform and least squares fit methods. The excess dielectric properties and Kirkwood correlation factor of the mixtures have also been determined. The Kirkwood angular correlation factor is greater than one (g ^eff?>?1) in FMD-rich region and less than one (g ^eff?<?1) in PLG-rich region, which indicates that in the mixture the dipole pairs have been formed in such a way that their orientation is parallel in FMD-rich region and antiparallel in the PLG-rich region.     

Resonance of relaxation time in the temperature modulated Schlögl model

We show the possibility to accelerate-in a resonant way-a nonlinear chemical reaction by imposing a small temperature modulation. This classical resonance, which happens for particular modulation frequencies, is illustrated on the athermic cubic Schlogl model, which allows us to get analytical expressions for both the reaction relaxation time and the frequency-resonant delay.     

Dielectric relaxation of Tripropylene glycol–water mixture using time domain reflectometry

The complex permittivity spectra of tripropylene glycol and water solutions have been obtained by time domain reflectometry (TDR) technique in the frequency range from 10 MHz to 30 GHz and the temperature range 20°C–05°C. The dielectric relaxation parameters such as static dielectric constant and relaxation time were obtained by using the non-linear least square fit method. The intermolecular hydrogen bonding of tripropylene glycol–water has been discussed using the Kirkwood correlation factor and thermodynamic parameters. The activation energy decreases with increase in water content in the mixture as expected in the Arrhenius behaviour. The dielectric constant for mixtures has been fitted to the Bruggeman mixture formula in the non-linear case.     

Dielectric relaxation study of aqueous α-amylase using time domain reflectometry technique

Time domain reflectometry technique has been used to study the complex permittivity spectra of aqueous α-amylase solution at different pH. Static dielectric constant and relaxation time were obtained from the complex permittivity spectra using nonlinear least square fit method. The dielectric relaxation parameter increases with an increase in molar concentration of α-amylase in water due to the formation of hydrogen bonding. The hydration numbers were also determined from the static dielectric constant.     

Acceleration of carbon-13 spin-lattice relaxation times in amino acids by electrolytes

A series of amino acids and carboxylic acids were determined by C NMR spectroscopy. 13 The results showed that addition of 3M MgCl2 led to the C NMR integral area of samples being 13 well proportional to number of carbon atoms that produce the particular signal with reliability over 95%. Measurements of C spin-lattice relaxation times (T1’s) are reported for a number of amino 13 acids. T1’s of all the carbons in amino acids generally tend to decrease with the increase of the c…     

Nuclear magnetic relaxation of protons in “polyantimonic acid–phosphate” composites

The results of studying MeH₂PO₄ (Me = K, Na)/Sb₂O₅ · 2.7H₂O composites using the pulsed NMR spectroscopy technique at the temperatures of 20–140°C are presented. The contribution of interfaces, a subsystem formed due to interaction between the components of the composite, is identified in the signals of transverse magnetization decay. Protons near the interfaces are in two states, mobile and bound, and the fraction of mobile protons increases with the temperature, as all protons prove to be in the mobile state at the temperatures above 80°C. The composition of the interface is determined by the ion exchange reaction between components and is close to phosphoric acid. The obtained results explain the observed increase in conductivity of composites as compared to pure components.     

Ultrafast excitation relaxation in light-harvesting complex LH2 from Rb.sphaeroides 601

The light-driven reactions of photosynthesis are the means by which nature converts solar energy into electrochemical potential, which is eventually stored as chemical energy. These initial reactions occur in two closely coupled pigment systems, the network of so-called antenna system in which the excitation en-ergy is absorbed by the pigments and efficiently transported to another system, the photosynthetic reac-tion center where the energy is converted into a stable trans-membrane charge sepa…     

Structural relaxation of PbO–WO3–P2O5 glasses

The structural relaxation of three compositional series of PbO–WO₃–P₂O₅ glasses with composition (0.5 ? x/2)PbO·xWO₃·(0.5 ? x/2)P₂O₅, x = 0, 0.1, 0.2, 0.3, 0.4, and 0.5; 0.5PbO·xWO₃·(0.5 ? x)P₂O₅, x = 0, 0.1, 0.2, and 0.3; and (0.5 ? x)PbO·xWO₃·0.5P₂O₅, x = 0, 0.1, 0.2, 0.3, 0.4, and 0.5 was studied by thermomechanical analysis. The structural relaxation was studied in the transformation region using the Tool–Narayanaswamy–Moynihan’s and Tool–Narayanaswamy–Mazurin’s models. The relaxation function of Kohlrausch Williams and Watts was used. The parameters of both models were calculated by nonlinear regression analysis of thermodilatometric curves measured by thermomechanical analyzer under the constant load. Both models very well describe the experimental data. It was found that the modulus is increasing with increasing amount of WO₃ in all glasses. On the contrary, the width of the spectrum of relaxation times is decreasing with increasing amount of WO₃ in all studied glasses. Both models possess the values of metastable melt thermal expansion coefficient equal to their experimental value.     

Temperature-dependent relaxation study of tertiary butyl alcohol–water mixtures using TDR technique

Using time-domain reflectometry (TDR) technique, we have measured the complex permittivity of tertiary butyl alcohol (TBA)–water mixtures in the frequency range of 10 MHz–30GHz, at temperatures 15°C, 20°C and 25°C. The complex permittivity of TBA–water mixture shows Debye-type behaviour. The dielectric parameters such as dielectric constant and relaxation time were obtained from the complex permittivity spectra. The Kirkwood correlation factor and Bruggeman factor have also been determined to investigate inter- and intramolecular interaction among associating liquids.     

Study of the copper(II)-Aztreonam™ system by potentiometry and spectrophotometry,and structural characterization by 13C NMR relaxation

Potentiometric and spectrophotometric results obtained for the Cu(II)-Aztreonam system give a clear indication of the cheating properties of this antibiotic toward the Cu²⁺ ion, coordinated already at pH ≌ 2. Only one single complex of 1:1 stoichiometry is formed. Measurements of ¹³C relaxation rates allow us to attribute a coordination scheme via the carboxylic and aminic groups.