Changes of the Molecular Mobility of Poly(<Emphasis Type="Italic">ε</Emphasis>-caprolactone) upon Drawing,Studied by Dielectric Relaxation Spectroscopy

Dielectric relaxation spectroscopy (DRS) of poly(ε-caprolactone) with different draw ratios showed that the mobility of polymer chains in the amorphous part decreases as the draw ratio increases.The activation energy of the α process,which corresponds to the dynamic glass transition,increases upon drawing.The enlarged gap between the activation energies of the αprocess and the β process results in a change of continuity at the crossover between the high temperature a process and the α and β processes.At low drawing ratios the a process connects with the βprocess,while at the highest drawing ratio in our measurements,the a process is continuous with the a process.This is consistent with X-ray diffraction results that indicate that upon drawing the polymer chains in the amorphous part align and densify upon drawing.As the draw ratio increases,the α relaxation broadens and decreases its intensity,indicating an increasing heterogeneity.We observed slope changes in the α traces,when the temperature decreases below that at which τα ≈ 1 s.This may indicate the glass transition from the ‘rubbery’ state to the non-equilibrium glassy state.     

Theory of aging in structural glasses

The random first-order transition theory of the dynamics of supercooled liquids is extended to treat aging phenomena in nonequilibrium structural glasses. A reformulation of the idea of "entropic droplets" in terms of libraries of local energy landscapes is introduced which treats in a uniform way the supercooled liquid (reproducing earlier results) and glassy regimes. The resulting microscopic theory of aging makes contact with the Nayaranaswamy-Moynihan-Tool nonlinear relaxation formalism and the Hodge-Scherer extrapolation of the Adam-Gibbs formula, but deviations from both approaches are predicted and shown to be consistent with experiment. The nonlinearity of glassy relaxation is shown to quantitatively correlate with liquid fragility. The residual non-Arrhenius temperature dependence of relaxation observed in quenched glasses is explained. The broadening of relaxation spectra in the nonequilibrium glass with decreasing temperature is quantitatively predicted. The theory leads to the prediction of spatially fluctuating fictive temperatures in the long-aged glassy state, which have non-Gaussian statistics. This can give rise to "ultraslow" relaxations in systems after deep quenches.     

Dielectric relaxations in PEEK by combined dynamic dielectric spectroscopy and thermally stimulated current

The molecular dynamics of a quenched poly(ether ether ketone) (PEEK) was studied over a broad frequency range from 10^?3 to 10⁶ Hz by combining dynamic dielectric spectroscopy (DDS) and thermo-stimulated current (TSC) analysis. The dielectric relaxation losses ε′′_KK has been determined from the real part ε′_T(ω) thanks to Kramers–Kronig transform. In this way, conduction and relaxation processes can be analyzed independently. Two secondary dipolar relaxations, the γ and the β modes, corresponding to non-cooperative localized molecular mobility have been pointed out. The main α relaxation appeared close to the glass transition temperature as determined by DSC; it has been attributed to the delocalized cooperative mobility of the free amorphous phase. The relaxation times of dielectric relaxations determined with TSC at low frequency converge with relaxation times extracted from DDS at high frequency. This correlation emphasized continuity of mobility kinetics between vitreous and liquid state. The dielectric spectroscopy exhibits the α_c relaxation, near 443 K, which has been associated with the rigid amorphous phase confined by crystallites. This present experiment demonstrates coherence of the dynamics of the PEEK heterogeneous amorphous phase between glassy and liquid state and significantly improve the knowledge of molecular/dynamic structure relationships.     

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     

Molecular motions in amorphous ibuprofen as studied by broadband dielectric spectroscopy

The molecular mobility of amorphous ibuprofen has been investigated by broadband dielectric relaxation spectroscopy (DRS) covering a temperature range of more than 200 K. Four different relaxation processes, labeled as alpha, beta, gamma, and D, were detected and characterized, and a complete relaxation map was given for the first time. The gamma-process has activation energy E a = 31 kJ.mol (-1), typical for local mobility. The weak beta-relaxation, observed in the glassy state as well as in the supercooled state was identified as the genuine Johari-Goldstein process. The temperature dependence of the relaxation time of the alpha-process (dynamic glass transition) does not obey a single VFTH law. Instead two VFTH regimes are observed separated by a crossover temperature, T B = 265 K. From the low temperature VFTH regime, a T g (diel) (tau =100 s) = 226 K was estimated, and a fragility or steepness index m = 93, was calculated showing that ibuprofen is a fragile glass former. The D-process has a Debye-like relaxation function but the temperature dependence of relaxation time also follows the VFTH behavior, with a Vogel temperature and a pre-exponential factor which seem to indicate that its dynamics is governed by the alpha-process. It has similar features as the Debye-type process observed in a variety of associating liquids, related to hydrogen bonding dynamics. The strong tendency of ibuprofen to form hydrogen bonded aggregates such as dimers and trimers either cyclic or linear which seems to control in particular the molecular mobility of ibuprofen was confirmed by IR spectroscopy, electrospray ionization mass spectrometry, and MD simulations.     

Secondary and primary relaxations in hyperbranched polyglycerol: a comparative study in the frequency and time domains

The non-Debye relaxation behavior of hyperbranched polyglycerol was investigated by broadband dielectric spectroscopy. A thorough study of the relaxations was carried out paying special attention to truncation effects on deconvolutions of overlapping processes. Hyperbranched polyglycerol exhibits two relaxations in the glassy state named in increasing order of frequency beta and gamma processes. The study of the evolution of these two fast processes with temperature in the time retardation spectra shows that the beta absorption is swallowed by the alpha in the glass-liquid transition, the gamma absorption being the only relaxation that remains operative in the liquid state. In heating, a temperature is reached at which the alpha absorption vanishes appearing the alphagamma relaxation. Two characteristics of alpha absorptions, decrease of the dielectric strength with increasing temperature and rather high activation energy, are displayed by the alphagamma process. Williams' ansatz seems to hold for these topologically complex macromolecules.     

Dynamics of the amorphous and crystalline alpha-, gamma-phases of indomethacin

Crystallization processes in indomethacin can be observed below Tg leading to different forms depending on the thermal treatment: a rapid and deep quench below Tg leads to the metastable alpha-phase and a slow cooling close to Tg gives rise to the stable gamma-phase. To understand this atypical behavior, we have studied the molecular mobility of the amorphous and crystalline forms of indomethacin by dielectric relaxation and 1H NMR spectroscopy. Two relaxations were detected in the glassy state obtained from the deeply quenched liquid. One, also present in the gamma-phase, was attributed to local rotations. The other one, of very low amplitude, was attributed to the Johari-Goldstein relaxation. The results allowed to discuss the relationship between these two relaxation processes and the crystallization properties of amorphous indomethacin.     

Dynamic light scattering in liquid and supercooled diphenylmethane

We use a dynamic light scattering technique to measure both polarized (VV) and depolarized (VH) spectra of liquid diphenylmethane (DPM) between 288 and 362 K, covering both normal and supercooled liquid ranges. Our results allow extracting information on structural relaxation processes, rotational motions, rotation-translation couplings, and molecular reorientation phenomena in liquid DPM. The VV spectra are modeled according to the microscopic theory of Wang, which assumes that a structural relaxation process dominates the spectrum. We find that the relaxation time of the structural relaxation in DPM follows an Arrhenius behavior. The Rayleigh dip was observed in the VH spectra, which are described using the Andersen-Pecora theory. Our results are discussed in terms of the rotation-translation coupling parameter, which we find independent of temperature over the experimental range. The collective reorientation time also follows an Arrhenius behavior with temperature. Finally, we calculate the hydrodynamic volumes for the reorientation process from geometric molecular models in two hydrodynamic limits: slip and stick boundary conditions. Our results suggest that the DMP molecule reorientates in quasi-slipping conditions in the bulk liquid.     

Glassy crystalline state and water sorption of alkyl maltosides

A differential scanning calorimetric and sorption calorimetric study of two alkyl maltosides, C8G2 and C10G2, was performed. In the dry state, C8G2 and C10G2 do not form solid crystals but undergo a glass transition upon temperature change. The glass is partly ordered and has the same lamellar structure as the liquid crystals formed by the two maltosides. To reflect the presence of the glass transition and the structure, the terms "glassy crystals" and "glassy liquid crystals" can be used. A mechanism of the relaxation of the glassy crystals based on the results of small-angle X-ray scattering experiments is proposed. Experiments on water sorption showed that the glassy crystals turn into lyotropic liquid crystals upon sorption of water at constant temperature. This isothermal glass transition can be characterized by water content and change of partial molar enthalpy of mixing of water. A method to calculate the phase diagram liquid crystals-glassy liquid crystals is proposed.     

Primary and secondary relaxations in supercooled eugenol and isoeugenol at ambient and elevated pressures: dependence on chemical microstructure

Dielectric loss spectra of two glass-forming isomers, eugenol and isoeugenol, measured at ambient and elevated pressures in the normal liquid, supercooled, and glassy states are presented. The isomeric chemical compounds studied differ only by the location of the double bond in the alkyl chain. Above the glass transition temperature T(g), the dielectric loss spectra of both isomers exhibit an excess wing on the high frequency flank of the loss peak of the alpha relaxation and an additional faster gamma process at the megahertz frequency range. By decreasing temperature below T(g) at ambient pressure or by elevating pressure above P(g), the glass transition pressure, at constant temperature, the excess wing of isoeugenol shifts to lower frequencies and is transformed into a secondary beta-loss peak, while in eugenol it becomes a shoulder. These spectral features enable the beta-relaxation time tau(beta) to be determined in the glassy state. These changes indicate that the excess wings in isoeugenol and eugenol are similar and both are secondary beta relaxations that are not resolved in the liquid state. While in both isoeugenol and eugenol the loss peak of the beta relaxation in the glassy state and the corresponding excess wing in the liquid state shifts to lower frequencies on elevating pressure, the locations of their gamma relaxation show little change with increasing pressure. The different pressure sensitivities of the excess wing and gamma relaxation are further demonstrated by the nearly perfect superposition of the alpha-loss peak together with excess wing from the data taken at ambient pressure and at elevated pressure (and higher temperature so as to have the same alpha-peak frequency), but not the gamma-loss peak in both isoeugenol and eugenol. On physical aging isoeugenol, the beta-loss peak shifts to lower frequencies, but not the gamma relaxation. Basing on these experimental facts, the faster gamma relaxation is a local intramolecular process involving a side group and the slower beta relaxation mimics the structural alpha relaxation in behavior, involves the entire molecule and satisfies the criteria for being the Johari-Goldstein beta relaxation. Analysis and interpretation of the spectra utilizing the coupling model further demonstrate that the excess wings seen in the equilibrium liquid states of these two isomers are their genuine Johari-Goldstein beta relaxation.     

Glassy state of pharmaceuticals. IV. Studies on glassy pharmaceuticals by thermomechanical analysis

The glassy state of indomethacin was examined by thermomechanical analysis (TMA). The influences of the method of preparation and the measurement conditions of the sample on the TMA curves were investigated. The TMA curves of glassy indomethacin having hemispherical and plane surfaces were examined. Expansion was observed on the TMA curves in the region of glass transition temperature (Tg), which had been confirmed by differential scanning calorimetry. The TMA curves for the sample with the plane surface showed distinct expansion. It was further found that the glass transition shifted to lower temperatures as the heating rate was decreased and the loading increased. The TMA curves of brucine, griseofulvin and phenobarbital were similar to that of indomethacin. The relaxation process of glassy indomethacin below Tg was followed in terms of the variation of mechanical properties of samples.     

Relationship between the α‐ and β‐relaxation processes in amorphous polymers: Insight from atomistic molecular dynamics simulations of 1,4‐polybutadiene melts and blends

Amorphous polymers exhibit a primary (glass, or α‐) relaxation process and a low‐temperature relaxation process associated with polymer backbone motion usually referred to as the β‐relaxation process. The latter process can be observed below the glass transition temperature of the polymer and usually merges with the α‐relaxation process at temperatures somewhat above the glass transition temperature. While it is widely held that both the α‐relaxation and β‐relaxation processes are engendered by localized (segmental) motions of the polymer backbone, and that there is a strong mechanistic connection between them, the molecular mechanisms of the α‐relaxation and β‐relaxation processes in amorphous polymers are not well understood. Recently, atomistic molecular dynamics simulations of melts and blends of 1,4‐polybutadiene have provided insight into the relationship between the α‐ and β‐relaxation processes in glass‐forming polymers and an improved understanding of their molecular origins. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 627–643, 2007     

Drastic changes in the raman spectrum of aqueous gallium chloride solution from liquid state to glassy state

Raman spectra of aqueous gallium chloride solutions are obtained in both liquid state at room temperature and glassy state. Large spectral changes are observed on going from liquid to glassy state and are discussed in terms of ionic equilibrium reactions.     

Dynamics of glass-forming liquids. XII. Dielectric study of primary and secondary relaxations in ethylcyclohexane

The dynamics of ethylcyclohexane are investigated by high resolution dielectric spectroscopy aiming to characterize the relevant relaxational features of this simple system in its fluid, supercooled liquid, and glassy states. The dielectric signature of structural relaxation is a primary loss peak with amplitude Deltaepsilon=0.01, and a secondary loss process is found in the glassy state. This beta relaxation is compared with a "slow" process revealed by ultrasonics and with previously found gamma and chi processes in similar materials containing the cyclohexyl group. The results suggest that this secondary process is an intramolecular mode rather than a Johari-Goldstein process, consistent with its persistence in the liquid state at slow relaxation times which exceed those of the alpha process. The dielectric activity of such a slow process requires that the dipole magnitude changes with the intramolecular transition, whereas a change in dipole direction only would be masked by the faster structural relaxation.     

The crystalline character of atactic poly(p-biphenyl acrylate) and poly(p-cyclohexylphenyl acrylate) in their dynamic mechanical response

Dynamic mechanical properties have been determined in atactic poly(p-biphenyl acrylate) (PPBA) and poly(p-cyclohexylphenyl acrylate) (PPCPA) in the temperature range from 80 to 540°K at frequencies in the range 10³–10⁴ Hz. The general behavior of the dynamic elastic modulus as a function of temperature shows a transition region from the glassy state at about 390°K for both polymers, a plastic region extending over a temperature interval of about 100°K, and another transition to the melt situated at 540 and 480°K for PPBA and PPCPA, respectively. The experimental data show that the mechanical behavior of both polymers strongly resembles that of crystalline polymers. The loss spectrum of PPBA shows the presence of several important maxima: one corresponding to the melting point, characterized by a very rapid increase of losses with increasing temperature (α′ relaxation), one in the glass-temperature range, characterized by a rather broad peak (α′ relaxation), and others below T_g, associated with secondary relaxation effects. The analysis of the different transitions and relaxations indicates that some of these processes can be ascribed to motions taking place in the ordered regions of the polymer. PPCPA shows a similar loss pattern; however, owing to the lower melting point the α maximum is partially submerged in the α′ relaxation associated with the melting process. Of particular interest is the γ process in the glassy state of this polymer, caused by the chair–chair transition of the cyclohexyl rings. The limited intensity of this relaxation as compared with that of most polymers containing cyclohexyl side groups, has been interpreted as due to the high ΔF associated with such a transition for cyclohexyl rings linked to phenylene groups. This leads to some interesting conclusions about the conformation of the side groups in PPCPA.     

Diamagnetic susceptibility of liquid crystalline copolyesters: Study of molecular relaxation

The diamagnetic susceptibility of a series of random copolyesters, P(HB/HN), of 4-hydroxybenzoic acid (HBA) with 2-hydroxy-6-naphtoic acid (HNA) has been investigated, both, as a function of composition and temperature. It is shown that the molecular susceptibility of the uniaxially oriented samples linearly decreases with HB content. Results are discussed in terms of the increase in magnetic anisotropy occurring with the introduction of the HN groups. Furthermore, the temperature dependence of the specific susceptibility has been investigated. The diamagnetic susceptibility of these copolymers rises at the beginning of the solid-liquid crystalline transition. Above this temperature, the specific susceptibility exhibits a conspicuous time-dependent behavior which is a function of the temperature at the mesophase. After long storage times at the mesophase, and upon cooling at room temperature, the susceptibility shows values which approach those of a macroscopically isotropic state, i.e., a state with no overall preferred orientation. X-ray diffraction measurements confirm a relaxation mechanism of the molecular orientation occurring at temperatures above the melting point. A similar relaxation process is observed for samples with an initial planar orientation. © 1996 John Wiley & Sons, Inc.     

The “Relaxed” state in a semicrystalline polymer: Experimental characterization and modeling

This work addresses the general issue of the mechanical behavior of the confined amorphous phase in rubbery semicrystalline polymers. Even far above the glassy transition temperature, the amorphous phase in semicrystalline polymers is known to remain constrained by crystals and is less mobile than a purely amorphous polymer close to its equilibrium rubbery state. The aim of this paper, based on Polyamide 11, is to investigate the existence and significance of a relaxed state in the amorphous phase of a semicrystalline polymer far above T _g. A strain-rate independent tensile curve (called the “asymptotic curve”) is evidenced below a critical strainrate, consistently with a fully relaxed state of the rubbery amorphous phase. Nevertheless, a contradictory mechanical phenomenology was observed at the same time (hysteretic unloading, relaxation, and creep involving the same strain-rates as the “asymptotic” loading regime), suggesting joint amorphous and crystalline processes. Modeling of this paradoxical behavior is attempted, based on the experimental results. The first one-dimensional simulations are presented. Published in Russian in Vysokomolekulyarnye Soedineniya, Ser. A, 2008, Vol. 50, No. 5, pp. 797–808. This article was submitted by the authors in English.     

Shear stress relaxation and physical aging study on simple glass-forming materials

Relaxation and aging behaviors in three supercooled liquids: m-toluidine, glycerol, and sucrose benzoate have been studied by shear stress relaxation experiments in the time domain above and below their nominal glass transition temperatures. For the equilibrium state, the current study provides new data on the behavior of organic complex fluids. The shape of the relaxation function as characterized by the stretching exponent beta is discussed considering that a time-temperature master curve can be constructed even though the beta's for the individual response curves at each temperature vary systematically. In the nonequilibrium state, isothermal physical aging experiments at different glassy structures reveal that the effect of the aging process on the mechanical shear relaxation in these simple glass formers is similar to that observed in polymeric and other systems. Departure from the Vogel-Fulcher-Tamman behavior after the samples have aged back to equilibrium in the glassy state is observed for m-toluidine and, less strongly, for glycerol but not for sucrose benzoate. An inherent structure-based energy landscape concept is briefly discussed to account for the slow dynamics during the physical aging process.     

Thermally induced low-temperature relaxation of plastic deformation in glassy organic polymers and silicate glasses

A deep analogy between the processes of low-temperature thermally induced relaxation of plastic deformation in amorphous polymers and inorganic glasses is observed. The results of the calculation of the activation energy and activation volume of this relaxation process in terms of the excited state model satisfactorily agree with the experimental data obtained for both epoxy polymer systems and sheet silicate glasses. This evidence allows us to conclude that the initial stage of macroscopic plastic deformation in glassy systems involves small critical displacements of excited atoms (groups of atoms) that are provided by local rearrangements of neighboring particles (entropy fluctuations). In the vicinity of the yield point, the number of excited atoms per unit volume induced by the action of mechanical stresses appears to be quite sufficient (10²⁶–10²⁷ m^?3) for promotion of a marked plastic deformation of glasses and preservation of appreciable amounts of internal energy.