Polymer Dynamics in Polyurethane/clay Nanocomposites Studied by Dielectric and Thermal Techniques

Differential scanning calorimetry (DSC), broadband dielectric relaxation spectroscopy (DRS), and thermally stimulated depolarization current (TSDC) techniques were employed to investigate glass transition and polymer dynamics in nanocomposites of polyurethane (PU) and organically modified montmorillonite (MMT) (weight fraction 0%–15%) prepared by solution casting. The PU matrix was obtained from oligo(oxytetramethylene glycol) of molar mass 1000 g/mol, 4,4′-diphenylmethane diisocyanate and 1,1-dimethylhydrazine as chain extender. Wide-angle X-ray scattering confirmed the formation of partly exfoliated structures at low MMT content. DSC, DRS, and TSDC show, in agreement with each other, that a fraction of polymer makes no contribution to the glass transition and to the corresponding α relaxation, whereas the rest exhibits similar glass transition dynamics as the pure matrix. This fraction of immobilized polymer reaches a maximum at about 5 wt% MMT. Effects of MMT on the microphase-separated structure of PU are negligible, as indicated by the study of glass transition and interfacial dielectric polarization/relaxation. No effects of MMT on the local, secondary γ and β relaxations were observed. Mechanical properties show a maximum improvement at about 5 wt% MMT, in good correlation with morphology and dynamics.     

Revisitation of the molecular mobility of the amorphous solid 4,4′-methylenebis(N,N-diglycidylaniline) (MBDA): New contributions from the TSDC technique

In the present work we revisit the previously published study by Thermally Stimulated Depolarisation Currents (TSDC) of the slow molecular mobility in the amorphous solid state of 4,4′-methylenebis(N,N-diglycidylaniline), MBDA (H. P. Diogo, J. J. Moura Ramos, J. Mol. Liq. 129(2006)138–146) in order to add two important points dealing with recent uses of the TSDC technique. One of them concerns a new method to account for nonexponentiality in Thermally Stimulated Depolarisation Currents (TSDC) data treatment which affects the analysis of the alpha relaxation peak and the determination of the fragility index of the glass-forming system. The other point concerns the analysis of the secondary relaxations in MBDA. It is shown that two kinds of secondary relaxations are differently influenced by aging. The faster components of the secondary relaxation are negligibly dependent on aging and may be ascribed to intramolecular modes of motion, while the slower motional modes show a significant dependence on aging and correspond to the genuine Johari-Goldstein β-relaxation.     

The determination of the glass transition temperature by thermally stimulated depolarization currents. Comparison with the performance of other techniques

Several experimental techniques are currently used for the determination of the glass transition temperature, T_g. Thermally stimulated depolarization currents (TSDC) is a thermal analysis technique whose experimental results display a very clean glass transition signature and that, nevertheless, is seldom used as a technique for T_g determination. In the present work we explain how to get the glass transition temperature from TSDC data, and we compare the values obtained for a vast number of glass forming systems (with T_gs in a wide range between ?145 and +180 °C and fragilities between m = 15 and m = 100), with the values obtained by differential scanning calorimetry (DSC) and dielectric relaxation spectroscopy (DRS). We conclude that the T_g determination by TSDC is direct, accurate and reproducible and that the obtained values correlate very well with those obtained by DSC and DRS. This general survey thus suggests TSDC as a valuable alternative technique for determining T_g.     

The Slow Molecular Mobility in Semicrystalline Poly(Ethylene Oxide)

The thermally stimulated depolarization current (TSDC) technique has been used to study the slow molecular mobility in the amorphous part of the semicrystalline polymer, poly(ethylene oxide) (PEO). Experiments were carried out in the temperature range that includes the glassy state, the glass transformation region and the rubber state. The dipole moments in the polymeric main chain originated a broad and low intensity secondary relaxation in the temperature region from ?130°C up to the glass transition region; the activation energy of the motional modes of this secondary relaxation was in the range between 35 and 100 kJ mol^?1. The glass transition temperature of the PEO, provided by the TSDC technique, was T_g = ?53°C, and the fragility index was found to be m = 43. A strong relaxation above T_g was observed, whose molecular origin was discussed. The thermal behavior of the PEO was also characterized by differential scanning calorimetry.     

The orientational glass transition in pentachloronitrobenzene: a study by differential scanning calorimetry and thermally stimulated currents

The orientational disorder that is a feature of the crystalline pentachloronitrobenzene above ∼−82 °C, can be frozen by cooling to produce an orientational glass. The number of degrees of freedom frozen on cooling, or released on heating, in this orientational glass transition is low, so that the heat capacity change associated with this transition is expected to be small. In the present work, we show that the calorimetric signature of this orientational glass transition is in fact very weak. Conversely, since the molecular motions associated with this relaxation drag strong dipoles, the technique of thermally stimulated depolarisation currents (TSDC) provides a very strong signature of this transition. The orientational glass transition in pentachloronitrobenzene was studied by TSDC and, from this study, it was shown that this orientational glass belongs to the class of very strong glasses in the fragility scale proposed by Angell.     

Molecular mobility of sorbitol and maltitol: A ^13C NMR and molecular dynamics approach

Molecular mobility in two similar organic glass formers, namely sorbitol and maltitol, is studied in order to understand their difference in the cross-over between and relaxations, far above their respective glass transition temperatures. In this goal, the individual mobility of each carbon atom of the 6 carbon chain present both in sorbitol and maltitol is studied by means of ^13C nuclear magnetic resonance and molecular dynamics simulations. Both techniques imply that the mobility of carbons located at the end of the 6 carbon chain is greater than that of any other carbon of this chain and that the difference in carbon mobility is greater within the sorbitol moiety of maltitol than in sorbitol. The relaxation time obtained by magnetic resonance for carbons at the end of the 6 carbon chain is related to the relaxation time and the one of carbons in the middle of the chain is in relation with the value of the relaxation time. This result may suggest that the merging between the and relaxation processes in both sugars would be related to the decrease of the differences in mobility between the atoms of 6 carbon chain. Received 4 October 1999 and Received in final form 27 December 1999     

Relaxation modes in glassy polymers: A temporal analysis by the simplex method of isothermal depolarisation current measurements

Molecular dynamics associated to relaxation phenomena in the glass transition temperature domain is often investigated by means of thermostimulated depolarisation current TSDC technique. It is a very sensitive method and the data are traditionally obtained according to two protocols leading to the well known complex spectra and elementary spectra. The aim of this work is to use a new TSDC protocol which analyses the relaxation current kinetics obtained after submitting the sample to an electrical field pulse at a constant temperature. A new temporal analysis of the return equilibrium isothermal transient current I(T) is proposed. The signal fitting is obtained by a simplex optimisation method. The entire signal recorded for all the temperatures can be fitted with a sum of two exponentials allowing the definition of two different relaxation times called τ₁ and τ₂. This new protocol has been used to analyse the glass transition domain of amorphous PET.     

TSDC studies of the effects of plasticizer and water on the sub-T g relaxations of an epoxy resin system

The sub-glass-transition-temperature (sub-T _g relaxations of an epoxy resin system based on diglycidyl ether of bisphenol-A (DGEBA) and cured with triethylenetetramine (TETA) were investigated by means of the thermally stimulated depolarization current (TSDC) technique in the temperature range 77 K to 300 K. Three relaxation regions were observed: the γ relaxation at about 150 K, the β relaxation at 160 K to 200 K and the ω relaxation at 240 K to 270 K. The plasticization effect on the aforementioned relaxations of a plasticizer chemically connected to the epoxy resin network was investigated. The amount of plasticizer (commercial name THIOCOL LP3) was varied between 0% and 60% by weight of the epoxy. The broad range of the β relaxation reflects the heterogeneous structure of the material. The activation energies of the γ and β relaxations were calculated using the thermal sampling technique. Physical aging strongly influenced the TSDC thermogram of the ω relaxation, indicating phase separation during the aging procedure. Water effects were systematically investigated from dry samples to water-saturated samples (water content, 2.5%). In all specimens, water induced plasticization, which is expressed by the shifting of the β relaxation toward lower temperatures. The mode of water absorption (immersion in water or exposure to humid environment) also influenced the evolution of the ω relaxation.     

Segment relaxation in PBT/PC and PA6/ABS blends as studied by thermally stimulated depolarization currents

The segment relaxation in two series of binary, finely dispersed poly(butylene terephthalate)/polycarbonate (PBT/PC) and polyamide-6/acrylonitrile-buta-diene-styrene (PA6/ABS) blends was studied by the method of thermally stimulated depolarization currents (TSDC) both in normal mode (global TSDC spectra) and in thermal-sampling mode (TSDC-TS). The resulting temperature dependencies and distribution functions of segment relaxation activation energy E_asr and the influence of annealing on the relaxation behavior of the mixed phases are discussed, considering the phase morphology. Common to all blends under study are lower E _asrp (the most probable value of E _asr), narrower E _asr distribution functions, and broader temperature ranges of the glass transitions in both phases of the blend compared to those of the initial components. The relationships are in good agreement with the hypothesis on the spontaneous fractionation of polymers in blends and on the breakdown of the cooperative segment mobility regions caused by the interactions between the molecular chains of different polymers. In finely dispersed small particles of the PBT-rich phase (particle diameter ≥ 0.5 μm), a degeneration of the cooperative segment (a) relaxation in a noncooperative segment (β) relaxation caused by the solution of PC molecules in PBT was detected.     

Specific heat of around the glass transition

Dynamic calorimetric measurements are performed for the quaternary metallic glass Zr₆₅Al_7.5Cu_17.5Ni₁₀ in order to analyse the dependence on different heating rates for the glass transition temperature T_g. We compare two different temperature programs used for sample relaxation, to estimate the influence of the thermal history on T_g. A lower limit for the glass transition temperature T_g was calculated according to two different models based on the fact, that width and temperature of the glass transition depend on the experimental time scale set by the heating rate: One model assumes a Vogel-Fulcher-Tammann type behaviour, as used to describe more or less “fragile” glass formers and the other assumes an Arrhenius-like behaviour, which is related to “strong” glass formers. The values obtained from both models differ by about 80K. From additional absolute specific heat capacity measurements we calculate the Kauzmann temperature T_K, as a lower limit for the temperature of the glass transition from thermodynamic aspects. Comparing T_K with the temperature values obtained from the two evaluation models we can classify the quaternary metallic glass Zr₆₅Al_7.5Cu_17.5Ni₁₀, to behave more like a “strong” glass former. Received: 23 January 1998 / Received in final form and Accepted: 31 August 1998     

Identification of dipolar relaxations in dielectric spectra of mid-voltage cross-linked polyethylene cables

A relaxational analysis using Thermally Stimulated Depolarization Currents (TSDC) can yield a lot of information about medium voltage XLPE cables. Nevertheless, it may be difficult to find the cause of a given relaxation because dipolar and space charge relaxations need large electric fields to behave differently. Alternatively, we have used correlation between TSDC and Isothermal Depolarization Currents (IDC) data to determine the cause of a characteristic peak found in the spectra of cable samples. The analysis must assume that the relaxation is dipolar to reach a good fit of IDC data. Finally, the physical mechanism of the relaxation is discussed.     

Localized and long-distance charge hopping in fresh and thermally aged conductive copolymers of polypyrrole and polyaniline studied by combined TSDC and dc conductivity

The charge trapping centers in fresh and thermally aged conductive polyaniline-polypyrrole copolymers (starting from pure polyaniline and ending in pure polypyrrole by steps of 10 wt%) were studied by thermally stimulated depolarization current (TSDC) spectroscopy and dc conductivity measurements. One low temperature (115-135 K) relaxation mechanism appears in polyaniline-rich copolymers and disappears after thermal anneal. It is attributed to polaron trapping in the vicinity of chlorine anion dopants. Another relaxation mechanism operates close to room temperature and is related to conformational relaxation, which corresponds to the influence of the annihilation of the conformons on the conduction mechanism. The relaxation is sensitive to thermal aging as a result of the thermal annealing on the conductivity. The temperature derivative of the dc conductivity supports the latter assertion. The activation energy values were obtained as a function of composition for both fresh and heated samples. The TSDC spectroscopy is a sensitive tool which is an alternative to the standard conductivity studies for the characterization of polypyrrole-polyaniline conductive copolymers and the study of the thermal degradation.     

Ageing exploration of the energy landscape of a glass by the TSDC technique

Different thermal treatments were used in order to follow the structural relaxation of m-toluidine by thermally stimulated depolarization currents (TSDC) in the sub-T _g temperature region. In some of these thermal treatments, the ageing time, t _a, and the probing (or polarization) time, t _P, are varied independently in order to allow a clear understanding of the exploration of the energy landscape which occurs as a consequence of the structural relaxation. The TSDC results show that ageing induces a shift to higher temperatures of the TSDC peaks, in a way similar to that observed in the calorimetric heat capacity overshoot. More importantly, TSDC results show that ageing induces a decrease of the activation energies with regard to the window defined by the probing time and a sharpening of the energy distribution of the modes of motion that are present in the glass, in the studied sub-T _g temperature region.     

Dielectric relaxation properties of tysonite-type solid solutions La1−xBaxF3−x

Dielectric relaxation properties of solid solutions La_1?xBa_xF_3?x (x ? 0105) have been studied by thermally stimulated depolanzation current (TSDC)- and a c. dielectric loss (DL) techniques.For x < 30 × 10^?3 the dielectric spectra show a relaxation peak which is ascribed to a simple associate of a substitutional dopant ion and a fluoride ion vacancy (Ba_LaV_F)^x in nearest-neighbour position, the vacancy being confined to the B sublattice For x values of about 1.3 × 10^?2 a relaxation peak appears which is tentatively attributed to a similar type of defect associate with the vacancy now confined to the A sublattice of the tysonite anion array One broad relaxation peak dominates the TSDC and DL spectra over the whole concentration range This peak is due to the relaxation of macroscopic space charge, i e ionic conductivity The low-temperature ion conductivity has been determined for several solid solutions, and extrapolates to the high-temperature conductivity determined previously with impedance spectroscopy Below liquid-nitrogen temperature three relaxations are observed, and ascribed to electronic transitions in cenum impurities. A computer programme has been developed to analyse TSDC relaxation peaks, taking dipole-dipole interactions into account Relaxation parameters and dipole concentrations are presented.     

Investigation of Pendant Group and Chain Segment Motions in P(MMA/BA) Copolymers by Thermally Stimulated Depolarization Current

Poly(methyl methacrylate/butyl acrylate) [P(MMA/BA)] copolymers (M_η ～2×10⁵) with different mass percentages of MMA were synthesized by the method of solution polymerization. Thermally stimulated depolarization current (TSDC) technique was used to investigate the effect of copolymerization on pendant group and chain segment motions. Three TSDC peaks were observed over the temperature range from 310 to 400 K. The highest temperature, ρ peak originates from the detrapping of trapped charge carriers. The lower temperature, α peak corresponds to the glass transition. The activation energy of the α relaxation decreases from 1.2 eV for PMMA to 0.98 eV for MMA(75)/BA(25). In the fitting process, another peak, β′, is separated on the low temperature side. The apparent energy barrier of the β′ for PMMA is 0.80 eV. The β′ relaxation is thought to correspond to the motion of pendant groups including intra‐ and inter‐molecular interactions. All three peaks move to lower temperatures with an increase in BA component, and the activation energy for the α and β′ relaxations also decreases with the increase of BA component in copolymers, indicating that the flexible side groups of BA have an effect of plasticization on the glass transition and motion of pendent groups. The temperatures of the α and β′ peaks of P(MMA/BA) copolymers follow the Fox equation. Fitting results gives the α peak at 238 K and β′ peak at 225 K for polybutyl acrylate (PBA).     

Viscosity at the dynamic crossover in o-terphenyl and salol under high pressure

The viscosities of two prototypical glass formers, o-terphenyl and phenyl salicylate (salol), are shown to exhibit a change in their temperature and pressure dependences at a constant value of the viscosity. This is the first evidence of a dynamic crossover in the viscosity induced by pressure. The characteristic value associated with the change in dynamics is material dependent, but independent of temperature and pressure. These results are in accord with the previous finding, for other glass formers, that the dielectric relaxation time assumes a density-independent value at the dynamic crossover.     

Miscibility in poly(L-lactide)- b -poly( $ \upvarepsilon$ -caprolactone) double crystalline diblock copolymers

Thermally stimulated depolarization currents, TSDC, wide-angle X-ray scattering, WAXS, differential scanning calorimetry, DSC, and polarized light optical microscopy, PLOM, have been used to examine poly(L-lactide)-b -poly( -caprolactone) diblock copolymers in a wide composition range. Both components are crystallizable and the miscibility in the amorphous phase has been determined from the behavior of the primary relaxations which are the dielectric manifestation of the glass transition, and also from the superstructural morphology revealed by PLOM and the compositional dependence of the melting points as determined by DSC. Distinct segmental mobilities in the amorphous phase which can be well resolved by TSDC are present; the mode of the slower component shifts to lower temperatures as the PCL content increases while the glass transition of neat PCL is present for all compositions. A relaxation times bimodal distribution is apparent for PCL-rich copolymers. The composition dependence of the multiple glass transitions detected in these weakly segregated copolymers are predicted by the self-concentration model for a miscible blend made of components with a large T_g contrast.     

Glassy aging dynamics

We present time-dependent dielectric loss data for various glass formers below the glass temperature. The observed aging dynamics is described using a modified Kohlrausch-Williams-Watts law taking into account the variation of the relaxation time during aging. It leads to values for the aging relaxation time and stretching exponent, fully consistent with the results from equilibrium measurements performed at higher temperatures. Irrespective of the dynamic process prevailing in the investigated frequency region, the aging dynamics is always determined by the structural relaxation process.     

Pressure evolution of the excess wing in a type-B glass former

Glass formers are defined as "type B" when they exhibit a distinct Johari-Goldstein (JG) relaxation, but lack an excess loss ("excess wing," EW) in their structural relaxation peak. By studying the dielectric spectra of a well-known type-B glass former under high pressure, we unequivocally show the existence of an EW, simultaneously with the JG relaxation. Moreover, at very high pressures (0.6 GPa), the EW becomes a distinct relaxation peak, although correlated with the structural relaxation. The implication is that the EW, rather than the higher frequency relaxation ascribed to the JG process, is perhaps a universal feature of glass formers, albeit not always discernible at ambient pressure. Our findings may reconcile all opposing points of view present in the literature, as well as indicate that the type-A or type-B classification of glass formers should be modified or even discontinued.     

Influence of chain length on the alpha-beta bifurcation in oligomeric glass formers

A series of oligo(propylene glycol) dimethyl ethers has been investigated using dielectric spectroscopy in order to relate features of the glass transition dynamics to the number of monomer units N in the chain. The results show that (i) when scaled with the glass transition temperature, the beta relaxations systematically become faster for larger N whereas the alpha relaxations display nearly identical temperature evolutions, i.e., the alpha-beta bifurcation shifts towards shorter times for larger N, (ii) the bifurcation scenario displays a crossover in behavior at N approximately 10 monomer units, signaling the transition from oligomeric to polymeric behavior, and (iii) the beta relaxation has a cooperative nature.