Mauro Lucchesi

Dielectric response analysis of a conducting polymer dominated by the hopping charge transport

The d.c. conductivity and the electric a.c. response from 100 Hz up to 40 MHz of poly(3n-decylpyrrole) were measured in the 80-330 K interval to characterize the charge transport behaviour of the system. The d.c. conductivity well fitted the variable range hopping model, and the loss factor, after having deducted the d.c. contribution, showed a relaxation peak when the conductivity versus frequency started to rise. The strength of this relaxation increased with temperature and became too large to be related to a dipolar relaxation; moreover, the temperature dependence of the loss peak frequency and d.c. conductivity coincided. The observed relaxation was attributed to the hopping charge transport, as further confirmed by the temperature behaviour of the relaxation strength and by the frequency dependence of the exponents of the power law which locally approximate the conductivity behaviour. As the activation energy of the d.c. conductivity differed from the frequency of the loss peak, the theoretical prediction concerning the selfsimilarity of the a.c. conductivity was roughly verified.

Interdependence of Primary and Johari-Goldstein Secondary Relaxations in Glass-Forming Systems

We report evidence from broadband dielectric spectroscopy that the dynamics of the primary alpha- and secondary Johari-Goldstein (JG) beta-processes are strongly correlated in different glass-forming systems over a wide temperature T and pressure P range, in contrast with the widespread opinion of statistical independence of these processes. The alpha-beta mutual dependence is quantitatively confirmed by (a) the overall superposition of spectra measured at different T-P combinations but with an invariant alpha-relaxation time; (b) the contemporary scaling of the isothermal-pressure and isobaric-temperature dependences of the alpha-and beta-relaxation times as plotted versus the reduced variable Tg(P)/T where Tg is the glass transition temperature. These novel and model-independent evidences indicate the relevance of the JG relaxation phenomenon in glass transition, often overlooked by most current theories.

Dynamics of supercooled and glassy dipropyleneglycol dibenzoate as functions of temperature and aging: Interpretation within the coupling model framework

Dielectric relaxation measurements of a typical small molecular glassformer, dipropyleneglycol dibenzoate show the presence of two secondary relaxations. Their dynamic properties differ in the equilibrium liquid and glassy states, as well as the changes during structural recovery after rapid quenching the liquid to form a glass. These differences enable us to identify the slower secondary relaxation as the genuine Johari-Goldstein (JG) beta-relaxation, acting as the precursor of the primary alpha-relaxation. Agreement between the JG beta-relaxation time and the independent relaxation time of the coupling model leads to predicted quantitative relations between the JG beta-relaxation and the alpha-relaxation that are supported by the experimental data.

Local dielectric spectroscopy of nanocomposite materials interfaces

Local dielectric spectroscopy is performed to study how relaxation dynamics of a polyvinyl-acetate ultrathin film is influenced by inorganic nanoinclusions of a layered silicate (montmorillonite). Dielectric-loss spectra are measured by electrostatic-force microscopy in the frequency-modulation mode in ambient air. Spectral changes in both shape and relaxation time are evidenced across the boundary between pure polymer and montmorillonite sheets. Dielectric-loss imaging is also performed, evidencing spatial variations of dielectric properties near nanostructures with nanometer-scale resolution.

Adam–Gibbs model for the supercooled dynamics in the ortho-terphenyl ortho-phenylphenol mixture

Dielectric measurements of the alpha-relaxation time were carried out on a mixture of ortho-terphenyl (OTP) with ortho-phenylphenol, over a range of temperatures at two pressures, 0.1 and 28.8 MPa. These are the same conditions for which heat capacity, thermal expansivity, and compressibility measurements were reported by Takahara et al. [S. Takahara, M. Ishikawa, O. Yamamuro, and T. Matsuo, J. Phys. Chem. B 103, 3288 (1999)] for the same mixture. From the combined dynamic and thermodynamic data, we determine that density and temperature govern to an equivalent degree the variation of the relaxation times with temperature. Over the measured range, the dependence of the relaxation times on configurational entropy is in accord with the Adam-Gibbs model, and this dependence is invariant to pressure. Consistent with the implied connection between relaxation and thermodynamic properties, the kinetic and thermodynamic fragilities are found to have the same pressure independence. In comparing the relaxation properties of the mixture to those of neat OTP, density effects are stronger in the former, perhaps suggestive of less efficient packing.

Correlation of structural and Johari–Goldstein relaxations in systems vitrifying along isobaric and isothermal paths

The effect of isobaric cooling (over the range 190-350 K) and isothermal compression (up to 700 MPa) on structural α- and secondary β-relaxations has been studied for low molecular weight glass-forming systems. The shape of the α-loss peak was found to change with temperature T and pressure P but to be constant for a combination of T and P giving the same T α (T, P). The invariance of shape at constant T α (T, P) involved also the excess wing, i.e. the process showing up at the high-frequency tail of the α-loss peak in systems with no well-resolved β-process. Likewise, systems where the excess wing evolved to a well-resolved β-peak showed that the timescale of the β-process was strongly related to that of the α-peak. Also in this case, once a given value T α (T, P) was fixed, a corresponding value Tp(T, P) was found for different T and P. Same results were found also for a binary mixture of a polar rigid molecule dissolved in an apolar solvent, i.e. a model system for Johari-Goldstein intermolecular relaxation. These evidences imply that a strong correlation exists between structural α- and Johari-Goldstein relaxation over a wide interval of temperature and density.

Relaxation dynamics in tert-butylpyridine/tristyrene mixture investigated by broadband dielectric spectroscopy.

We investigated, by means of dielectric spectroscopy, the relaxation dynamics of glass forming binary mixtures composed by the quite rigid polar molecules tert-butylpyridine dissolved in the apolar solvent tristyrene. By changing the relative concentration of the components we observed a transition from a relaxation scenario with a structural process and an excess wing to that with a structural process and a well resolved secondary process. Another relaxation process, slower than the latter, was observed, well below Tg. Our detailed analysis evidenced that the secondary relaxation with shorter relaxation time can be identified as the Johari-Goldstein relaxation for all the mixtures, whereas the new relaxation process was attributed to a different type of motion of tert-butylpyridine needing a larger amount of free volume for the molecular rotation.

Pressure and temperature dependence of structural relaxation dynamics in polymers: a thermodynamic interpretation

We analyse the slowing down of the structural relaxation dynamics of polymers in terms of the Adam and Gibbs theory. We consider a previously derived general relation between the configurational and the excess entropy, which was used to derive an analytical equation for the dependence of the structural relaxation time from the pressure and temperature. The model proved to successfully fit the relaxation dynamics of poly(methyl methacrylate), poly(propylene glycol) and poly(propylene glycol dimethylether), of different molecular weights, over a wide region of temperature and pressure values above the glass transition.

Influence of the wettability on the electrical response of microporous systems

The permittivity of different microporous systems, including sintered glass filters, Berea sandstones and reservoir rocks, was measured in the frequency range 102 -1010 Hz. For each system, the natural pore wettability was modified to get two different sets of samples: those strongly oil-wet and those water-wet. The samples were saturated with a hydrocarbon oil and water at different degrees of water content. Dielectric spectra showed a conductivity contribution due to ionic carriers in addition to a Maxwell-Wagner-Sillars relaxation, active up to high frequencies. Because of the dominant role that wettability plays in the electrical response of partially saturated microporous solids, water-wet and oil-wet samples showed remarkable differences in the loss tangent spectra, as well as different times and strengths of the Maxwell-Wagner-Sillars relaxation. The dielectric spectra were analysed by using some standard models for extracting valuable information about the pore wettability. Moreover, the use of impedance measurements for in situ determination of the wettability of reservoir rocks was evaluated.

Dynamics of a glass-forming triepoxide studied by dielectric spectroscopy

Dielectric measurements of an epoxy resin, N, N-diglycidyl-4-glycidyloxyaniline, have been carried out in the supercooled and glassy phase over a broad frequency range (10 2-6 109 Hz). The measurements reveal electrical transport due to ionic impurities as well as three different dipolar relaxations—in addition to the - and -relaxation, a slower 0 -relaxation is recognized, whose loss peak is disclosed after subtraction of the dc conductivity contribution. The glass transition is found to affect markedly the secondary relaxation, whose strength and shape parameters change across Tg. The major inference from the results concerns the existence of a transition in the dynamics, occurring some tens of degrees above Tg, in the vicinity of the temperature TS where the peaks of the - and -relaxations merge. Evidence in favour of such a transition is given by: (i) the change in the temperature dependence of the -relaxation time; (ii) independently, the change in the temperature dependence of the dc conductivity; (iii) the breakdown of the Debye-Stokes-Einstein model, replaced at lower temperatures by a fractional regime. Concerning the 0 -process, it shows a Vogel-Fulcher behaviour with the same temperature T0 as the -relaxation but, unlike this last, it is not involved in a splitting phenomenon with the -relaxation. Several hypotheses concerning the nature of the 0 -process are explored.