Complex structural rearrangements in As-Se glasses.

Structural relaxation of As-Se glasses through the glass-to-supercooled liquid transition interval is studied with temperature-modulated differential scanning calorimetry. It is shown that connectivity of glass network and long-term physical ageing change not only the full width at half maximum of the out-of-phase component of complex heat capacity, which is conventionally used for analysis, but also its asymmetry value. The latter is shown to carry very important information on the dynamic heterogeneity in glasses. Raman spectroscopy is used as complementary technique to reveal possible structural rearrangements in the investigated glass network.

Cooperativity length scale in nanocomposites: interfacial and confinement effects.

Interfacial and confinement effects on the evolution of cooperativity on approaching the glass transition have been studied in poly(propylenecoethylene) functionalized with diethylmaleate, polyethylene 1,4-cyclohexylenedimethylene terephthalate glycol and their nanocomposites with montmorillonite. A small increase of the structural dynamic cooperativity, a weak alteration of the temperature dependence of the characteristic relaxation frequency, and no changes in the glass transition temperature observed in poly(propylenecoethylene)-based samples can be rationalized in terms of interfacial interactions between polymer and exfoliated clay. On the other hand, confinement of polymer chains in the galleries of clay (intercalated nanocomposite) produces a strong reduction of cooperativity, of the temperature dependence of the characteristic relaxation frequency, and of the glass transition temperature in polyethylene 1,4-cyclohexylenedimethylene terephthalate glycol samples. Finally, by investigating the temperature dependence of a generalized fragility and of cooperativity, we evidenced that fragility of glass formers is determined not only by cooperativity.

Temperature dependence of the characteristic length scale for glassy dynamics: combination of dielectric and specific heat spectroscopy.

The temperature dependence of characteristic length scales associated to the glass transition such as the cooperativity length scale introduced by Adam and Gibbs [cooperative rearranging region (CRR)] or the dynamic heterogeneity as estimated from the four point correlation function chi4, is at the center of large interests. Broadband dielectric spectroscopy and temperature modulated differential scanning calorimetry allow to study the CRR size temperature dependence in the temperature range of ergodicity loss for glass-forming liquids, starting from the onset of cooperativity in the crossover region down to the glass transition temperature. Furthermore, the correlation between these two techniques allows to explore a large frequency range (from 1 mHz to 10 MHz). The goal of this work is to follow the cooperativity evolution along the Arrhenius plot for two different polymeric systems: poly(ethylene 1,4-cyclohexylenedimethylene terephthalate glycol) and poly(bisphenol A carbonate).

Bond fluctuation model to describe physical aging in polymeric materials.

The thermal behavior of a polymeric material during a cooling ramp was simulated by means of the bond fluctuation model. By introducing both an intramolecular and an intermolecular potential, if the cooling rate is fast enough, the glass transition occurs, and the states attained at low temperatures can be characterized as disordered glasses. The evolution of the resulting amorphous systems was then studied during isothermal periods both for systems starting as an amorphous liquid and as an amorphous glass. The results show that after a very long annealing time at temperatures above the glass transition, an excess of energy loss appears in the system when compared to the usual glass theory. The Monte Carlo method was used to simulate the physical aging phenomena at long time scales.

Cooperative rearranging region size and free volume in As-Se glasses.

Glasses of the As-Se system have been used as model objects of the covalent disordered inorganic polymers to investigate the correlation between the cooperative rearranging region (CRR) size determined at the glass transition temperature and the free volume fraction in the glassy state. The CRR size has been determined using temperature modulated differential scanning calorimetry data according to Donth's approach, while the free volume fraction in the investigated materials has been estimated using positron annihilation lifetime spectroscopy data. The obtained results testify that the appearance of open-volume defects greater than 80 Å(3) leads to a significant decrease in the CRR size.

Transmission line matrix modelling of thermal injuries to skin.

A numerical model based on the transmission line matrix method is presented for the quantitative prediction of skin burn resulting from exposure of a specific region of human skin surface to a high temperature heat source. Transient temperatures were numerically estimated by Pennes' bioheat equation, and the damage function denoting the extent of burn was calculated using the Arrhenius assumptions for protein damage rate. A two-dimensional transmission line matrix model was used to predict the effects of exposure time and structure thicknesses on the transient temperature distribution and damage extent. Compared with other numerical sources the transmission line matrix results revealed good agreement, suggesting that this method may be an effective tool for the thermal diagnostic of burns.

The kinetics of the structural relaxation process in PHEMA-silica nanocomposites based on an equation for the configurational entropy.

The enthalpy relaxation of polymer-silica nanocomposites prepared by simultaneous polymerization of poly(2-hydroxyethyl methacrylate) (PHEMA) and tetraethyloxysilane, TEOS, a silica precursor, is investigated. Both the glass transition temperature, Tg, and the temperature interval of the glass transition, DeltaTg , increase as the silica content in the sample does. Structural relaxation experiments show that the temperature interval in which conformational motions take place broadens as the silica content in the hybrid increases. A phenomenological model based on the evolution of the configurational entropy during the structural relaxation process, the SC model, has been used for determining the temperature dependence of the relaxation times during the process. The results show an increase of the fragility of the polymer as the silica content increases, a feature that can be related to the broadening of the distribution of relaxation times characterized by the beta parameter of the stretched exponential distribution. On another hand the silica content increase produces a significant change of the relaxation times in the glassy state.

Occurrence of sessile Pseudomonas oryzihabitans from a karstified chalk aquifer.

Pseudomonas oryzihabitans is an uncommon pathogen that may cause opportunistic infections. Although it has been previously isolated from the environment, the source of human infection has not been well documented. In this study, we describe the presence of P. oryzihabitans adhering on suspended particulate matters recovered from karst groundwaters. The isolated pathogen was capable of forming biofilms on silicon supports and clay beads. Adherent P. oryzihabitans cells displayed a high resistance to chlorine as compared with the same organisms cultured in the planktonic mode. These results demonstrate that aquifer biofilms are potential environmental sources for water-born P. oryzihabitans infections and that bacterial attachment might affect drinking water purification.