Eric Dantras

Surface, core, and structure modifications of phosphorus-containing dendrimers. Influence on the thermal stability

Three new series of phosphorus-containing dendrimers are described. Their solubility depends on the type of end groups they bear. Perfluoroalkyl chains give dendrimers soluble in chlorofluorocarbons, whereas guanidinium and pyridinium derivatives give watersoluble compounds. The thermal stability of these compounds, as well as of 19 other dendrimers of various generations, having various cores, or various end groups, or branching points is studied. The main feature of this study is that the internal structure of these dendrimers is thermally stable at least up to 3768C. The number of the generation has practically no influence, whereas the principal criterion influencing the thermal stability is the type of end groups. The water-soluble cationic dendrimers are the least stable, but even those are stable up to 2258C. For most of these dendrimers, an important percentage of mass (around 50%) is retained even at a temperature as high as 10008C. In the best case, up to 70% of the initial mass is retained at 10008C.

Influence of hydrogen bonds on glass transition and dielectric relaxations of cellulose

The molecular dynamics in hydrated cellulose has been investigated by a combination of thermal analyses and dielectric spectroscopy. Differential scanning calorimetry shows the dependence upon hydration of the glass transition temperature Tg. A physical ageing phenomenon has been observed. At the molecular scale, bound water is hydrogen bonded to polar sites of cellulose macromolecules. At the macroscopic scale, water molecules play the role of a plasticizer for cellulose lowering its Tg. Dynamic dielectric spectroscopy combined with thermostimulated currents have allowed us to follow more localized molecular mobility. The β relaxation mode is characterized by activation entropies that vanish for higher water contents indicating molecular mobility localization. It is plasticized by water like the glass transition. This analogy is explained by a common origin of both mechanisms: the mobility of the cellulose backbone. The evolution of the γ mode upon hydration follows an anti-compensation law. Water acts as an anti-plasticizer in a hydrogen bonded network.

Structural and electrical properties of gold nanowires/P(VDF-TrFE) nanocomposites

High aspect ratio gold nanowires were uniformly dispersed into a poly(vinylidene difluoride–trifluoroethylene) [P(VDF-TrFE)] matrix. The nanowires were synthesized by electrodeposition using nanoporous anodic alumina oxide templates. The intrinsic optical conductivity of the gold nanowires was determined by valence electron energy loss spectroscopy. The effect of increasing volume fraction of Au nanowires on the morphology and crystallization of P(VDF-TrFE) matrix was investigated by differential scanning calorimetry. The crystallinity of P(VDF-TrFE) is strongly depressed by the randomly dispersed nanowires. Above 30 vol% the crystallization of P(VDF-TrFE) is suppressed. The bulk electrical conductivity of nanocomposite films, at room temperature, obeys a percolation behaviour at a low threshold of 2.2 vol% and this was confirmed using the surface resistivity value. An electrical conductivity of 100 S m−1 is achieved for a 3 vol% filler content.

Piezoelectric properties of polyamide 11/NaNbO3nanowire composites

Polyamide 11(PA 11)/sodium niobate nanowire (NW) 0–3 composites with different volume fractions of NWs were synthesized. The electric polarization (P) was measured as a function of the applied electric field (E). The P–E hysteresis loop was used to work out the remanent polarization Pr of these materials. The dielectric permittivity and the piezoelectric strain constant were determined. Good impedance matching between inorganic and organic phases leads to higher electroactivity than conventional lead-free 0–3 composites. The piezoelectric voltage of the PA 11/NaNbO3 NW composites is of the same order as those obtained for fluorinated piezoelectric polymers. These composites could have some applications in flexible, low-cost, environmentally friendly piezoelectric sensors and actuators.

Dynamic mechanical properties of oral mucosa: Comparison with polymeric soft denture liners

The purpose of this work was to characterize the viscoelastic behaviour of oral mucosa and compare it with the dynamic mechanical properties of different soft liners. For this purpose, a sample of pig oral mucosa and six commercialized soft liner samples have been investigated. A comparison was also carried with the first suitable hard rubber for dental prosthetics: vulcanite. Creep recovery (CR) and dynamic mechanical analysis (DMA) have been used to determine the mechanical modulus of oral mucosa and soft liners respectively. The Poisson ratio is used to compare mucosa bulk modulus and soft liner shear modulus. The biomechanical concept of conventional complete dentures needs a good adjustment of dynamic mechanical impedance between the base and oral mucosa. The viscoelastic mechanical property of the oral mucosa as a referent biopolymer has been confirmed in vitro. The modulus value, adjusted for old patients in physiological conditions, is in the order of 3 MPa. This study underlines the plasticization effect of absorbed water on the mechanical properties of the underlying tissue. This study allows us to define some characteristics of the most adapted biomaterial according to the clinical exigency. The required biomaterial must display the following properties: compatibility and chemical resistance with biological environment perpetuated mechanical properties during physiological conditions and clinical use, good adjustment of dynamic mechanical impedance with supporting mucosa and easy sample processing.

Aging Effect and Induced Electric Phenomena on Dielectric Materials Irradiated With High Energy Electrons

The high radiation dose received by space used polymers may greatly alter their electric properties. This effect could, for instance, reduce significantly radiation-induced conductivity (RIC) leading to high charging risks that were not predicted from pristine sample. For an optimized qualification and prediction, it is therefore highly important to characterize the charging properties of polymers and their evolution as a function of the received dose. This paper aimed at studying aging of electric properties of four different polymers (Teflon FEP, Kapton, polyepoxy DP 490 adhesive, and silicon QS1123 adhesive) at high dose level (105 and 106 Gy). We have been able to demonstrate that aging could lead to the reduction of RIC on some polymers (for polyepoxy and silicone adhesives, and FEP) or inversely to the increase of RIC on others (e.g., Kapton). Ionization effect must, however, be considered in the analysis of the results. Relaxation processes could drastically affect the charging profile and macroscopic electric properties.

Dielectric study of local relaxations in dendritic macromolecules

The aim of this work is to characterize the dielectric properties of amorphous dendritic macromolecules as a function of architectural complexity. By combining thermostimulated currents and dynamic dielectric spectroscopy, the dielectric permittivity has been obtained as a function of temperature, in a very broad frequency range (10−4–106 Hz). Generations g = 0 to g = 2 were investigated. The molecular origin of the quasi-Debye mode observed for g = 0 at low temperature is common to all generations: localized reorientations of aldehyde end groups. The interactions with the phosphorus/sulfur (P = S) dipoles are probably responsible for the broadening pointed out in upper generations.

Dielectric relaxations in amorphous polymers with complex chain architectures

By combining thermostimulated current and dynamic dielectric spectroscopies, the dielectric properties characteristic of the molecular mobility can be described over a very broad frequency range. The study of dielectric relaxations of phosphorus-containing dendrimers in the sub-glass transition region, and of poly(n-alkyl methacrylates) at and above the glass transition region allows us to gain insight into the molecular dynamics of complex architecture systems. From these sets of data we make an attempt to propose a structural interpretation of molecular mobility through the glass transition.

Polymerization study and rheological behavior of a RTM6 epoxy resin system during preprocessing step

Curing process and rheological behaviors of a monocomposant epoxy resin used in structural aeronautic applications are investigated. This study helped settle the basic parameters in order to optimize the infusion process of carbon fibers in an epoxy matrix. The effect of carbon nanotube dispersion during the preinjection step is also studied to improve electrical behavior of composite parts. The curing process has been analyzed at isothermal temperature using differential scanning calorimetry technique. Viscosity measurements were achieved with a Couette geometry, suitable for low viscosity resin. A shear-thinning effect caused by adding CNTs in the epoxy matrix is detected. It is more pronounced at high temperature for increasing CNT mass content.

Electrical behaviour of a silicone elastomer under simulated space environment

The electrical behavior of a space-used silicone elastomer was characterized using surface potential decay and dynamic dielectric spectroscopy techniques. In both cases, the dielectric manifestation of the glass transition (dipole orientation) and a charge transport phenomenon were observed. An unexpected linear increase of the surface potential with temperature was observed around Tg in thermally-stimulated potential decay experiments, due to molecular mobility limiting dipolar orientation in one hand, and 3D thermal expansion reducing the materials capacitance in the other hand. At higher temperatures, the charge transport process, believed to be thermally activated electron hopping with an activation energy of about 0.4 eV, was studied with and without the silica and iron oxide fillers present in the commercial material. These fillers were found to play a preponderant role in the low-frequency electrical conductivity of this silicone elastomer, probably through a Maxwell–Wagner–Sillars relaxation phenomenon.