TPV Foaming by CO2 Extrusion: Processing and Modelling.

This work focuses on the extrusion foaming under CO2 of commercial TPV and how the process influences the final morphology of the foam. Moreover, numerical modelling of the cell growth of the extrusion foaming is developed. The results show how a precise control on the saturation pressure, die geometry, temperature and nucleation can provide a homogeneous foam having a low density (<500 kg/m3). This work demonstrates that an optimum of CO2 content must be determined to control the coalescence phenomenon that appears for high levels of CO2. This is explained by longer residence times in the die (time of growth under confinement) and an early nucleation (expansion on the die destabilizes the polymer flow). Finally, this work proposes a model to predict the influence of CO2 on the flow (plasticizing effect) and a global model to simulate the extrusion process and foaming inside and outside the die. For well-chosen nucleation parameters, the model predicts the final mean radius of the cell foam as well as final foam density.

Kinetics of geopolymerization followed by rheology: a general model.

The geopolymerization process necessitates the activation of an aluminosilicate source by an alkaline solution. Its kinetics is followed by rheology. The storage modulus (G') and loss modulus (G'') are monitored through oscillatory rheological measurements from the early stage, geopolymer paste, to the gel point with the formation of a geopolymer network. The results show that the temperature increase shortens the reaction time. The principle of Reaction Time-Temperature Superposition (RTTS) is introduced to predict this phenomenon. Furthermore, it is pointed out that using metakaolin blends with different reactivities allows modifying and controlling the reaction time. A critical weight fraction of reactive metakaolin is identified as necessary for the formation of the geopolymer network. The reaction times of the different formulations are linked to the temperature and the weight fraction of metakaolin by the Arrhenius law. A model is established to predict the reaction time according to the temperature and the weight fraction between the two metakaolins used.

Thermo-mechanical properties and blend behaviour of cellulose acetate/lactates and acid systems: Natural-based plasticizers.

This work brings together thermo-mechanical and structural information for plasticized cellulose acetate (CA) by lactates and octanoic acid. CA are processed with plasticizer due to their high Tg and their strong H-bonding network. We prepared CA / plasticizer blends by corotative twin screw extruder and by solvent casting methods. The study of the different relaxations and of the glassy zone modulus was performed by dynamic mechanical analysis (DMA). The miscibility range of cellulose acetate blends were identified by the analysis of the tan δ. Depending on the composition of the system, one or two transitions are noted, this last result indicates the presence of a phase rich in CA and another in plasticizer. To connect this information to crystallinity and molecular organization, X-ray diffraction analyses were carried out. The disappearance of crystallinity allows the plasticization of previously inaccessible zones, causing a glassy modulus drop of more than 1000 MPa.

Plasticizing effect of ionic liquid on cellulose acetate obtained by melt processing.

Cellulose acetate (CA) plasticized by 1-butyl-3-methylimidazolium chloride (BMIMCl) and with diethylphtalate (DEP) was obtained by melt processing at 150°C. The effect and the interaction of ionic liquid with the cellulose acetate and their influence on structural, thermo-mechanical, rheological and tensile properties of CA materials were investigated. Ionic liquid (BMIMCl) has shown a good plasticization and more efficient destruction of the crystalline structure of cellulose acetate than the DEP plasticized CA. BMIMCl interacts intensively with CA molecules due to the pronounced van der Waals interactions, hydrogen bonding and electrostatic nature of ionic liquid. The tensile test and the low Young's modulus for plasticized CA suggest a strong reduction of the interaction between the CA chains due to the presence of the ionic liquid.

Effects of relative humidity and ionic liquids on the water content and glass transition of plasticized starch.

The purpose of the present work was to investigate the relationship between the glass transition temperature of the materials produced by the melting method and the water content, as well as the nature and concentration of the plasticizer used. Native starch was successfully treated with ionic liquid to obtain thermoplastic starch (TPS). Ionic liquids have shown a better plasticization, and low absorption of water compared to glycerol, which means a better interaction of starch with ionic liquids. The water binding properties of TPS were studied by commenting the water absorption for the plasticized starch at different % RH and with different ratios of plasticizers. An amount of 22.5 wt% AMIMCl is the maximum that can act as a plasticizer. Above this composition, an increase in the wt% water and wt% AMIMCl induces a phase separation. This value corresponds to a chemical interpretation, which corresponds to a ratio of 1:3 AMIMCl/anhydro-glucose. A schematic representation of the different binding between starch, plasticizer and water has been proposed.