Daniela Rusu

The objective of this study was to prepare crosslinked epoxy networks containing liquid silicone particles in order to improve their mechanical properties and obtain less brittle materials. Different copolymers were used as compatibilizers. These copolymers vary in their chemical composition and structure. All of the copolymers contain hydrophobic (PDMS sequences) and hydrophilic groups. The effect of their chemical structure and architecture on the morphology of the dispersed phase, and on the final physico-chemical and flexural characteristics of epoxy/silicone blends, was explored. The morphology of crosslinked formulations was studied by scanning electron microscopy (SEM), and the thermal characteristics (glass transition temperature, T_g, and curing exothermic peak) were determined by differential scanning calorimetry (DSC). The experimental results have shown that the average diameter and particle size distribution of silicone particles depend on the chemical structure and architecture of the compatibilizers. One copolymer has been identified as the best compatibilizer, allowing a lower mean diameter and particle size distribution in addition to the best mechanical properties of the final network (less brittle character). This study has consequently evidenced the possibility of creating in situ silicone capsules inside an epoxy network by adding tailored compatibilizers to epoxy/silicone formulations.

Partly bio-based segmented thermoplastic polyurethane (TPU) formulations were developed to fulfill the requirements of the reactive rotational molding process. They were obtained by one-shot bulk polymerization between an aliphatic diisocyanate (1,6-hexamethylene diisocyanate), a polyether polyol as macrodiol (polyethylene glycol) and a biobased corn-derived 1,3-propanediol as chain extender (CE), in presence of a catalyst, at an initial temperature of 45°C. Equivalent TPU formulations with classical petroleum-based 1,3-propanediol were also prepared for a purpose of comparison. TPU with different soft to hard segment (SS/HS) ratios were synthesized by varying the macrodiol and CE concentrations in the formulations. For each formulation, the evolution of the reaction temperature as a function of time was monitored and the kinetics of polymerization was studied by Fourier Transform infrared spectroscopy in attenuated total reflection mode (FTIR-ATR). The morphology, thermal properties, solubility in different solvents and tensile properties of the final products were analyzed. All synthesized polyurethanes are 100% linear polymers and the extent of microphase separation, as well as the thermal and mechanical properties highly depends on the HS content, and glass transition temperature and Young modulus can be tuned by adjustment of the SS/HS ratio. All results indicate that petrochemical CE can be replaced by its recently available corn-derived homologue, without sacrificing any use properties of the final polyurethanes

Low odour-emissive polylactide/cellulose fibre biocomposites, intended for car interior, were prepared and characterised. The impact of the different stages of processing (drying cycles, compounding, injection moulding) on the extent of polylactide degradation and on biocomposites properties was investigated by size exclusion chromatography, thermogravimetry, differential scanning calorimetry. In parallel, the odour emission of these materials was quantified via dynamic dilution olfactometry and Field of odours (R) method. The changes in molecular weight and global odour emission indicated that compounding had a strong impact on polylactide degradation and odour emission, while injection moulding had no significant impact. Adding 0.5 wt% of an absorbent agent based on poly(1-methylpyrrol-2-ylsquaraine could) divide the global odour concentration by a factor 2. The morphology, mechanical and thermal properties of injection moulded PLA-biocomposites were not affected by the presence of the absorbent agent

Rheological behaviour of poly(vinyl alcohol) (PVA) aqueous systems was systematically investigated at 30 °C for different concentrations, molecular weights and hydrolysis degrees. The viscosity of very dilute polymer solutions was studied by means of viscometry, while the concentrated solutions were analyzed by steady shear flow measurements. The limit between the entangled and non-entangled states of PVA aqueous solutions was determined as the crossover of two scaling laws describing the dependence of specific viscosity as a function of coil overlap parameter, c[η]. Then, physical gels with good elastic properties were prepared in situ by freezing/thawing/ageing (200 min per cycle) of entangled PVA solutions. The influence of each stage of the applied cryogenic treatment on the gel formation and elastic properties of the final network was followed by means of dynamic rheological measurements at low strain, in the linear domain of viscoelasticity. It was shown that the gel properties largely depend on the initial state of PVA solutions, as described by the c[η] value, and on the degree of hydrolysis, as well as on the thermal history, i.e., the number of cryogenic cycles, thawing rate, and ageing step. For a given coil overlap parameter, the elastic modulus of cryogels tends to a limiting value, which can be reached faster by adding an ageing sequence to the classical freezing/thawing cryogenic cycles. This maximum value of the elastic modulus increases with increasing the coil overlap value of the initial solution.

Water blown biobased thermoplastic polyurethane (TPU) foams were prepared using synthetic and biobased chain extender. The concentration of chain extender, blowing agent (BA) and surfactant were varied and their effects on physical, mechanical and morphological properties of foams were investigated. Density, compressive strength and modulus of foams decreases with an increase in BA content and increased with chain extender concentration, but do not change significantly with change in surfactant concentration. The glass-transition temperatures of the foam samples increases with an increase in BA and chain extender concentration. The cell size of the foam sample increases slightly with an increase in BA whereas chain extender concentration has no effect on cell size.

Water‐blown bio‐based thermoplastic polyurethane (TPU) formulations were developed to fulfill the requirements of the reactive rotational molding/foaming process. They were prepared using synthetic and bio‐based chain extenders. Foams were prepared by stirring polyether polyol (macrodiol), chain extender (diol), surfactant (silicone oil), chemical blowing agent (distilled water), catalyst, and diisocyanate. The concentration of chain extender, blowing agent, and surfactant were varied and their effects on foaming kinetics, physical, mechanical, and morphological properties of foams were investigated. Density, compressive strength, and modulus of foams decrease with increasing blowing agent concentration and increase with increasing chain extender concentration, but are not significantly affected by changes in surfactant concentration. The foam glass‐transition temperatures increase with increasing blowing agent and chain extender concentrations. The foam cell size slightly increases with increasing blowing agent content and decreases upon surfactant addition (without any dependence on concentration), whereas chain extender concentration has no effect on cell size. Bio‐based 1,3‐propanediol can be used successfully for the preparation TPU foams without sacrificing any properties. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

Bromine-containing methacrylate, 2-(2-bromoisobutyryloxy) ethyl methacrylate (BIEM), had been used in the formulation of acrylic radiopaque cements. The effect of this monomer incorporated into the liquid phase of acrylic bone cement (ABC), on the curing parameters, thermal properties, water absorption, density, compression tests and radiopacity was studied. A decrease of maximum temperature and an increase of the setting time were observed with the addition of the brominecontaining monomer in the radiolucent cement composition. Adding BIEM in radiolucent ABCs composition results in the decrease of glass transition temperature and increase in its thermal stability. The ABCs modified with bromine-containing comonomer are characterized by polymerization shrinkage lower than the radiolucent cement. Addition of bromine-containing comonomer in radiolucent ABC composition determines the increase of compressive strength. The ABCs modified with brominecontaining comonomer proved to be radiopaque.