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[h]. 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[h] 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.

International audienceThis work presents an in situ experimental investigation of the shear-induced coalescence mechanism in low concentration polymer blends (1%-10%). An original sizing method based on small-angle light scattering and optical microscopy were used to determine the evolution of the drop size distributions as a function of time. In order to study the pure coalescence mechanisms, measurements were conducted according to a specific flow protocol. The influences of the shear rate, initial morphology, concentration of the polymer blend and phase inversion on the coalescence kinetics were investigated. The investigated blends are mixtures of polydimethylsiloxane and polyisobutene. The amount of strain, the step-down rate ratio and the concentration squared are identified as relevant parameters to describe the coalescence kinetics. The dependence of the steady state drop sizes on the applied shear rate is well described by a coalescence model considering partially mobile interfaces

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.

Abstract. 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 ® 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 PLAbiocomposites were not affected by the presence of the absorbent agent.

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The aim of this work was to investigate the rheological properties of different saline solutions of sodium hyaluronate (NaHA) with special interest for medical applications. The experimental results were compared with literature data for commercial ophthalmic viscosurgical devices (OVDs) used in cataract surgery. We offer some tools to tailor the rheological behavior of OVDs for different purposes. We have investigated to which extent surgical requirements can be fulfilled by adjusting either the molecular weight of NaHA or its concentration, parameters that are in some respects equivalent but not in others. Furthermore, we demonstrate that moduli and complex viscosities of NaHA saline solutions are adequately falling on master curves, using either empirical or calculated shift factors, the latest ones being based on a modified Rouse model.

Abstract. 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.

A method for determining diffusion coefficients during shear by dynamic light scattering is presented. The direct determination of diffusion coefficient during flow is hampered by the domination of the convection terms over the diffusion terms except in a very narrow azimuthal scattering angle range that is impossible to reach experimentally. The method described here offers the advantage to this constraint. The technique is based on a double measurement of homodyne spectrum of light scattered from small scatterers immersed in a medium subjected to a simple shear flow. This can be applied to polymer solutions. Verification is provided using suspensions of polystyrene spheres in Newtonian media and a transparent rheometer. ᭧