Bruno Vergnes

Influence of amylose content on the viscous behavior of low hydrated molten starches

Starches with various amylose contents (0%–70%) were processed on a twin‐screw extruder equipped with a special slit die rheometer. Relationships between thermomechanical treatment and starch macromolecular degradation are defined, and flow curves are discussed in order to determine the role of moisture content, product temperature, and mechanical energy on melt viscosity. The viscous behavior is described by a power‐law expression. Viscosity is more sensitive to moisture content and macromolecular degradation at lower amylose contents. Using multiple regression analysis, expressions for the different starches are proposed to describe the influence on the viscosity of amylopectin, which is the macromolecular component with short chain branching. The main differences observed when decreasing the amylose content are a lower viscosity and less pronounced shear thinning. These effects are interpreted in terms of entanglements.

RELATIONSHIP BETWEEN STRUCTURE AND VISCOELASTIC BEHAVIOR OF PLASTICIZED STARCH

The linear viscoelastic behavior of starches from various origins, blended with different amounts of a plasticizer using a twin screw extruder, has been investigated. Conditions of stability for reliable measurements and linearity domain have been determined. At low strain, the plasticized starch is found to behave as a viscoelastic gel-like material. This behavior is partially explained by its semicrystalline structure, as evidenced by x-ray diffraction patterns. Crystallites are assumed to participate in the formation of an elastic network, embedded in a viscoelastic amorphous phase. Additional thermomechanical treatment reduces crystallinity and leads to a decrease of the storage and loss moduli. The plasticizing role of water is found to be important. The higher molecular weight of the potato starch is responsible for its larger moduli. In the case of maize starch, the highly branched amorphous amylopectin softens the structured behavior, resulting in lower moduli compared to those of rich-content amy...

Viscous Properties of Thermoplastic Starches from Different Botanical Origin

Abstract Starches from various botanical origins were plasticized in a twin screw extruder with different glycerol contents (from 23 to 32%, total wet basis) in order to prepare pellets of amorphous thermoplastic starches (TPS) that can further be processed for manufacturing purposes. The viscous behaviour of these starches was studied with a capillary pre-shearing rheometer, which achieved an homogeneous molten phase under controlled thermomechanical conditions. After performing Bagley corrections and Rabinowitsch analysis, it was found that all samples exhibited a non-Newtonian shear-thinning behaviour, which could be modeled in the range 1 to 103 s−1 either by a simple power law or by a Herschel-Bulkley relationship. For the consistency index, the influence of temperature and plasticizer content was accounted for by Arrhenius-like laws, applying time-temperature and time-plasticizer superposition. For the same plasticizer content and temperature, comparison of starches from different botanical origins showed that shear viscosity values usually increased with the starch amylose content. This trend was partly confirmed for the elongational behaviour, estimated by the Cogswells analysis of entrance effects. These results can be interpreted by the greater ability of linear molecules of amylose to entangle, compared to the more compact amylopectin molecules.

Grafting of maleic anhydride on polypropylene by reactive extrusion: effect of maleic anhydride and peroxide concentrations on reaction yield and products characteristics

Abstract A series of polypropylenes (PPs) grafted with maleic anhydride (MA), prepared by reactive extrusion in a twin screw extruder with different contents of peroxide and MA, was characterized. For each sample, the amount of grafted MA, the molecular weight distribution, the viscoelastic properties in small amplitude oscillatory shear and the transition temperatures and enthalpies were measured. The respective influence of initial MA and peroxide concentrations on these parameters was characterized. In particular, it was shown that the rheological properties are only controlled by the molecular weight, whatever the way it has been obtained, by varying either MA content or peroxide concentration. Moreover, it is clearly shown that the presence of MA tends to enhance the PP degradation due to the peroxide.

Phenomenological model of maize starches expansion by extrusion

During extrusion of starchy products, the molten material is forced through a die so that the sudden abrupt pressure drop causes part of the water to vaporize giving an expanded, cellular structure. The objective of this work was to elaborate a phenomenological model of expansion and couple it with Ludovic® mechanistic model of twin screw extrusion process. From experimental results that cover a wide range of thermomechanical conditions, a concept map of influence relationships between input and output variables was built. It took into account the phenomena of bubbles nucleation, growth, coalescence, shrinkage and setting, in a viscoelastic medium. The input variables were the moisture content MC , melt temperature T, specific mechanical energy SME , shear viscosity η at the die exit, computed by Ludovic®, and the melt storage moduli E’(at T > T g ). The outputs of the model were the macrostructure (volumetric expansion index VEI, anisotropy) and cellular structure (fineness F) of solid foams. Then a general model was established: VEI = α (η/η 0) n in which α and n depend on T, MC , SME and E’ and the link between anisotropy and fineness was established.