Antoine Rouilly

Thermo-mechanical processing of sugar beet pulp. III. Study of extruded films improvement with various plasticizers and cross-linkers

Thermoplastic sugar beet pulp (thermo-mechanical processing was discussed in previous studies) was formed into film strips by extrusion. Film tensile properties are discussed according to the molecular structure of external plasticizer. Sorbitol, fructose and adipic acid have a marked antiplasticizing effect, while urea and xylitol gave higher ultimate tensile stress than glycerol for a comparable strain at break. Xylitol can be considered as the best plasticizer with UTS and EL of, respectively, 4.9 MPa and 11.3% and water absorption (85% RH, 25 degrees C) was less than 25%. Glycidyl methacrylate was directly used in the extrusion process as cross-linker. In high humidity atmosphere (97% RH, 25 degrees C), film water absorption was then kept under 40% while tensile strength and strain were improved of 50% and with a 30 min UV post-treatment the mass gain in absorption was even less than 30% after 5 days.

Influence of DE-value on the physicochemical properties of maltodextrin for melt extrusion processes

In this study, five different types of maltodextrins (DE-2, DE-6, DE-12, DE-17 and DE-19) were characterized for the physico-chemical properties. TGA, DVS and SEC analyses were carried out and additionally apparent melt-viscosity (in a micro-extruder) and the glass transition temperature (analyzed by DMA) of maltodextrin/plasticizer mixtures were also measured in order to evaluate both the effect of plasticizer nature and content and the effect of the DE-value. For this, three plasticizing agents were compared: water, d-sorbitol and glycerin. The adsorption isotherms showed that depending on the DE-value and the relative humidity they were exposed to, different behavior could be obtained. For example, for relative humidities below 60% RH maltodextrin DE-2 was the least hygroscopic. And on the contrary for relative humidities above 75% RH maltodextrin DE-2 was the most hygroscopic. The rheology measurements showed that the viscosity decreased with the increase of the DE-value and with the plasticizer content, as expected. On the contrary, no direct correlation could be established between the DE-value and the glass transition temperature. These results demonstrated that to predict maltodextrins behavior and to better adapt the process conditions, combined analyses are mandatory as the DE-value alone is not sufficient. The most compelling evidence was obtained by size exclusion chromatography, which pointed out that maltodextrins had a bimodal molecular weight distribution composed of high and low molecular weight oligo-saccharides. Indeed, maltodextrins are highly polydisperse materials (i.e. polydispersity index ranging from 5 to 12) and that should be the reason why such distinct behaviors were observed in some of the physico-chemical analyses that were preformed.

Melt Extrusion Encapsulation of Flavors: A Review

Encapsulation of flavor and aroma compounds has been largely explored in order to meet appraisal demands from consumers by improving the impact of flavor during the consumption of food products. Even though several techniques have been used for encapsulating volatile compounds, i.e., spray drying, fluidized bed coating, coacervation, and melt extrusion, those most frequently used in the food industry are spray drying and melt extrusion. In this article, the different techniques of encapsulation of flavors and fragrances in polymer-based matrices by extrusion are reviewed and partly re-defined, emphasizing the differences between the various techniques reported so far and the role of matrix types, additives, and operative conditions. Also, the role of water as a key parameter for controlled release and shelf stability of the delivery system will be discussed.

CHAPTER 7:Industrial Use of Oil Cakes for Material Applications

Sunflower is an ideal example of a totally utilisable nonfood industrial crop. The oil is used to produce biodiesel and the oil cake, the extraction byproduct, is a valuable candidate to make 100% natural thermoplastic composites. Made of the remainings of crushed kernel and husks, sunflower oil cake (SFOC) is composed mainly of storage proteins and lignocellulosic fibres, which can be considered, respectively, as matrix and fibre reinforcement. Sunflower proteins, structurally close to soy proteins, are known for their plastic properties. They are discussed in the chapter through their thermal behavior (glass transition, denaturation) and their mechanical characteristics of formed materials by casting, thermomoulding and extrusion. Thermomechanical twin-screw extrusion processing of the raw SFOC is a way to perform, in one-step, the plasticisation of the protein matrix, the defibration of the husk and the compounding of the thermoplastic composite. The conditions of such processing are presented including their influence on the SFOC microstructure, protein denaturation and melt rheology of the composite. The effect of the compounding treatment is then related to the mechanical properties of materials obtained by injection moulding. A specific chemical treatment using a food-reducing agent allows optimum properties to be achieved. A preindustrial study of the process is lastly discussed. Examples of industrial materials are presented, some as agricultural transplanting pots, which take advantage of the specific water resistance of these protein-based composites. This example is then developed in terms of economic feasibility (the scale up of the process) and environmental benefits.

Twin-Screw Extrusion: A Key Technology for the Biorefinery

For more than 30 years, the Laboratory of Agro-industrial Chemistry (LCA) develops an ambitious and multi-scale research topic on the use of twin-screw extrusion (TSE) for the processing of biomass for non-food applications. This chapter will give an overview of past and present projects, discussing specific operating conditions and their consequences on biopolymer native organization. For the production of agro-materials, compounding processes have been designed and in some cases industrialized integrating specific targeted actions such as the plasticization of primary cell-walls (sugar beet, tobacco), the “fusion” of storage polymers (starch, oilseed proteins) and/or the destructuring of secondary cell-walls (lignocellulosic fibers). For the pretreatment of lignocellulosic fibers, the conjugated use of chemicals is also discussed. Those processes have also been coupled with biodegradable polyester blending (involving compatibilization with acid citric) and compounding. In integrated biorefining processes, TSE may also be used simultaneously as a continuous liquid-solid extractor through mechanical pressing or solvent extraction, for extracting oil, polysaccharides, proteins, polyphenols or hydroxycinnamic acids and as a pre-treatment of the fibrous raffinate. This is especially efficient for the processing of oilseed crops and the production of binderless fiberboards or to prepare technical fibers for composite applications. This has been widely demonstrated on sunflower, jatropha or more recently coriander. Finally, in the bioenergy field, a specific pretreatment process for the production of bioethanol from lignocellulosic feedstock has been developed and is actually in the up-scaling phase. Integrating the use of enzymes in a one-step TSE, this process has been called “bioextrusion”.

Characterization of Non-Derivatized Cellulose Samples by Size Exclusion Chromatography in Tetrabutylammonium Fluoride/Dimethylsulfoxide (TBAF/DMSO)

This paper deals with the use of tetrabutylammonium fluoride/dimethylsulfoxide (TBAF/DMSO) to characterize the molar mass distribution of non-derivatized cellulosic samples by size exclusion chromatography (SEC). Different cellulose samples with various average degree of polymerization (DP) were first solubilized in this solvent system, with increasing TBAF rates, and then analyzed by SEC coupled to a refractive index detector (RID), using DMSO as mobile phase. The Molar Masses (MM) obtained by conventional calibration were then discussed and compared with suppliers’ data and MM determined by viscosimetry measurements. By this non-classic method, molar mass of low DP samples (Avicel® and cotton fibers) have been determined. For high DP samples (α-cellulose and Vitacel®), dissolution with TBAF concentration of 10 mg/mL involved elution of cellulose aggregates in the exclusion volume, related to an incomplete dissolution or the dilution of TBAF molecules in elution solvent, preventing the correct evaluation of their molar mass.

Chapter 2:Farming and Harvesting

The competitiveness and sustainability of the biodiesel and vegetable oil market can be achieved through increasing the quantity of total biomass cultivated and the yield of the vegetable oil. Furthermore, pre-treatment technologies aiming to increase the bulk density and decrease the water content of the biomass can be employed to reduce the cost of biomass transportation and storage. The valorisation of the by-products (straw, stalk, leaves) through conversion processes into high-value-added chemicals and biomaterials as well as energy also contributes to improving the economics of the whole biorefinery scheme.