Manufacturing of renewable and biodegradable fiberboards from cake generated during biorefinery of sunflower whole plant in twin-screw extruder: Influence of thermo-pressing conditions

The starting material used in this study was a cake generated during thermo-mechanical fractionation of sunflower (Helianthus annuus L.) whole plant in a twin-screw extruder. It was slightly deoiled (16.7% of oil in dry matter). Composed mainly of fibers and proteins, it could be considered as a natural composite and was processed successfully into fiberboards by thermo-pressing. This study aimed to evaluate the influence of thermo-pressing conditions on mechanical and heat insulation properties of fiberboards manufactured from this cake. All fiberboards were cohesive, proteins and fibers acting respectively as binder and reinforcing fillers. Highest cake quantity (1000 mg/cm²) led to the highest breaking load (60.7 N) with a flexural strength at break quite low (2.9 MPa), lowest elastic modulus (216.6 MPa), and highest Charpy impact strength (6.5 kJ/m² for resilience). The increase of pressure applied during molding (from 320 to 360 kgf/cm²) led to an important increase of elastic modulus (from 352.6 to 728.6 MPa). Besides, fiberboard molded at 360 kgf/cm² was the most rigid of this study, and logically revealed the most important Shore D surface hardness (52.6°). Moreover, lowest molding time (60 s) led to the highest flexural strength at break (3.9 MPa). The low density of the fiberboards (less than 0.97) involved promising heat insulation properties. Indeed, thermal conductivity of fiberboards at 25 °C was low (from 103.5 to 135.7 mW/m K), and decreased with the increase of thickness. According to their mechanical and heat insulation properties, fiberboards would be potentially usable as inter-layer sheets for pallets, for the manufacture of biodegradable containers (composters, crates for vegetable gardening) by assembly of fiberboards, or for their heat insulation properties in building industry. Moreover, thermo-pressing was not only a molding operation. It also improved the oil extraction efficiency as a part of residual oil was expressed from cake during molding, and total oil yield reached 79.3% with a pressure applied of 360 kgf/cm²

Thermo-mechanical processing of sugar beet pulp. I. Twin-screw extrusion process

Sugar beet pulp (SBP) is the raffinate of sugar extraction. Composed of empty vegetal cells, three quarters of it consist of polysaccharides. As it is cheap and produced in great quantities SBP is a potential raw material for industrial applications other than cattle feeding. Twin-screw extrusion modified its structure and destructuring level depended on the specific mechanical energy provided (SME). By gradually increasing this energy, the rate of soluble matter increased, cell structure was progressively destroyed and SBP rheological behaviour was modified. For an SME of 745 W h kg-1, SBP examined through a scanning electron microscope showed a structure similar to that of a composite formed by a continued matrix consisting mainly of pectin and hemicelluloses filled with cellulose microfibres. Plasticized SBP was then formed by injection-molding. Thus treated, SBP becomes a cheap alternative to the use of thermoplastic starch for the production of biodegradable materials

Synthesis and properties of composites of starch and chemically modified natural rubber

A means is developed for forming polysaccharide-based composites with useful material properties through use of unmodified and chemically modified natural rubber latex (NRL). Starch was used as a model for polysaccharides. The NRL was modified by grafting with dimethylaminoethyl methacrylate (DMAEMA) to form a latex with cationic water-soluble polymeric “hairs” of polyDMAEMA, which should form hydrogen bonds with starch. Starch solutions, containing 20% glycerol as a film-forming aid, and the modified NRL were mixed and films allowed to form. The unmodified latex acted only as filler in the starch films, but with modified NRL, the mechanical properties of the films were significantly altered. The elastic modulus was greatly decreased and strain at break greatly increased. The glass transition temperature increased from –48°C to –32°C, suggesting significant compatibilization. Freeze-fracture TEM micrographs indicate strong interactions between the surface of the modified NRL and starch. The polyDMAEMA chains are more hydrophilic than the starch, and the addition of grafted latex results in a 20° drop of the water contact angle of the formed film, and a 25% increase of the water absorption compared to the native starch; with unmodified NRL, the opposite effect was observed

Thermo-mechanical processing of sugar beet pulp. II. Thermal and rheological properties of thermoplastic SBP

Thermoplastic properties of extruded sugar beet pulp (SBP) are closely linked to water–polymer relationships. DSC analyses of water evaporation, water fusion and biopolymer relaxation according to SBP moisture content gave a more accurate estimation of SBP hydration steps than classical water adsorption isotherm. Three moisture contents (8%, 26%, 41% db) were then defined as limits of the different hydration behaviours. Melt viscosity measurements of SBP showed its shear thinning behaviour and the measured apparent viscosity is in the same range as thermoplastic starch viscosity. Using only water as plasticizer, to one temperature corresponded one moisture content to reach the optimal flowing properties: 110°C/35%, 120°C/25% and 130°C/20%. This "plasticization" temperature has been estimated through DSC measurements of large amounts of moistened SBP in pressure-resistant pans. This new kind of DSC measurement revealed a new sample mass dependent second order transition between 140 and 180°C, which temperature is linearly linked to the sample mass

New Natural Injection-Moldable Composite Material from Sunflower Oil Cake

Through a twin-screw extrusion process the native structure of sunflower oil cake was completely transformed (globular protein denaturation/texturization and husk fiber defibration) into a simpler matrix-fiber structure, as could be seen on SEM micrographs. Further chemical reduction of protein disulfide bridges greatly reduced the melt viscosity of the moistened composite that it could be injection-molded. The molded specimens were tested and their tensile and flexural properties and water absorption calculated. Their water resistance appeared to be particularly high, and could be enhanced further after a thermal treatment (N2, 200°C). The proteic matrix seemed to behave like a natural thermoset resin. Sunflower oil cake could be used without any additives to make biodegradable, water resistant and exceptionally cheap material

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°C) was less than 25%. Glycidyl methacrylate was directly used in the extrusion process as cross-linker. In high humidity atmosphere (97%RH, 25°C), film water absorption was then kept under 40% while the tensile properties were improved of 50% and with a 30 minute UV post-treatment the mass gain in absorption was even less than 30% after 5 days

New thermal insulation fiberboards from cake generated during biorefinery of sunflower whole plant in a twin-screw extruder

The objective of this study was to manufacture new thermal insulation fiberboards by thermo-pressing. The starting material was a slightly deoiled cake (17.6% oil content), generated during the biorefinery of sunflower (Helianthus annuus L.) whole plant in a co-rotating (Clextral BC 45, France) twin-screw extruder. All fiberboards produced were cohesive mixtures of proteins and lignocellulosic fibers, acting respectively as binder and reinforcing fillers in what could be considered as a natural composite. The molding experiments were conducted using a 400 ton capacity heated hydraulic press (Pinette Emidecau Industries, France). The influence of molding conditions on board density, mechanical properties and heat insulation properties was examined. Molding conditions included mold temperature (140-200°C), pressure applied (150-250 kgf/cm²) and molding time (40-76 s), and these greatly affected board density and thus the mechanical and heat insulation properties. Board density increased with increasingly extreme molding conditions, rising from 500 to 858 kg/m³. The mechanical properties increased at the same time (from 52 to 660 kPa for flexural strength at break, from 5.9 to 49.4 MPa for elastic modulus, from 0.5 to 7.7 kJ/m² for Charpy impact strength, and from 19.2 to 47.1° for Shore D surface hardness). Conversely, heat insulation properties improved with decreasing board density, and the lowest thermal conductivity (88.5 mW/m K at 25°C) was obtained with the least dense fiberboard. The latter was produced with a 140°C mold temperature, a 150 kgf/cm² pressure applied and a 40 s molding time. A medium mold temperature (160°C) was needed to obtain a good compromise between mechanical properties (272 kPa for flexural strength at break, 26.3 MPa for elastic modulus, 3.2 kJ/m² for Charpy impact strength, and 37.3° for Shore D surface hardness), and heat insulation properties (99.5 mW/m K for thermal conductivity).The corresponding board density was medium (687 kg/m³). Because of their promising heat insulation properties, these new fiberboards could be positioned on walls and ceilings for thermal insulation of buildings. The bulk cake also revealed very low thermal conductivity properties (only 65.6 mW/m K at 25°C) due to its very low bulk density (204 kg/m³). It could be used as loose fill in the attics of houses

Film extrusion of sunflower protein isolate

Film extrusion of sunflower protein isolate (SFPI) was studied. The influence of die temperature (85 to 160°C), water and glycerol contents were investigated through appearance, mechanical and thermo-mechanical properties and swelling behavior in water of films. It was demonstrated that highest temperature, well above SFPI denaturation temperature in the compound, highest glycerol content (70 parts for 100 parts of SFPI) and medium water content (20 parts for 100 parts of SFPI) gave the most regular and smoothest film (as seen on SEM micrographs). Its ultimate tensile strength, Young’s modulus and strain at break were respectively: 3.2 MPa, 17.7 MPa and 73%. Soaked in water, its swelling was about 186% w/w but the film was quiet insoluble. Effect of temperature and plasticizer content were discussed in relation to the kinetic of SFPI denaturation. These first results are very promising for the development of biodegradable protein-based films

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

International audienceThis 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

Registry of BioBricks Models using CellML

A poster presented at BioSysBio 2007 and at SB3.0One of the main goals in Synthetic Biology is to assess the feasibility of building novel biological systems from interchangeable and standardized parts. In order to collect and share parts, a Registry of standardized DNA BioBricks[1] has been established at MIT. BioBricks can be assembled to form devices and systems to operate in living cells. Design of reliable devices and systems would benefit from accurate models of system function. To predict the function of systems built from many parts, we need to have accurate models for the parts and mechanisms to easily compose those part models into a system model. Therefore, in parallel to increasing the number of parts available and characterising them experimentally, a logical extension to the Registry would be to build a Registry of BioBrick models to complement the physical parts