Numerical and experimental analyses of biocomposites reinforced with natural fibres

n the last decades the biocomposites have been widely used in the construction, automobile and aerospace industries. Not only the interface transition zone (ITZ) but also the heterogeneity of natural fibres affects the mechanical behaviour of these composites. This work focuses on the numerical and experimental analyses of a polymeric composite fabricated with epoxy resin and unidirectional sisal and banana fibres. A three-dimensional model was set to analyze the composites using the elastic properties of the individual phases. In addition, a two-dimensional model was set taking into account the effective composite properties obtained by micromechanical models. A tensile testing was performed to validate the numerical analyses and evaluating the interface condition of the constitutive phases.

Garlic powder and wheat bran as fillers: Their effect on the physicochemical properties of edible biocomposites

Biocomposites with two different fillers, garlic and wheat bran, were studied. They were based on cassava starch and contained glycerol as a plasticizer and potassium sorbate as an antimicrobial agent and were characterized by scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and infrared spectroscopy (IR). The mechanical performance at room and lower temperatures was also studied. SEM micrographies of fractured surfaces of the wheat bran composite films showed some ruptured particles of fiber while fibrils of garlic on the order of nanometers were observed when garlic composite films were studied. Mechanical tests, at room temperature, showed that the addition of wheat bran led to an increment in the storage modulus (E`) and hardening and a decrease in Tan delta, while the garlic composite showed a diminishing in the E` and hardening and did not produce significant changes in Tan delta values when compared with systems without fillers (matrix). In the range between -90 degrees C and 20 degrees C. all the materials studied presented two peaks in the Tan delta curve. In the case of the wheat bran composite, both relaxation peaks shifted slightly to higher temperatures, broadened and diminished their intensity when compared with those of the matrix; however garlic composite showed a similar behavior to the matrix. DSC thermograms of aqueous systems showed a slight shift of gelatinization temperature (T(gelatinization)) to higher values when the fillers were present. Thermograms of films showed that both, garlic and wheat bran composites, had a lower melting point than the matrix. IR data indicated that interaction between starch and fillers determined an increase in the availability of hydroxyl groups to be involved in a dynamic exchange with water. (C) 2010 Elsevier B.V. All rights reserved.

Agro-Based Biocomposites for Industrial Applications

Leaf fibers are fibers that run lengthwise through the leaves of most monocotyledonous plants such as pineapple, banana, etc. Pineapple (Ananas comosus) and Banana (Musa indica) are emerging fiber having a very large potential to be used for composite materials. Over 150,000 ha of pineapple and over 100,000 ha of banana plantations are available in Brazil for the fruit production and enormous amount of agricultural waste is produced. This residual waste represents one of the single largest sources of cellulose fibers available at almost no cost. The potential consumers for this fiber are pulp and paper, chemical feedstock, textiles and composites for the automotive, furniture and civil construction industry.

Agro-Based Biocomposites for Industrial Applications

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Nano- and macroscale structural and mechanical properties of in situ synthesized bacterial cellulose/PEO-b-PPO-b-PEO biocomposites

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Bacterial cellulose biocomposites for guided tissue regeneration

Bacterial cellulose (BC) has become established as a remarkably versatile biomaterial and can be used in a wide variety of scientific applications, especially for medical devices. In this work, the bacterial cellulose fermentation process is modified by the addition of chondroitin sulfate and hyaluronic acid (1% w/w) to the culture medium before the bacteria is inoculated. Besides, biomimetic precipitation of calcium phosphate of biological interest from simulated body fluid on bacterial cellulose was studied. Chondroitin sulfate and hyaluronic acid influences in bacterial cellulose were analyzed using transmission infrared spectroscopy (FTIR), XRD (X-ray diffraction) and scanning electron microscopy (SEM). FTIR analysis showed interaction between bacterial cellulose nanobiocomposites and calcium phosphate and XRD demonstrated amorphous calcium phosphate and calcium chloride on bacterial cellulose nanobiocomposites. SEM images confirmed incorporation of calcium phosphate in bacterial cellulose nanobiocomposites surface with different calcium phosphate particles morphology.

Elaboration and Characterization of Nano-Biocomposites Based on Plasticized Poly(Hydroxybutyrate-Co-Hydroxyvalerate) with Organo-Modified Montmorillonite

Nano-biocomposites based on a biodegradable bacterial copolyester, poly(hydroxybutyrate-co-hydroxyvalerate), have been elaborated with an organo-modified montmorillonite (OMMT) clay as nanofiller, and acetyl tributyl citrate as plasticizer. The corresponding (nano)structures, thermal and mechanical properties, permeability, and biodegradability have been determined. Polyhydroxyalkanoates are very thermal sensitive then to follow the degradation the corresponding matrices have been analyzed by size exclusion chromatography. The results indicate that the addition of the plasticizer decreases the thermo-mechanical degradation, during the extrusion. These nano-biocomposites show an intercalated/exfoliated structure with good mechanical and barrier properties, and an appropriated biodegradation kinetic. Intending to understand the changes in the thermal properties, the nano-biocomposites were characterized by thermal gravimetric analysis and differential scanning calorimetry. The presence of the OMMT clay did not influence significantly the transition temperatures. However, the filler not only acted as a nucleating agent which enhanced the crystallization, but also as a thermal barrier, improving the thermal stability of the biopolymer. The results indicated that the addition of the plasticizer reduces the glass transition temperature and the crystalline melting temperature. The plasticizer acts as a processing aid and increases the processing temperature range (lower melting temperature).

Combined effects of cellulose nanocrystals and silver nanoparticles on the barrier and migration properties of PLA nano-biocomposites

Poly(lactic acid) (PLA)-based high performance nano-biocomposites were prepared to be used in active food packaging. Pristine (CNC) and surfactant modified cellulose nanocrystals (s-CNC) with silver (Ag) nanoparticles were used as the matrix modifiers. Binary and ternary systems were prepared. Morphological investigations revealed the good distribution of silver nanoparticles in PLA ternary systems. The combination of s-CNC and Ag nanoparticles increased the barrier effect of the produced films while the results of overall migration for the PLA nano-biocomposites revealed that none of the samples exceeded the overall migration limit, since results were well below 60 mg kg−1 of simulant.

Processing and Characterization of Nano-biocomposites Based on Mater-Bi® with Layered Silicates

The development of new nano-biocomposites has been one of the main research areas of interest in polymer science in recent years, since they can combine the intrinsic biodegradable nature of matrices with the ability to modify their properties by the addition of selected nano-reinforcements. In this work, the addition of mineral nanoclays (montmorillonites and sepiolites) to a commercial starch-based matrix is proposed. A complete study on their processing by melt-intercalation techniques and further evaluation of the main properties of nano-biocomposites has been carried out. The results reported show an important influence of the nano-biocomposites morphology on their final properties. In particular, the rheological and viscoelastic characteristics of these systems are very sensitive to the dispersion level of the nanofiller, but it is possible to assess that the material processing behaviour is not compromised by the presence of these nano-reinforcements. In general, both nanofillers had a positive influence in the materials final properties. Mechanical performance shows improvements in terms of elastic modulus, without important limitations in terms of ductility. Thermal properties are improved in terms of residual mass after degradation and low improvements are also observed in terms of oxygen barrier properties.

Biocomposites of non-crosslinked natural and synthetic polymers

Biocomposite films comprising a non-crosslinked, natural polymer (collagen) and a synthetic polymer, poly(var epsilon-caprolactone) (PCL), have been produced by impregnation of lyophilised collagen mats with a solution of PCL in dichloromethane followed by solvent evaporation. This approach avoids the toxicity problems associated with chemical crosslinking. Distinct changes in film morphology, from continuous surface coating to open porous format, were achieved by variation of processing parameters such as collagen:PCL ratio and the weight of the starting lyophilised collagen mat. Collagenase digestion indicated that the collagen content of 1:4 and 1:8 collagen:PCL biocomposites was almost totally accessible for enzymatic digestion indicating a high degree of collagen exposure for interaction with other ECM proteins or cells contacting the biomaterial surface. Much reduced collagen exposure (around 50%) was measured for the 1:20 collagen:PCL materials. These findings were consistent with the SEM examination of collagen:PCL biocomposites which revealed a highly porous morphology for the 1:4 and 1:8 blends but virtually complete coverage of the collagen component by PCL in the1:20 samples. Investigations of the attachment and spreading characteristics of human osteoblast (HOB) cells on PCL films and collagen:PCL materials respectively, indicated that HOB cells poorly recognised PCL but attachment and spreading were much improved on the biocomposites. The non-chemically crosslinked, collagen:PCL biocomposites described are expected to provide a useful addition to the range of biomaterials and matrix systems for tissue engineering.

Hemp fines - an agricultural by-product for biocomposites? A holistic approach

The technical, environmental and economic potential of hemp fines as a natural filler in bioplastics to produce biocomposites is the subject of this study – giving a holistic overview. Hemp fines are an agricultural by-product of the hemp fibres and shives production. Shives and fibres are for example used in the paper, animal bedding or composite area. About 15 to 20 wt.-% per kg hemp straw results in hemp fines after processing. In 2010 about 11,439 metric tons of hemp fines were produced in Europe. Hemp fines are an inhomogeneous material which includes hemp dust, shives and fibre. For these examinations the hemp fines are sieved in a further step with a tumbler sieving machine to obtain more specified fractions. The untreated hemp fines (ex work) as well as the sieved fractions are combined with a polylactide polymer (PLA) using a co-rotating twin screw extruder to produce biocomposites with different hemp fine content. By using an injection moulding machine standard test bars are produced to conduct several material tests. The Young’s modulus is increased and the impact strength reduced by hemp fines. With a content of above 15 wt.-% hemp fines are also improving the environmental (global warming potential) and economic performance in comparison to pure PLA.

Greffage d’un film mince de nano-TiO2 sur les fibres naturelles cellulosiques pour le renforcement de biocomposites polymériques

Abstract : Natural materials have received a full attention in many applications because they are degradable and derived directly from earth. In addition to these benefits, natural materials can be obtained from renewable resources such as plants (i.e. cellulosic fibers like flax, hemp, jute, and etc). Being cheap and light in weight, the cellulosic natural fiber is a good candidate for reinforcing bio-based polymer composites. However, the hydrophilic nature -resulted from the presence of hydroxyl groups in the structure of these fibers- restricts the application of these fibers in the polymeric matrices. This is because of weak interfacial adhesion, and difficulties in mixing due to poor wettability of the fibers within the matrices. Many attempts have been done to modify surface properties of natural fibers including physical, chemical, and physico-chemical treatments but on the one hand, these treatments are unable to cure the intrinsic defects of the surface of the fibers and on the other hand they cannot improve moisture, and alkali resistance of the fibers. However, the creation of a thin film on the fibers would achieve the mentioned objectives. This study aims firstly to functionalize the flax fibers by using selective oxidation of hydroxyl groups existed in cellulose structure to pave the way for better adhesion of subsequent amphiphilic TiO[subscript 2] thin films created by Sol-Gel technique. This method is capable of creating a very thin layer of metallic oxide on a substrate. In the next step, the effect of oxidation on the interfacial adhesion between the TiO[subscript 2] film and the fiber and thus on the physical and mechanical properties of the fiber was characterized. Eventually, the TiO[subscript 2] grafted fibers with and without oxidation were used to reinforce poly lactic acid (PLA). Tensile, impact, and short beam shear tests were performed to characterize the mechanical properties while Thermogravimetric analysis (TGA), Differential Scanning Calorimetry (DSC), Dynamic mechanical analysis (DMA), and moisture absorption were used to show the physical properties of the composites. Results showed a significant increase in physical and mechanical properties of flax fibers when the fibers were oxidized prior to TiO[subscript 2] grafting. Moreover, the TiO[subscript 2] grafted oxidized fiber caused significant changes when they were used as reinforcements in PLA. A higher interfacial strength and less amount of water absorption were obtained in comparison with the reference samples.

Fabricación y caracterización físico-mecánica de biocomposites reforzados con fibras naturales. Aplicaciones en el sector náutico.

156 p.

New biomaterials for packaging: a green approach to biopolymers and biocomposites

The impellent global environmental issues related to plastic materials can be addressed by following two different approaches: i) the development of synthetic strategies towards novel bio-based polymers, deriving from biomasses and thus identifiable as CO2-neutral materials, and ii) the development of new plastic materials, such as biocomposites, which are bio-based and biodegradable and therefore able to counteract the accumulation of plastic waste. In this framework, this dissertation presents extensive research efforts have been devoted to the synthesis and characterization of polyesters based on various bio-based monomers, including ω-pentadecalactone, vanillic acid, 2,5-furan dicarboxylic acid, and 5-hydroxymethylfurfural. With the aim of achieving high molecular weight polyesters, different synthetic strategies have been used as melt polycondensation, enzymatic polymerization, ring-opening polymerization and chain extension reaction. In particular, poly(ethylene vanillate) (PEV), poly(ω-pentadecalactone) (PPDL), poly(ethylene vanillate-co-pentadecalactone) (P(EV-co-PDL)), poly(2-hydroxymethyl 5-furancarboxylate) (PHMF), poly(ethylene 2,5-furandicarboxylate) (PEF) with different amount of diethylene glycol (DEG) unit amount, poly(propylene 2,5-furandicarboxylate) (PPF), poly(hexamethylene 2,5-furandicarboxylate), (PHF) have been prepared and extensively characterized. To improve the lacks of poly(hydroxybutyrate-co-valerate) (PHBV), its minimal formulations with natural additives and its blending with medium chain length PHAs (mcl-PHAs) have been tested. Additionally, this dissertation presents new biocomposites based on polylactic acid (PLA), poly(butylene succinate) (PBS), and PHBV, which are polymers both bio-based and biodegradable. To maintain their biodegradability only bio-fillers have been taken into account as reinforcing agents. Moreover, the commitment to sustainability has further limited the selection and led to the exclusive use of agricultural waste as fillers. Detailly, biocomposites have been obtained and discussed by using the following materials: PLA and agro-wastes like tree pruning, potato peels, and hay leftovers; PBS and exhausted non-compliant coffee green beans; PHBV and industrial starch extraction residues.

Composite materials of thermoplastic starch and fibers from the ethanol-water fractionation of bagasse

The aim of this study was to evaluate the potential of the fibrous material obtained from ethanol-water fractionation of bagasse as reinforcement of thermoplastic starches in order to improve their mechanical properties. The composites were elaborated using matrices of corn and cassava starches plasticized with 30 wt%glycerin. The mixtures (0,5,10 and 15 wt% bagasse fiber) were elaborated in a rheometer at 150 degrees C. The mixtures obtained were pressed on a hot plate press at 155 degrees C. The test specimens were obtained according to ASTM D638. Tensile tests, moisture absorption tests for 24 days (20-23 degrees C and 53% RH, ASTM E104), and dynamic-mechanical analyses (DMA) in tensile mode were carried out. Images by scanning electron microscopy (SEM) and X-ray diffraction were obtained. Fibers (10 wt% bagasse fiber) increased tensile strength by 44% and 47% compared to corn and cassava starches, respectively. The reinforcement (15 wt% bagasse fiber) increased more than fourfold the elastic modulus on starch matrices. The storage modulus at 30 C (E(30 degrees C)`) increased as the bagasse fiber content increased, following the trend of tensile elastic modulus. The results indicate that these fibers have potential applications in the development of biodegradable composite materials. (c) 2011 Elsevier B.V. All rights reserved.