Properties of biocomposites based on lignocellulosic fillers

This paper is focused on the analysis of the thermal and mechanical behaviour of processed biocomposites (biodegradable composites). These materials have been created by extrusion and injection moulding. The matrix, a biodegradable and aromatic copolyester (polybutylene adipate-co-terephthalate), has been fully characterised (NMR, SEC). The lignocellulosic materials used as fillers are a by-product of an industrial fractionation process of wheat straw. Different filler fractions have been selected by successive sieving, and then carefully analysed (granulometry, chemical structure). Cellulose, lignin, and hemicellulose contents have been determined through different techniques. The biocomposites thermal behaviour has been investigated by TGA (thermal degradation) and DSC (transition temperatures, crystallinity). These materials present good mechanical behaviour due to high filler-matrix compatibility. The impacts of filler content, filler size and the nature of each fraction have been analysed. To predict the mechanical behaviour, Takayanagi’s equation seems to provide an accurate answer to evaluate the modulus in a range, 0–30 wt% of fillers.     

Effect of filler content and size on transport properties of water vapor in PLA/calcium sulfate composites

Starting from calcium sulfate (gypsum) as fermentation byproduct of lactic acid production process, high-performance composites have been produced by melt-blending polylactide (PLA) and beta-anhydrite II (AII) filler, i.e., calcium sulfate hemihydrate previously dried at 500 degrees C. Characterized by attractive properties due to good filler dispersion throughout the polyester matrix and favorable interactions between components, these composites are interesting for potential use as biodegradable rigid packaging. The effect of filler content and mean particle diameter on the barrier properties such as sorption and diffusion to water vapor has been examined and compared to unfilled PLA. Even without additional treatments, the presence of the filler introduced constraints on molecular mobility in the permeable phase of amorphous PLA and the amount of solvent absorbed appears lower in the highly filled composites. Surprisingly, for PLA-30% AII compositions, by addition of filler characterized by high mean particle diameter (e.g., 43 microm) the thermodynamic diffusion parameter, D(0), decreased up to 2 orders of magnitude. The dimension of filler particles and their percentage in the continuous polymeric phase seem to be the most important parameters that determine the barrier properties of the PLA-AII composites to water vapor.     

Morphology and properties of soy protein isolate thermoplastics reinforced with chitin whiskers

Environmentally friendly thermoplastic nanocomposites were successfully developed using a colloidal suspension of chitin whiskers as a filler to reinforce soy protein isolate (SPI) plastics. The chitin whiskers, having lengths of 500 +/- 50 nm and diameters of 50 +/- 10 nm on average, were prepared from commercial chitin by acid hydrolysis. The dependence of morphology and properties on the chitin whiskers content in the range from 0 to 30 wt % for the glycerol plasticized SPI nanocomposites was investigated by dynamic mechanical thermal analysis, scanning electron microscopy, swelling experiment, and tensile testing. The results indicate that the strong interactions between fillers and between the filler and SPI matrix play an important role in reinforcing the composites without interfering with their biodegradability. The SPI/chitin whisker nanocomposites at 43% relative humidity increased in both tensile strength and Young's modulus from 3.3 MPa for the SPI sheet to 8.4 MPa and from 26 MPa for the SPI sheet to 158 MPa, respectively. Further, incorporating chitin whisker into the SPI matrix leads to an improvement in water resistance for the SPI based nanocomposites.     

Properties of biodegradable citric acid-modified granular starch/thermoplastic pea starch composites

Pea starch-based composites reinforced with citric acid-modified pea starch (CAPS) and citric acid-modified rice starch (CARS), respectively, were prepared by screw extrusion. The effects of granular CAPS and CARS on the morphology, thermal stability, dynamic mechanical thermal analysis, the relationship between the mechanical properties and water content, as well as the water vapor permeability of the composite films were investigated. Scanning electron microscope and X-ray diffraction reveal that the reinforcing agents, the granules of CAPS and CARS, are not disrupted in the thermoplastic process, while the pea starch in the matrix is turned into a continuous TPS phase. Granular CAPS and CARS can improve the storage modulus, the glass transition temperature, the tensile strength and the water vapor barrier, but decrease thermal stability. CARS/TPS composites exhibit a better storage modulus, tensile strength, elongation at break and water vapor barrier than CAPS/TPS composites because of the smaller size of the CARS granules.     

New nanocomposite materials reinforced with cellulose whiskers in atactic polypropylene: effect of surface and dispersion characteristics

New nanocomposite films were prepared with atactic polypropylene as the matrix and either of three types of cellulose whiskers, with various surface and dispersion characteristics, as the reinforcing phase: aggregated without surface modification, aggregated and grafted with maleated polypropylene or individualized and finely dispersed with a surfactant. Films obtained by solvent casting from toluene were investigated by means of scanning electron microscopy, dynamic mechanical analysis, and tensile testing. In the linear region, the mechanical properties above the glass-rubber transition were found to be drastically enhanced for the nanocomposites as compared to the neat polypropylene matrix. These effects were ascribed to the formation of a rigid network with filler/filler interactions. In addition, interactions between the filler and the matrix as well as the dispersion quality were found to play a major role on the mechanical properties of the composites when investigation of the films was performed in the nonlinear region.     

Polylactic acid composites incorporating casein functionalized cellulose nanowhiskers

Background

Polylactic acid (PLA) is considered to be a sustainable alternative to petroleum-based polymers for many applications. Using cellulose fiber to reinforce PLA is of great interest recently due to its complete biodegradability and potential improvement of the mechanical performance. However, the dispersion of hydrophilic cellulose fibers in the hydrophobic polymer matrix is usually poor without using hazardous surfactants. The goal of this study was to develop homogenously dispersed cellulose nanowhisker (CNW) reinforced PLA composites using whole milk casein protein, which is an environmentally compatible dispersant.

Results

In this study, whole milk casein was chosen as a dispersant in the PLA-CNW system because of its potential to interact with the PLA matrix and cellulose. The affinity of casein to PLA was studied by surface plasmon resonance (SPR) imaging. CNWs were functionalized with casein and used as reinforcements to make PLA composites. Fluorescent staining of CNWs in the PLA matrix was implemented as a novel and simple way to analyze the dispersion of the reinforcements. The dispersion of CNWs in PLA was improved when casein was present. The mechanical properties of the composites were studied experimentally. Compared to pure PLA, the PLA composites had higher Young’s modulus. Casein (CS) functionalized CNW reinforced PLA (PLA-CS-CNW) at 2 wt% filler content maintained higher strain at break compared to normal CNW reinforced PLA (PLA-CNW). The Young’s modulus of PLA-CS-CNW composites was also higher than that of PLA-CNW composites at higher filler content. However, all composites exhibited lower strain at break and tensile strength at high filler content.

Conclusions

The presence of whole milk casein improved the dispersion of CNWs in the PLA matrix. The improved dispersion of CNWs provided higher modulus of the PLA composites at higher reinforcement loading and maintained the strain and stress at break of the composites at relatively low reinforcement loading. The affinity of the dispersant to PLA is important for the ultimate strength and stiffness of the composites.

     

Biodegradable starch based nanocomposites with low water vapor permeability and high storage modulus

Nanocomposite materials based on a starch matrix reinforced with very small amounts of multi-walled carbon nanotubes (MWCNTs) (from 0.005 wt% to 0.055 wt%) were developed. The material's dynamic-mechanical and water vapor permeability properties were investigated. An increasing trend of storage modulus (E′) and a decreasing trend of water vapor permeability (WVP) with filler content were observed at room temperature. For the composite with 0.055 wt% of filler, E′ value was about 100% higher and WVP value was almost 43% lower than the corresponding matrix values. MWCNTs were wrapped in an aqueous solution of a starch-iodine complex before their incorporation into the matrix, obtaining exceptionally well-dispersed nanotubes and optimizing interfacial adhesion. This excellent filler dispersion leads to the development of an important contact surface area with the matrix material, producing remarkable changes in the starch-rich phase glass transition temperature even in composites with very low filler contents. This transition is shifted towards higher temperatures with increasing content of nanotubes. So at room temperature, some composites are in the rubber zone while others, in the transition zone. Therefore, this change in the material glass transition temperature can be taken as responsible for the important improvements obtained in the composites WVP and E′ values for carbon nanotubes content as low as 0.05 wt%.     

New nanocomposite materials reinforced with flax cellulose nanocrystals in waterborne polyurethane

New nanocomposite films were prepared from a suspension of cellulose nanocrystals as the filler and a polycaprolactone-based waterborne polyurethane (WPU) as the matrix. The cellulose nanocrystals, prepared by acid hydrolysis of flax fiber, consisted of slender rods with an average length of 327 +/- 108 nm and diameter of 21 +/- 7 nm, respectively. After the two aqueous suspensions were mixed homogeneously, the nanocomposite films were obtained by casting and evaporating. The morphology, thermal behavior, and mechanical properties of the films were investigated by means of attenuated total reflection Fourier transform infrared spectroscopy, wide-angle X-ray diffraction, differential scanning calorimetry, scanning electron microscopy, and tensile testing. The results indicated that the cellulose nanocrystals could disperse in the WPU uniformly and resulted in an improvement of microphase separation between the soft and hard segments of the WPU matrix. The films showed a significant increase in Young's modulus and tensile strength from 0.51 to 344 MPa and 4.27 to 14.86 MPa, respectively, with increasing filler content from 0 to 30 wt %. Of note is that the Young's modulus increased exponentially with the filler up to a content of 10 wt %. The synergistic interaction between fillers and between the filler and WPU matrix played an important role in reinforcing the nanocomposites. The superior properties of the new nanocomposite materials could have great potential applications.     

Preparation and characterization of wheat straw fibers for reinforcing application in injection molded thermoplastic composites

The potential of wheat straw fibers prepared by mechanical and chemical processes as reinforcing additives for thermoplastics was investigated. Fibers prepared by mechanical and chemical processes were characterized with respect to their chemical composition, morphology, and physical, mechanical and thermal properties. Composites of polypropylene filled with 30% wheat straw fibers were prepared and their mechanical properties were also evaluated. The fibers prepared by chemical process exhibited better mechanical, physical and thermal properties. Wheat straw fiber reinforced polypropylene composites exhibited significantly enhanced properties compared to virgin polypropylene. However, the strength properties of the composites were less for chemically prepared fiber filled composites. This was due to the poor dispersion of the fibers under the processing conditions used. These results indicate that wheat straw fibers can be used as potential reinforcing materials for making thermoplastic composites.     

Effect of fiber treatments on tensile and thermal properties of starch/ethylene vinyl alcohol copolymers/coir biocomposites

Coir fibers received three treatments, namely washing with water, alkali treatment (mercerization) and bleaching. Treated fibers were incorporated in starch/ethylene vinyl alcohol copolymers (EVOH) blends. Mechanical and thermal properties of starch/EVOH/coir biocomposites were evaluated. Fiber morphology and the fiber/matrix interface were further characterized by scanning electron microscopy (SEM). All treatments produced surface modifications and improved the thermal stability of the fibers and consequently of the composites. The best results were obtained for mercerized fibers where the tensile strength was increased by about 53% as compared to the composites with untreated fibers, and about 33.3% as compared to the composites without fibers. The mercerization improved fiber–matrix adhesion, allowing an efficient stress transfer from the matrix to the fibers. The increased adhesion between fiber and matrix was also observed by SEM. Treatment with water also improved values of Young’s modulus which were increased by about 75% as compared to the blends without the fibers. Thus, starch/EVOH blends reinforced with the treated fibers exhibited superior properties than neat starch/EVOH.     

Superior reinforcement effect of TEMPO-oxidized cellulose nanofibrils in polystyrene matrix: optical, thermal, and mechanical studies

Polystyrene (PS) composites reinforced with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-oxidized cellulose nanofibrils (TOCNs) with various weight ratios were fabricated by casting and vacuum-drying mixtures of PS/N,N-dimethylformamide (DMF) solution and TOCN/DMF dispersion. TOCNs of 3 to 4 nm width were dispersed homogeneously at the individual nanofibril level in the PS matrix, such that the TOCN/PS nanocomposite films exhibited high optical transparencies and their tensile strengths, elastic moduli, and thermal dimensional stabilities increased with increasing TOCN content. Dynamic mechanical analysis showed that the storage modulus of the TOCN/PS films increased significantly with TOCN content above the glass-transition temperature of PS by the formation of an interfibrillar network structure of TOCNs in the PS matrix, based on percolation theory. The outstanding and effective polymer reinforcement by TOCNs results from their high aspect ratio, high crystallinity, and nanodispersibility in the PS matrix.     

Effects of lignin content on the properties of lignocellulose-based biocomposites

The paper is focused on the analysis of the behaviour of biocomposites (biodegradable composites) which are reinforced with different fillers fractions, with varying lignin contents. These materials have been carried-out by extrusion and injection moulding. The matrix, an aromatic copolyester (polybutylene adipate-co-terephthalate), is biodegradable. The lignocellulose fillers are a by-product of an industrial fractionation process of wheat straw. From the raw agro-material and by lignin extractions, various fillers fractions have been obtained by varying the fractionation conditions, both on the liquid media (aqueous or organic) and on the temperature. The fillers lignin contents vary from 30 to 14 wt% with a resultant increase of the cellulose content. We have analysed the impact of the different extraction conditions on the fillers surface and size distribution, and also on the final thermal and mechanical properties of the biocomposites. These materials present significant differences of behaviour which can fulfil some requirements for applications, such as non-food packaging or other short-lived applications (agriculture, sport …) where long-lasting polymers are not entirely adequate.     

Preparation and properties of carboxylated styrene-butadiene rubber/cellulose nanocrystals composites

A series of carboxylated styrene-butadiene rubber (XSBR)/cellulose nanocrystals (CNs) latex composites were successfully prepared. The vulcanization process, morphology, dynamic viscoelastic behavior, dynamic mechanical property, thermal and mechanical performance of the XSBR/CNs composites were investigated in detail. The results revealed that CNs were dispersed uniformly in the XSBR matrix and formed a strong filler–filler network. The dynamic mechanical analysis (DMA) showed that the glass transition temperature (T_g) of XSBR matrix was shifted from 48.45 to 50.64 °C with 3 phr CNs, but decreased from 50.64 to 46.28 °C when further increasing CNs content up to 15 phr. The composites exhibited a significant enhancement in tensile strength (from 16.9 to 24.1 MPa) and tear strength (from 43.5 to 65.2 MPa) with loading CNs from 0 to 15 phr. In addition, the thermo-gravimetric analysis (TGA) showed that the temperature at 5% weight loss of the XSBR/CNs composites decreased slightly with an increase of the CNs content.     

Effect of morphological features and surface area of hydroxyapatite on the fatigue behavior of hydroxyapatite-polyethylene composites

The effect of surface area and morphological features of filler particles on the fatigue behavior of hydroxyapatite-filled high-density polyethylene composites was studied. Composites containing 40 vol % filler were injection-molded into tensile bars, gamma-irradiated, and subjected to sinusoidal tensile fatigue at a frequency of 2 Hz. To simulate the physiological environment, the tests were conducted at 37 degrees C in saline. Results showed that properties such as secant modulus, cyclic energy dissipation, dynamic creep strain, hysteresis loops, and even fracture surfaces differ depending on the morphology and surface area of the fillers used.     

Origins of B-type crystallinity in glycerol-plasticised, compression-moulded potato starches

The amount of B-type crystallinity in compression-moulded, glycerol-plasticised potato starches was strongly dependent on both the properties of the potato starch used and the applied processing conditions. The presence of amylose and the morphology of the potato starch used, but also processing parameters such as moulding temperature and water content during moulding affected the amount of B-type crystallinity in the materials and thus the ultimate mechanical properties of the plasticised starches. This indicated that the direct relation between composition and physical properties of processed starches is not always valid; processing parameters are important tools for controlling the physical properties of processed starches as they influence the amount of B-type crystallinity in the material. It was shown that the total amount of B-type crystallinity in the glycerol-plasticised potato starches should be considered as a summation of residual amylopectin crystallinity and recrystallisation of both amylose and amylopectin, being strongly dependent on the applied processing conditions. In order to explain the observed amount of B-type crystallinity in these starches, partial (co-)crystallisation of both amylose and amylopectin should occur at high moulding temperatures. The measured mechanical properties of the plasticised potato starches correlated well with the amount of B-type crystallinity observed in the materials.     

Composite materials derived from biodegradable starch polymer and jute strands

In this work, starch-based composites reinforced with jute strands were obtained by injection moulding procedure. The influence of the degree of adhesion at fibre–matrix interface to the mechanical properties of the composites was evaluated. For this purpose, partial delignification of jute strands by means of NaOH treatment was carried out and the mechanical properties of the corresponding composites determined. The alkali treatment resulted in an increase of the strength and stiffness of the jute strand/starch composites. The enhancement was analysed in terms of compatibility and extension of the adhesion at fibre–matrix interface. The application of a blocking reaction to the surface hydroxyl groups of jute strands corroborated the influence of the mechanical properties to the extension of the interfacial adhesion. Thus, higher extension of the hydrogen bonds at fibre–matrix interface gave higher strength and stiffness of the jute strand/starch-based composites.     

Flexural and Dynamic Mechanical Properties of Alkali-Treated Coir/Pineapple Leaf Fibres Reinforced Polylactic Acid Hybrid Biocomposites

Polylactic acid(PLA)possesses good mechanical and biodegradability properties which make it a suitable material for polymer composites whereas brittleness and high costs limit its utilization in various applications.The reinforcement of natural fibres with biopolymers has been formed to be an efficient technique to develop composites having the ability to be fully biodegradable.This study concerns with the incorporation of various percentages of untreated and alkali-treated Coir Fibres(CF)and pineapple leaf fibres(PALF)in PLA biocomposites and characterizations of flexural,morphological and dynamic mechanical properties.Flexural properties showed that the treated C1P1 hybrid composites(C1P1A)displayed highest flexural strength(35.81 MPa)and modulus(5.28 GPa)among all hybrid biocomposites.Scanning Electron Micros-copy(SEM)revealed a behaviour of fibre-matrix adhesion in untreated treated biocomposites.SEM observation revealed good dispersion of the fillers in PLA.Dynamic mechanical analysis revealed that C1P1A showed highest glass transition temperature(Tg)and storage modulus(E')while untreated C3P7 displayed the least Tg and E'.Overall findings showed that alkali-treated hybrid biocomposites(CF/PALF/PLA)especially C1P1A have improved flexural properties,dynamic and morphological properties over untreated biocomposites.Success of these findings will provide attracting consideration of these hybrid biocomposites for various lightweight uses in a broad selection of industrial applications such as biomedical sectors,automobile,construction,electronics equipment,and hardware tools.     

Effects of modified cellulose nanocrystals on the barrier and migration properties of PLA nano-biocomposites

The aim of this paper is to report the impact of the addition of cellulose nanocrystals on the barrier properties and on the migration behaviour of poly(lactic acid), PLA, based nano-biocomposites prepared by the solvent casting method. Their microstructure, crystallinity, barrier and overall migration properties were investigated. Pristine (CNC) and surfactant-modified cellulose nanocrystals (s-CNC) were used, and the effect of the cellulose modification and content in the nano-biocomposites was investigated. The presence of surfactant on the nanocrystal surface favours the dispersion of CNC in the PLA matrix. Electron microscopy analysis shows the good dispersion of s-CNC in the nanoscale with well-defined single crystals indicating that the surfactant allowed a better interaction between the cellulose structures and the PLA matrix. Reductions of 34% in water permeability were obtained for the cast films containing 1wt.% of s-CNC while good oxygen barrier properties were detected for nano-biocomposites with both 1wt.% and 5wt.% of modified and un-modified cellulose nanocrystals, underlining the improvement provided by cellulose on the PLA films. Moreover, the migration level of the studied nano-biocomposites was below the overall migration limits required by the current normative for food packaging materials in both non-polar and polar simulants.     

Thermoplastic corn starch/clay hybrids: Effect of clay type and content on physical properties

Thermoplastic corn starch (TPS) hybrids, plasticized with glycerol and reinforced with two types of clay (sodium montmorillonite and Cloisite^® 30B), were prepared by melt-extrusion. Scanning electron microscopy was used to visualize extrudates morphology. The effects of clay content and of glycerol content on the physical properties of extrudates were evaluated. As determined by contact angle measurements and X-ray diffraction, the increase in glycerol content led to materials with higher hydrophilicity, and higher B-type crystallinity. Addition of clay resulted in hybrid materials with improved properties in relation to TPS alone, even after conditioning at a high relative humidity for 90 days. X-ray diffraction was also used to evaluate clay intercalation within the polymeric matrix, before and after conditioning. Soil burial biodegradation tests, carried out for TPS alone and for TPS/Cloisite 30B hybrids, and followed by weight loss measurements, revealed that biodegradation was enhanced for the hybrid materials in comparison with TPS.     

Ultrastrong and high gas-barrier nanocellulose/clay-layered composites

Nanocellulose/montmorillonite (MTM) composite films were prepared from 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized cellulose nanofibrils (TOCNs) with an aspect ratio of >200 dispersed in water with MTM nanoplatelets. The composite films were transparent and flexible and showed ultrahigh mechanical and oxygen barrier properties through the nanolayered structures, which were formed by compositing the anionic MTM nanoplatelet filler in anionic and highly crystalline TOCN matrix. A composite film with 5% MTM content had Young's modulus 18 GPa, tensile strength 509 MPa, work of fracture of 25.6 MJ m(-3), and oxygen permeability 0.006 mL μm m(-2) day(-1) kPa(-1) at 0% relative humidity, respectively, despite having a low density of 1.99 g cm(-3). As the MTM content in the TOCN/MTM composites was increased to 50%, light transmittance, tensile strength, and elongation at break decreased, while Young's modulus was almost unchanged and oxygen barrier property was further improved to 0.0008 mL μm m(-2) day(-1) kPa(-1).