Mechanical Properties and Isothermal Crystallization Behaviour of Poly(lactide)/Poly(methyl methacrylate)/α-Cellulose Composites

Polylactide (PLA)/polymethylmethacrylate (PMMA)/α-cellulose composites were fabricated using a twin-screw extruder. During fabrication, α-cellulose short fibres were incorporated for improving the toughness of the brittle PLA and a chain extender was used for reducing PLA hydrolysis. Highly transparent PLA and PMMA were blended to obtain miscible and transparent blends. For evaluating the performance of the PLA/PMMA/α-cellulose composites, a series of measurements, including tensile and Izod impact tests, light transmission and haze measurements, thermomechanical analysis, and determination of isothermal crystallisation behaviour, was conducted. Adding the chain extender considerably reduced the occurrence of hydrolytic degradation. Both the chain extender and α-cellulose short fibres increased the elongation at break and Izod impact strength of the composites. Compared with the neat PLA, including 1.0 wt% α-cellulose short fibres increased the elongation at break and Izod impact strength of the composite PLA by approximately 211 and 219 %, respectively. According to the observed mechanical performance, the optimal blending ratios for PLA and PMMA were between 90:10 and 80:20. The total light transmittance of the composites was as high as 91 %, indicating that the PLA/PMMA blend was highly miscible. The haze value of the PLA/PMMA/α-cellulose composites was lower than 32 %. Incorporating cellulose short fibres increased the number of crystallisation sites and crystallinity of the PLA/PMMA/α-cellulose composites while reducing the spherulite dimensions.     

Vegetable fibres from agricultural residues as thermo-mechanical reinforcement in recycled polypropylene-based green foams

Novel lightweight composite foams based on recycled polypropylene reinforced with cellulosic fibres obtained from agricultural residues were prepared and characterized. These composites, initially prepared by melt-mixing recycled polypropylene with variable fibre concentrations (10-25 wt.%), were foamed by high-pressure CO₂ dissolution, a clean process which avoids the use of chemical blowing agents. With the aim of studying the influence of the fibre characteristics on the resultant foams, two chemical treatments were applied to the barley straw in order to increase the α-cellulose content of the fibres. The chemical composition, morphology and thermal stability of the fibres and composites were analyzed. Results indicate that fibre chemical treatment and later foaming of the composites resulted in foams with characteristic closed-cell microcellular structures, their specific storage modulus significantly increasing due to the higher stiffness of the fibres. The addition of the fibres also resulted in an increase in the glass transition temperature of PP in both the solid composites and more significantly in the foams.     

PLA Based Biopolymer Reinforced with Natural Fibre: A Review

In recent years renewed interest on the development of biopolymers, based on constituents obtained from natural resources is gaining much attention. Natural fibres such as kenaf, hemp, flax, jute, bamboo, elephant grass and sisal based polymer with thermoplastic and thermoset matrices offer reductions in weight, cost and carbon dioxide emission, less reliance on foreign oil resources and recyclability. Reinforced biopolymer with natural fibres is the future of “green composites” addressing many sustainability issues. Among the available biopolymer, PLA (polylactide) is the only natural resource polymer produced at a large scale of over 140,000 tonnes per year. Natural fibre reinforced PLA based biocomposites are widely investigated by the polymer scientists in the last decade to compete with non renewable petroleum based products. The type of fibre used plays an important role in fibre/matrix adhesion and thereby affects the mechanical performance of the biocomposites. The aim of this review is to investigate the effects of processing methods, fibre length, fibre orientation, fibre-volume fraction, and fibre-surface treatment on the fibre/matrix adhesion and mechanical properties of natural-fibre-reinforced PLA composites. Although much work has been performed to engineer the design of such superior biocomposites, the information is scattered in nature. A comprehensive review on the major technical considerations undertaken to prepare such biocomposites over the last decade is investigated to address the feasibility of wide scale industrial acceptance to such biocomposites. A brief review on the available natural fibres and biopolymer is also given for a comparative study.     

Influence of Hygrothermal Ageing on the Physico-Mechanical Properties of Alkali Treated Industrial Hemp Fibre Reinforced Polylactic Acid Composites

30 wt% aligned untreated long hemp fibre/polylactic acid (AUL) and aligned alkali treated long hemp fibre/polylactic acid (AAL) composites were produced by film stacking and subjected to hygrothermal ageing environment along with neat polylactic acid (PLA). Hygrothermal ageing was carried out by immersing samples in distilled water at 25 and 50 °C over a period of 3 months. It was found that both neat PLA and composites followed Fickian diffusion. Higher temperature generally increased the Diffusion coefficient, D of neat PLA and composites, as well as shortening the saturation time. Neat PLA had the lowest D value followed by AAL composites and then AUL composites. After hygrothermal ageing, tensile and flexural strength, Young’s and flexural modulus and K _Ic were found to decrease and impact strength was found to increase for both AUL and AAL composites. AUL composites had greater overall reduction in mechanical properties than that for AAL composites after hygrothermal ageing. Crystallinity contents of the hygrothermal aged composites support the results of the deterioration of mechanical properties upon exposure to hygrothermal ageing environment.     

Effect of Fiber Surface Treatments on Thermo-Mechanical Behavior of Poly(Lactic Acid)/Phormium Tenax Composites

In the present study, Phormium Tenax fiber reinforced PLA composites were processed by injection molding and twin screw compounding with a fiber content ranging from 10 to 30 wt%. Three surface treatment methods have been used to improve the Phormium Tenax fiber-matrix interfacial bonding that are as follows: (1) aqueous alkaline solution, (2) silane coupling agent, and (3) a combination of alkaline and silane treatment. The mechanical, thermal and morphological properties of the resulting composites were investigated. The results have shown that the moduli of surface treated fiber reinforced composites are lower than the ones obtained for untreated composites (as a consequence of the decrease in fiber modulus caused by the chemical treatments) and no significant increase in strength was observed for any of the composites compared to neat PLA. SEM micrographs of composite fractured surfaces confirmed an improvement in the interfacial strength, which was insufficient nonetheless to significantly enhance the mechanical behavior of the resulting composites. Results from thermogravimetric analysis and differential scanning calorimetry suggest that surface treatment of Phormium affects the ability of PLA to cold crystallize, and the thermal stability of the composites at the different fiber contents was reduced with introduction of alkali and silane treated Phormium fibers.     

Stiff Biodegradable Polylactide Composites with Ultrafine Cellulose Filler

Polylactide (PLA) composites with 10–30 wt% of commercial fine grain filler of native cellulose were prepared by melt-mixing, and examined. The composite films had esthetic appearance, glossy surface, creamy color and density close to that of neat PLA. Good dispersion of the filler in PLA matrix was achieved. The composites were stiffer than neat PLA; in the glassy region the storage modulus increased by approx. 30 %. The tensile strength of the composite materials in the temperature range from 25 to 45 °C was similar to that of neat PLA. No marked decrease in molar mass of PLA in the composites occurred during processing in comparison to neat PLA. Moreover, thermogravimetry experiments demonstrated good thermal stability of the composites; 5 % weight loss occurred well above 300 °C.     

Green Composites of Poly (Lactic Acid) and Sugarcane Bagasse Residues from Bio-refinery Processes

Twin-screw extrusion was used to prepare the composites consisting of PLA and three types of sugarcane bagasse residues (up to 30 wt%) derived from different steps of a biorefinery process. Each residue had different composition, particle size and surface reactivity due to chemical and biological (enzyme, microbes) treatments that the biomass was subjected to. The effects of different residue characteristics on properties, crystallization behaviors and morphologies of PLA composites were investigated. Besides, a small amount (2 wt%) of coupling agent, Desmodur^® VKS 20 (DVKS), was used to improve the interfacial bonding between PLA and bagasse residues. The results indicated that in the presence of 2 % DVKS, PLA composite with pretreated residue exhibited the maximum strength properties (98.94 % tensile strength and 93.91 % flexural strength of neat PLA), while PLA composite with fermentation residue exhibited the minimum strength properties (88.98 % tensile strength and 81.91 % flexural strength of neat PLA).     

Single-Plant Biocomposite from Ricinus Communis: Preparation, Properties and Environmental Performance

A single-plant biobased composite material was prepared from fibre and matrix constituents produced from the castor plant, ricinus communis. It is shown that the mechanical properties of the castor plant fibres are comparable to those of other bast fibres and that the stiffness and strength characteristics of the castor fibre/polyamide 11 biocomposite compare well with those of other natural fibre composites. By using a biobased thermoplastic matrix material the reliance on non-renewable feedstock sources is reduced and end-of-lifetime recyclability is improved. The analysis of the environmental performance of the new castor plant composite suggests that the biobased material has great potential as a sustainable alternative replacing glass fibre-reinforced plastics.     

Effects of Alkali Treatment on the Properties of Short Flax Fiber–Poly(Lactic Acid) Eco-Composites

In this study, the influence of alkali (NaOH) treatment on the mechanical, thermal and morphological properties of eco-composites of short flax fiber/poly(lactic acid) (PLA) was investigated. SEM analysis conducted on alkali treated flax fibers showed that the packed structure of the fibrils was deformed by the removal non-cellulosic materials. The fibrils were separated from each other and the surface roughness of the alkali treated flax fibers was improved. The mechanical tests indicated that the modulus of the untreated fiber/PLA composites was higher than that of PLA; on the other hand the modulus of alkali treated flax fiber/PLA was lower than PLA. Thermal properties of the PLA in the treated flax fiber composites were also affected. T_g values of treated flax fiber composites were lowered by nearly 10 °C for 10% NaOH treatment and 15 °C for 30% NaOH treatment. A bimodal melting behavior was observed for treated fiber composites different than both of neat PLA and untreated fiber composites. Furthermore, wide angle X-ray diffraction analysis showed that the crystalline structure of cellulose of flax fibers changed from cellulose-I structure to cellulose-II.     

End-Of-Life Textiles as Reinforcements in Biocomposites

A number of attempts have been made to recycle cotton/polyester blend woven fabrics after use; however, most of these fabrics are disposed of in landfills. Major part of these blend fabrics are not recycled due to complexity of the fibre arrangement and cannot be separated economically. This study shows that these discarded woven fabrics could be directly used as reinforcements in composites without fibre separation. Uniform alignment in the woven fabric provided consistent properties to the composites. The fabrics were reinforced by soybean-based-bioresins to produce biocomposites. The composites were analysed for mechanical, thermal, viscoelastic and morphological properties. Porosity and wettability of the composites were also evaluated. Results demonstrate that the tensile strength and modulus of over 100 and 10 MPa, respectively, can be obtained without any fibre treatment. Furthermore, impact strength over 70 kJ/m² was obtained without any chemical treatment on fibres. The porosity of the composites produced was less than 9 vol%. Additionally, the fabrics were treated with alkali in order to improve the fibre–matrix interface and the composite properties were studied. From the economical perspective, these composites can be produced at a low cost as the major component is available for free or low cost.     

Enhanced Interfacial Adhesion and Characterisation of Recycled Natural Fibre-Filled Biodegradable Green Composites

The structural, thermal, mechanical, and biodegradable properties of composite materials made from polylactide (PLA) and agricultural residues (arrowroot (Maranta arundinacea) fibre, AF) were evaluated. Melt blended glycidyl methacrylate-grafted polylactide (PLA-g-GMA) and coupling agent-treated arrowroot fibre (TAF) formed the PLA-g-GMA/TAF composite, which had better properties than the PLA/AF composite. The water resistance of the PLA-g-GMA/TAF composite was greater than that of the PLA/AF composite; the release of PLA in water from the PLA/AF and PLA-g-GMA/TAF composites indicated good biological activity. The PLA-g-GMA/TAF material had better mechanical properties than PLA/AF. This behaviour was attributed to better compatibility between the grafted polymer and TAF. The results indicated that the T_g of PLA was increased by the addition of fibre, which may have improved the heat resistance of PLA. Furthermore, the mass losses following burial in soil compost indicated that both materials were biodegradable, especially at high levels of AF or TAF substitution.     

Mechanical Recycling of PLA Filled with a High Level of Cellulose Fibres

Composites consisting of 30 vol% PLA and 70 vol% cellulose fibres were prepared with compression moulding. In the first part of the study, the recyclability of this composite material was investigated by grinding the material and using the recyclate obtained as a filler for PLA. Thus, the recyclate was compounded with PLA in loadings ranging from 20 to 50 wt%. The composites obtained were characterised by tensile tests, Charpy impact tests, DMTA, and SEM. Tests showed that the recyclate had a relatively good reinforcing effect. Stress at break increased from about 50 to 77 MPa and the modulus increased from 3.6 to 8.5 GPa. In the second part of the study, the ability to mechanically recycle the composites obtained was evaluated by repeated processing. Composite with two loadings of the recyclate (20 wt% and 50 %) was injection moulded repeatedly, six times. Tests showed that the composite material with 20 wt% recyclate could withstand six cycles relatively well, while the composite with the higher load degraded much more quickly. For the composites with 50 wt% recyclate, signs of polymer degradation could be seen already after reprocessing the composite once.     

Method of Producing Biodegradable Reference Material and its Biodegradability Based on International Standard Evaluation Method (ISO 14855-2)

Returnable cups made of poly(lactic acid) (PLA) are employed as an example of products made of biodegradable plastics. Two kinds of PLA samples plates and powders with different shapes were prepared from PLA cups. The plates were cut from a cup using nippers. Powders were prepared using a rotation mechanical mixer for 45 min. PLA powders were separated by sieves with 60 meshes (250 μm) into a size ranging from 0 to 250 μm. An average diameter of powders separated by a sieve is 169 μm. Biodegradation tests of PLA plates, PLA powders and cellulose powders in controlled compost at 58 °C were performed using a Microbial Oxidative Degradation Analyzer (MODA) instrument according to ISO 14855-2. PLA powders showed almost the same biodegradation curve as that of cellulose powders. PLA plates biodegraded at a slower rate than PLA powders.     

All-Cellulose Composite Fibers Obtained by Electrospinning Dispersions of Cellulose Acetate and Cellulose Nanocrystals

All-cellulose composite fibers were produced by electrospinning dispersions containing cellulose acetate (CA) and cellulose nanocrystals (CNCs). Precursor polymer matrices were obtained after dispersion of CA with different degrees of substitution in a binary mixture of organic solvents. The obtained fibers of CA loaded with CNCs had typical widths in the nano- and micro-scale and presented a glass transition temperature of 145?°C. The CA component was converted to cellulose by using alkaline hydrolysis to yield all-cellulose composite fibers that preserved the original morphology of the precursor system. Together with Fourier Transform Infrared Spectroscopy fingerprints the thermal behavior of the all-cellulose composite fibers indicated complete conversion of cellulose acetate to regenerated cellulose. Noticeable changes in the thermal, surface and chemical properties were observed upon deacetylation. Not only the thermal transitions of cellulose acetate disappeared but the initial water contact angle of the web was reduced drastically. Overall, we propose a simple method to produce all-cellulose composite fibers which are expected to display improved thermo-mechanical properties while keeping the unique features of the cellulose polymer.     

Tensile,Flexural and Chemical Resistance Properties of Sisal Fibre Reinforced Polymer Composites: Effect of Fibre Surface Treatment

In this study, effect of fibre surface treatment on tensile, flexural and chemical resistance properties were studied for sisal fibre reinforced composites. Natural ligno cellulosic sisal fibre reinforced composites were prepared by different surface treatments by hand lay-up method. Fibre surface treatments were carried out to produce good interface between the fibre and the matrix to improve the mechanical properties. Fibre surface treatments were done by boiled the sisal fibres in different % of NaOH and treated the fibres in different % of NaOH, treated in acetic acid and methanol. Unsaturated polyester resin was used as the matrix for preparing the composites. For comparison, these properties for untreated sisal fibre reinforced composites were also studied. From the results it was observed that 18% aqueous NaOH boiled sisal fibre reinforced composites have higher tensile, flexural properties than other composites. Untreated sisal fibre composites show lower properties than treated composites. Chemical resistance properties indicate that all sisal fibre reinforced composites are resistance to all chemicals except carbon tetra chloride. The tests are carried out as per the ASTM standards.     

Interfaces in Cross-Linked and Grafted Bacterial Cellulose/Poly(Lactic Acid) Resin Composites

This article presents approaches to maximize the mechanical performance of bacterial cellulose/poly(lactic acid) composites through chemical modification of the interface. This is achieved by both cross-linking the layered bacterial cellulose structure and by grafting maleic anhydride to the matrix material. Unmodified and glyoxalized bacterial cellulose (BC) networks have been embedded in poly(lactic acid) (PLA) resin and then in maleated resin using a compression molding method. The effect of these chemical modifications on the physical properties of these composites is reported. The tensile properties of the composites showed that Young??s moduli can be increased significantly when both BC networks and PLA were chemically modified. Interface consolidation between layers in BC networks has been achieved by glyoxalization. The effect of these modifications on both stress-transfer between the fibers and between the matrix and the fibers was quantified using Raman spectroscopy. Two competitive deformation mechanisms are identified; namely the mobility between BC layers, and between BC and PLA. The coupling strength of these interfaces could play a key role for optimization of these composites?? mechanical properties.     

Comparison of Polylactic Acid/Kenaf and Polylactic Acid/Rise Husk Composites: The Influence of the Natural Fibers on the Mechanical, Thermal and Biodegradability Properties

This paper investigates and compares the performances of polylactic acid (PLA)/kenaf (PLA-K) and PLA/rice husk (PLA-RH) composites in terms of biodegradability, mechanical and thermal properties. Composites with natural fiber weight content of 20% with fiber sizes of less than 100 μm were produced for testing and characterization. A twin-screw extrusion was used to compound PLA and natural fibers, and extruded composites were injection molded to test samples. Flexural and Izod impact test, TGA, soil burial test and SEM were used to investigate properties. All results were compared to a pure PLA matrix sample. The flexural modulus of the PLA increased with the addition of natural fibers, while the flexural strength decreased. The highest impact strength (34 J m⁻¹), flexural modulus (4.5 GPa) and flexural strength (90 MPa) were obtained for the composite made of PLA/kenaf (PLA-K), which means kenaf natural fibers are potential to be used as an alternative filler to enhance mechanical properties. On the other hand PLA-RH composite exhibits lower mechanical properties. The impact strength of PLA has decreased when filled with natural fibers; this decrease is more pronounced in the PLA-RH composite. In terms of thermal stability it has been found that the addition of natural fibers decreased the thermal stability of virgin PLA and the decrement was more prominent in the PLA-RH composite. Biodegradability of the composites slightly increased and reached 1.2 and 0.8% for PLA-K and PLA-RH respectively for a period of 90 days. SEM micrographs showed poor interfacial between the polymer matrix and natural fibers.     

Effect of Matrix–Particle Interfacial Adhesion on the Mechanical Properties of Poly(lactic acid)/Wood-Flour Micro-Composites

The influence of interfacial matrix/particle adhesion on the mechanical properties of poly(lactic acid) (PLA) micro-composites was investigated. The tensile strength of PLA/wood-flour micro-composites is almost independent of wood-flour content, suggesting only weak adhesion exists between the PLA matrix and the wood-flour particles. The addition of wood-flour resulted in an increase of up to 95% in the tensile modulus, in comparison with pure PLA, which showed a more resilient matrix. The addition of a coupling agent, methylenediphenyl-diisocyanate (MDI) to the composition resulted in an increase in tensile strength and tensile modulus of the micro-composites, of 10 and 135%, respectively, indicating enhanced matrix–particle interfacial adhesion. SEM and electron probe microanalysis provided evidence of improved interfacial adhesion between PLA and wood-flour particles from the addition of MDI. In contrast, addition of PEAA resulted in a micro-composite displaying substantially reduced tensile strength, up to 35% and a slightly increased in impact strength, up to 15%, consistent with the introduction of the rubbery PEAA component into the polymeric matrix. No evidence for increased matrix–particle adhesion was found for the PLA/wood-flour micro-composites containing PEAA.     

Processing Stability and Biodegradation of Polylactic Acid (PLA) Composites Reinforced with Cotton Linters or Maple Hardwood Fibres

Polylactic acid (PLA) composites comprising up to 25 wt% cotton linter (CL) or up to 50 % maple wood fibre (WF) were prepared by compounding and injection moulding. A reduction of crystallinity in the PLA matrix was observed as a result of the thermal processing method. These PLACL and PLAWF composites provided excellent improvements in both stiffness (with increases in tensile and flexural modulus) and toughness (increases in notched impact strength) properties over the neat PLA resin, while the tensile and flexural strengths of the composites were generally unchanged, while the strain at break values were reduced in comparison to the neat PLA. DMA results indicated incorporating these fibres caused the mechanical loss factor (tan δ) to decrease, suggesting better damping capabilities were achieved with the composites. SEM analysis of the impact fractured surfaces of the PLACL composites showed debonding-cavitation at the matrix-fibre interface while the PLAWF composites showed good wetting along its matrix-fibre interface. The composting of these composites up to 90 days showed that the degradation onset time was increased when increasing the fibre loadings, but the maximum degree of degradation and the maximum daily rates of degradation were decreased compared to neat PLA. On a weight basis of fibre loading, the PLACL composites had a quicker onset of biodegradation, a higher maximum daily rate of biodegradation and, overall, a higher degree of biodegradation at 90 days than the PLAWF composites, possibly due to the quicker thermal hydrolysis observed in the PLA matrix of the PLACL composites during processing and composting.     

Dispersion and Reinforcing Potential of Carboxymethylated Nanofibrillated Cellulose Powders Modified with 1-Hexanol in Extruded Poly(Lactic Acid) (PLA) Composites

Bionanocomposites of poly(lactic acid) (PLA) and chemically modified, nanofibrillated cellulose (NFC) powders were prepared by extrusion, followed by injection molding. The chemically modified NFC powders were prepared by carboxymethylation and mechanical disintegration of refined, bleached beech pulp (c-NFC), and subsequent esterification with 1-hexanol (c-NFC-hex). A solvent mix was then prepared by precipitating a suspension of c-NFC-hex and acetone-dissolved PLA in ice-cold isopropanol (c-NFC-hex_sm), extruded with PLA into pellets at different polymer/fiber ratios, and finally injection molded. Dynamic mechanical analysis and tensile tests were performed to study the reinforcing potential of dried and chemically modified NFC powders for PLA composite applications. The results showed a faint increase in modulus of elasticity of 10?% for composites with a loading of 7.5?% w/w of fibrils, irrespective of the type of chemically modified NFC powder. The increase in stiffness was accompanied by a slight decrease in tensile strength for all samples, as compared with neat PLA. The viscoelastic properties of the composites were essentially identical to neat PLA. The absence of a clear reinforcement of the polymer matrix was attributed to poor interactions with PLA and insufficient dispersion of the chemically modified NFC powders in the composite, as observed from scanning electron microscope images. Further explanation was found in the decrease of the thermal stability and crystallinity of the cellulose upon carboxymethylation.