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.     

Investigation on the Influence of EVA Content on the Mechanical and Thermal Characteristics of Poly(lactic acid) Blends

Poly(lactic acid) (PLA) has gained considerable attention nowadays as a biocompatible polymer owing to its advantage of being prepared from renewable resources. PLA exhibits excellent tensile strength, fabricability, thermal plasticity and biocompatibility properties comparable to many petroleum based plastics. However, low heat distortion temperature, brittleness and slow crystallization rate limit the practical applications of PLA. In order to address these limitations, an attempt has been made in the current work to prepare binary blends of PLA with ethylene vinyl acetate (EVA) at different compositions via melt mixing technique. Systematic investigation on the mechanical properties, thermal degradation and crystallization behavior for PLA-EVA blends was carried out. The impact strength of binary blends of PLA–EVA was found to increase significantly by 176% for 15 wt% of EVA compared to virgin PLA. This is due to the strong interfacial adhesion among PLA and EVA resulting in brittle to ductile transition. Scanning electron microscopy analysis for impact fractured surfaces of binary blends of PLA implied the toughening effect of PLA by EVA. Thermogravimetry analysis results revealed that the activation energy of PLA–EVA blends decreased with increase in EVA content in the PLA matrix. While, differential scanning calorimetry results obtained for PLA–EVA blends revealed the improvement in crystallinity when compared with neat PLA. The effect of EVA on non-isothermal melt crystallization kinetics of PLA was also examined via DSC at various heating rates. Decreasing trend in the t_1/2 values indicated the faster rate of crystallization mechanism after addition of EVA in the PLA matrix.     

Biodegradable Blends with Potential Use in Packaging: A Comparison of PLA/Chitosan and PLA/Cellulose Acetate Films

Poly(lactic acid) (PLA) is a biodegradable polymer that exhibits high elastic modulus, high mechanical strength, and feasible processability. However, high cost and fragility hinder the application of PLA in food packaging. Therefore, this study aimed to develop flexible PLA/acetate and PLA/chitosan films with improved thermal and mechanical properties without the addition of a plasticizer and additive to yield extruder compositions with melt temperatures above those of acetate and chitosan. PLA blends with 10, 20, and 30 wt% of chitosan or cellulose acetate were processed in a twin-screw extruder, and grain pellets were then pressed to form films. PLA/acetate films showed an increase of 30 °C in initial degradation temperature and an increase of 3.9 % in elongation at break. On the other hand, PLA/chitosan films showed improvements in mechanical properties as an increase of 4.7 % in elongation at break. PLA/chitosan film which presented the greatest increase in elongation at break proved to be the best candidate for application in packaging.     

Reactive Compatibilization of Biobased Polyurethane Prepolymer Toughening Polylactide Prepared by Melt Blending

Polylactide (PLA) is a major biodegradable polymer, which has received extensive interests over the past decades and holds great potential to replace several petroleum-based polymeric materials. Nevertheless, the inherent brittleness and low impact strength have restricted its invasion to niche markets. In this paper, the authors demonstrate that the entirely bio-sourced blends, namely PLA and castor oil-based polyurethane prepolymer (COPUP), were first melt-compounded in an effort to prepare novel biodegradable materials with an excellent balance of properties. NCO-terminated COPUP was successfully synthesized and subsequently mixed with variable concentration of PLA matrix using melt-compounded by twin-screw extrusion technique. The miscibility, phase morphology, mechanical properties, and thermal resistance of the blends were investigated. During FTIR analysis, it suggests that the interfacial compatibilization between COPUP and PLA phase occurred by the reaction of –NCO group of MDI with terminal hydroxyl group of PLA. DMA analysis showed that COPUP and PLA showed some limited miscibility with shifted glass transition temperature. The morphologies of fracture surface showed a brittle-to-ductile transition owing by the addition of COPUP. The crystallization behavior was studied by differential scanning calorimeter (DSC). The strain at break and notched impact strength of PLA/COPUP blends were increased more than 112–15.4 times elegant of neat PLA; the increase is superior to previous toughening effect by using petroleum-based tougheners. Furthermore, the thermal resistances and melt flow properties of the materials were also examined by analysis of the melt flow index and heat deflection temperature use in the work. With enhanced toughness, the PLA/COPUP blends could be used as replacements for some traditional petroleum-based polymeric materials.     

Biodegradable Polyester-Based Blend Reinforced with Curauá Fiber: Thermal,Mechanical and Biodegradation Behaviour

Biodegradable composites can be produced by the combination of biodegradable polymers (BP) as matrix and vegetal fibers as reinforcement. Composites of a commercial biodegradable polymer blend and curauá fibers (loaded at 5, 15 and 20 wt%) were prepared by melt mixing in a twin-screw extruder. Chemical treatments such as alkali treatment of the fiber and addition of maleic anhydride grafted polypropylene (MA-g-PP) as coupling agent were performed to promote polymer/fiber interfacial adhesion so that mechanical performance can be improved. The resulting composites were evaluated through hardness, melt flow index and tensile, flexural and impact strengths as well as water absorption. Thermal analysis and Fourier transform infrared spectroscopy were also employed to characterize the composites. The polymer/fiber interface was investigated through scanning electron microscopy analysis. The biodegradability of composites was evaluated by compost-soil burial test. The addition of curauá fiber promoted an increase in the mechanical strengths and composites treated with 2 wt% MA-g-PP with 20 wt% curauá fiber showed an increase of nearly 75% in tensile and 56% in flexural strengths besides an improvement in impact strength with respect to neat polymer blend. Nevertheless, treated composites showed an increase in water absorption and biodegradation tests showed that the addition of fiber retards degradation time. The retained mass of BP/20 wt% fiber composite with MA-g-PP and neat BP was 68 and 26%, respectively, after 210 days of degradation test.     

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.     

Poly(Ethylene Glycol) as a Compatibilizer for Poly(Lactic Acid)/Thermoplastic Starch Blends

A new route to prepare poly(lactic acid) (PLA)/thermoplastic starch (TPS) blends is described in this work using poly(ethylene glycol) (PEG), a non-toxic polymer, as a compatibilizer. The influence of PEG on the morphology and properties of PLA/TPS blends was studied. The blends were processed using a twin-screw micro-compounder and a micro-injector. The morphologies were analyzed by scanning and transmission electron microscopies and the material properties were evaluated by dynamic-mechanical, differential scanning calorimetry, thermogravimetric analysis and mechanical tests. PLA/TPS blends presented large TPS phase size distribution and low adhesion between phases which was responsible for the lower elastic modulus of this blend when compared to pure PLA. The addition of PEG resulted in the increase of PLA crystallization, due to its plasticizing effect, and improvement of the interfacial interaction between TPS and PLA matrix. Results show that incorporation of PEG increased the impact strength of the ternary blend and that the elastic modulus remained similar to the PLA/TPS blend.     

Renewable Resource-Based Composites of Acorn Powder and Polylactide Bio-Plastic: Preparation and Properties Evaluation

Renewable resource-based composites were prepared with acorn powder and Thermoplastic resin poly(lactic acid) (PLA) by twin-screw extrusion followed by injection molding processing or hot-compression molding processing. The study of the composites microstructure showed poor adhesion between acorn powder and PLA matrix. The hygroscopicity, mechanical properties and melt flow property of composites were promising even though the composites had a 70 wt% content of acorn powder. Silane coupling agent, 4,4′-Methylenebis (phenyl isocyanate) and PLA grafted with maleic anhydride did not show obvious effect on mechanical properties of composites. The impact resistance strength of reinforced composites with steel fiber webs were improved greatly in comparison with those having no steel fiber webs. Thermal properties results of DSC and DMA showed that the presence of acorn powder significantly affected the crystallinity, crystallization temperature (T_c), glass transition temperature (T_g) and melting temperature (T_m) of PLA matrix. The study results proved that composites had superior mechanical properties, enough to partially replace the conventional thermoplastic plastics.     

Molding Method, Thermal and Mechanical Properties of Jute/PLA Injection Molding

Natural composites have been important materials system due to preservation of earth environments. Natural fibers such as jute, hemp, bagasse and so on are very good candidate of natural composites as reinforcements. On the other hand regarding matrix parts thermosetting polymer and thermoplastic polymer deriver form petrochemical products are not environmental friendly material, even if thermoplastic polymer can be recycled. In order to create fully environmental friendly material (FEFM) biodegradable polymer which can be deriver from natural resources is needed. Therefore poly(lactic acid) (PLA) polymer is very good material for the FEFM. In this paper jute fiber filled PLA resin (jute/PLA) composites was fabricated by injection moldings and mechanical properties were measured. It is believable that industries will have much attention to FEFM, so that injection molding was adopted to fabricate the composites. Long fiber pellet fabricated by pultrusion technique was adopted to prepare jute/PLA pellet. Because it is able to fabricate composite pellets with relative long length fibers for injection molding process, where, jute yarns were continuously pulled and coated with PLA resin. Here two kinds of PLA materials were used including the one with mold releasing agent and the other without it. After pass through a heated die whereby PLA resin impregnates into the jute yarns and sufficient cooling, the impregnated jute yarns were cut into pellets. Then jute/PLA pellets were fed into injection machine to make dumbbell shape specimens. In current study, the effects of temperature of PLA melting temperature i.e. impregnation temperature and the kinds of PLA were focused to get optimum molding condition. The volume fractions of jute fiber in pellet were measured by several measuring method including image analyzing, density measurement and dissolution methods. Additionally, thermal and mechanical properties were investigated. It is found that 250° is much suitable for jute/PLA long fiber pultrusion process because of its less heat degradation of jute, better impregnation, acceptable mechanical property and higher production efficiency. Additionally the jute fibers seem much effective to increase deflection temperature under load, tensile modulus and Izod strength.     

Aging of Toughened Polylactic Acid Nanocomposites: Water Absorption,Hygrothermal Degradation and Soil Burial Analysis

The environmental aging behaviour of montmorillonite (MMT) filled polylactic acid (PLA) nanocomposites (PLA/MMT) and linear low density polyethylene (LLDPE)-toughened PLA (PLA/LLDPE ratio = 90/10) nanocomposites (PLA/LLDPE/MMT) were investigated in this study. The nanocomposites were subjected to water absorption, hygrothermal degradation and soil burial analysis. Both PLA/MMT and PLA/LLDPE/MMT nanocomposites were immersed in distilled water at three different temperatures (room temperature, 60, and 90 °C) and the weight difference before and after immersion was calculated. The kinetics of water absorption for both nanocomposites followed the Fick’s second law of diffusion, where a linear relationship exists between the initial moisture absorption at any time t and t ^1/2 (the square root of time), followed by a horizontal plateau (saturation). The equilibrium moisture content (M _m ) and diffusion coefficient (D) of PLA nanocomposites increased with the addition of MMT (2 phr) and LLDPE. However, the D values of both nanocomposites decreased by increasing MMT (4 phr). The M _m for PLA/MMT and PLA/LLDPE/MMT nanocomposites increased by increasing immersion temperature (60 °C) and prolonged immersion resulted in hygrothermal degradation of both nanocomposites. The hygrothermal degradation studies showed that PLA degrades much faster at 90 °C as compared to 60 °C in both the nanocomposites. The addition of MMT and LLDPE improved the hygrothermal stability of PLA in both nanocomposites. Soil burial test revealed deterioration of impact strength in all samples while the rate of biodegradation was retarded in the presence of MMT and LLDPE.     

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.     

Performance of Cow Dung Reinforced Biodegradable Poly(Lactic Acid) Biocomposites for Structural Applications

In this work, performance of cow dung (CD) reinforced poly(lactic acid) (PLA) biocomposites was investigated for the potential use in load bearing application. CD of average 4 mm size was blended with PLA at different CD ratios (0–50 wt%) and their effects on the biocomposite properties were studied. The results showed an improvement in the flexural properties, while the tensile and impact strength dropped by 20 and 28% with the addition of 50% CD. The decline in the tensile and impact strength was due to micro-cracking and voids formation at higher CD content. Also, the incorporation of CD slightly decreased the thermal stability of the biocomposite. However, dynamic mechanical properties of the biocomposites generally improved. SEM analysis of tensile and impact fractured surfaces indicated that the CD had a reasonable adhesion with matrix. Moreover, the SEM micrographs of soil burial studies showed an accelerated degradation of higher CD wt% biocomposites.     

Effect of Hydrothermal Aging on Injection Molded Short Jute Fiber Reinforced Poly(Lactic Acid) (PLA) Composites

This work focused on the durability of short jute fiber reinforced poly(lactic acid) (PLA) composites in distilled water at different temperatures (23, 37.8 and 60 °C). Morphological, thermal and mechanical properties (tensile, flexural, and impact) of jute/PLA composites were investigated before and after aging. Different from traditional synthetic fiber reinforced polymer composites, the stability of jute/PLA composites in water was significantly influenced by hydrothermal temperature. The mechanical properties of the composites and molecular weight of PLA matrix declined quickly at 60 °C, however, this process was quite slower at temperatures of 23 and 37.8 °C. Impact properties of the composites were hardly decreased, but the tensile and flexural properties suffered a drop though to various degrees with three degradation stages at 23 and 37.8 °C. The poor interface of composites and the degradation of PLA matrix were the main damage mechanism induced by hydrothermal aging. Furthermore, considering the hydrolysis of PLA matrix, the cleavage of PLA molecular chain in different aging time was quantitatively investigated for the first time to illustrate hydrolysis degree of PLA matrix at different aging time.     

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.     

Poly(3-Hydroxybutyrate-co-3-Hydroxyvalerate)/Polylactide Blends: Thermal Stability,Flammability and Thermo-Mechanical Behavior

Blends of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) and polylactide (PLA) with different PHBV/PLA weight ratios (100/0, 75/25, 50/50, 25/75, 0/100) were prepared by melt compounding. Their mutual contributions in terms of thermal stability, flammability resistance, mechanical properties and rheological behavior were investigated. The study showed that the increase in PLA content in PHBV/PLA blends leads to enhanced properties. Consequently, thermal stability and flammability resistance were improved. Further, the rheological measurements indicated an increase in storage modulus and loss modulus of PHBV matrix by addition of PLA.     

Effect of Nucleating Agents on Physical Properties of Poly(lactic acid) and Its Blend with Natural Rubber

Poly(lactic acid) (PLA) presents high strength and modulus, but very low toughness as well as slow crystallization. Natural rubber (NR) was blended to enhance the toughness and nucleating agent was added to improve the crystallization. Cyclodextrin (CD), considered as a green compound, as well as calcium carbonate (CaCO₃) and talc were used as nucleating agents. Effects of these nucleating agents on crystallization, mechanical properties and morphology of neat PLA and PLA/NR blend were investigated. It was found that the addition of talc and CD decreased cold crystallization temperature (T_cc) of the PLA. Same result was obtained in PLA/NR blend containing talc. All nucleating agents increased the degree of crystallinity (Χ_C) of PLA, whereas only talc and CaCO₃ increased Χ_C of PLA in PLA/NR blends. The enhanced toughness of PLA by the addition of nucleating agent was attributed to its increased crystallinity, as well as decreased spherulite size. For PLA/NR blends, the increase in toughness was mainly contributed by the presence of the rubber.     

Effects of Temperature and Relative Humidity on Polylactic Acid Plastic Degradation

Three high molecular weight (120,000 to 200,000 g mol^–1) polylactic acid (PLA) plastic films from Chronopol (Ch-I) and Cargill Dow Polymers (GII and Ca-I) were analyzed for their degradation under various temperature and relative humidity (RH) conditions. Two sets of plastic films, each containing 11 samples, were randomly hung in a temperature/humidity-controlled chamber by means of plastic-coated paper clips. The tested conditions were 28, 40, and 55°C at 50 and 100% RH, respectively, and 55°C at 10% RH. The three tested PLA films started to lose their tensile properties when their weight-average molecular weight (M _w) was in the range of 50,000 to 75,000 g mol^–1. The average degradation rate of Ch-I, GII, and Ca-I was 28,931, 27,361, and 63,025 M _w/week, respectively. Hence, GII had a faster degradation rate than Ch-I and Ca-I under all tested conditions. The degradation rate of PLA plastics was enhanced by the increase in temperature and relative humidity. This trend was observed in all three PLA plastics (Ca-I, GII, and Ch-I). Of the three tested films, Ch-I was the first to lose its mechanical properties, whereas Ca-I demonstrated the slowest loss, with mechanical properties under all tested conditions.     

Effect of Compatibilizing Agent on the Properties of Highly Crystalline Composites Based on Poly(lactic acid) and Wood Flour and/or Mica

This article contains a concept of the mechanical properties improvement of the highly crystalline poly(lactic acid) (PLA) and filled composites. PLA as a semi-crystalline thermoplastic polymer was plasticized with poly(ethylene glycol) and filled with 30 vol% of organic and/or inorganic filler. The degree of crytallinity was intentionally increased by annealing. The filler/polymer matrix interphase was modified with the addition of 4, 4′-Methylenediphenyl diisocyanate (MDI). The effect of compatibilizing as well as plasticizing agent on the thermal and mechanical properties, the water-absorption behaviour and crystallization characteristics were studied. The results indicated that high content of filler and crystallites have a strong influence on the composite′s mechanical properties despite of the plasticizer content, showing a high Young modulus. The MDI seems to react in preference easy with plasticizing agent and then alternatively with filler due to the low functionality of commercial PLA grade.     

Chemically Functionalized Plant Fibers and Carbon Nanotubes for High Compatibility and Reinforcement in Polylactic Acid (PLA) Composite

In this study, surface modification is used to improve the compatibility of Kenaf fibers (KFs) and multi-walled carbon nanotubes (MWCNTs) in a polylactic acid (PLA) matrix, as well as to enhance the mechanical properties. Through the use of a silane coupling agent, the KF is grafted with functional groups to generate a chemical bond with the PLA; the modified KF shows high compatibility in the PLA matrix. Compared to the bare PLA, the optimal KF/MWCNT/PLA composite (PC1F30-OX) shows increases of 58% in tensile strength, and 113% in impact strength. A small addition of MWCNTs (1 wt%) dramatically improves the antistatic ability by lowering the surface resistance to 3.47 GΩ. With the addition of hydrophilic KF into the PLA, the composite becomes much more environmentally friendly, and the biodegradation rate can be controlled by the amount of KF added. The addition of hydrophilic KF allowed the composite to accommodate more enzyme to hasten the biodegradation; almost complete decomposition occurred after 11 weeks.     

The Effect of Nanoclays on the Properties of PLLA-modified Polymers Part 1: Mechanical and Thermal Properties

Organically modified montmorillonite clays were incorporated at a 5% loading level into film grade of poly-L-lactic acid (PLLA) using a variety of masterbatches based on either semi-crystalline or amorphous poly-(lactic acid), as well as biodegradable aromatic aliphatic polyester. The PLLA masterbatches and compounded formulations were prepared using a twin screw compounding extruder, while the films were prepared using a single screw cast film extruder. The thermal and mechanical properties of the films were examined in order to determine the effect of the clay and different carriers on the polymer–clay interactions. In the optimal case, when a PLLA-based masterbatch was used, the tensile modulus increased by 30%, elongation increased by 40%, and the cold crystallization temperature decreased by 15 °C, compared to neat PLLA. The properties improvement of PLLA films containing nano clays demonstrated the possibility to extend the range of biodegradable film applications, especially in the field of packaging.