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.     

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.     

Rheological and Thermal Properties of the PLA Modified by Electron Beam Irradiation in the Presence of Functional Monomer

Polylactic acid (PLA) has been modified by electron beam radiation in the presence of glycidyl methacrylate (GMA) to enhance the melt strength of PLA. The modified PLA was prepared by varying both the amount of GMA and the irradiation dose and was characterized by observing the thermal properties, the melt viscoelastic properties and the gel fraction. For comparison, virgin PLA was also irradiated. All irradiated virgin PLA had a lower complex viscosity and a storage modulus compared to virgin PLA due to irradiation-induced chain scission. However, these properties were remarkably improved due to formation of long chain branching and retarding chain scission if GMA was introduced in this system. The increase in melt viscoelastic property was much dependent on the irradiation dose. At optimum doses of radiation, it showed maximum complex viscosity and storage modulus. The PLA irradiated with 20 kGy in the presence of 3 phr GMA showed a complex viscosity of about 10 times higher and a storage modulus of 100 times higher than those of virgin PLA at 0.1 rad/s. Gel fraction measurement revealed that chain scission and branching was more dominant than crosslinking. The biodegradability of irradiated PLA was slightly decreased by the presence of GMA.     

Pyrolysis of virgin and waste polypropylene and its mixtures with waste polyethylene and polystyrene

A comparison of waste and virgin polypropylene (PP) plastics under slow pyrolysis conditions is presented. Moreover, mixtures of waste PP with wastes of polyethylene (PE) and polystyrene (PS) were pyrolyzed under the same operating conditions. Not only the impact of waste on degradation products but also impacts of the variations in the mixing ratio were investigated. The thermogravimetric weight loss curves and their derivatives of virgin and waste PP showed differences due to the impurities which are dirt and food residues. The liquid yield distribution concerning the aliphatic, mono-aromatic and poly-aromatic compounds varies as the ratio of PP waste increases in the waste plastic mixtures. In addition to this, the alkene/alkane ratio of gas products shows variations depending on the mixing ratio of wastes.     

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.     

Poly(Ethylene Glycol) Grafted Starch Introducing a Novel Interphase in Poly(Lactic Acid)/Poly(Ethylene Glycol)/Starch Ternary Composites

The main purpose of this study is challenging to dramatically improve the toughness of poly(lactic acid) (PLA)/starch by adding poly (ethylene glycol) (PEG) into the composites and grafting PEG molecules onto the surface of starch particles. It was found that the surface grafting of PEG onto starch induced the presence of PEG-rich regions located around the starch particles, caused by migration and aggregation of free PEG molecules. A novel interphase transition layer between PLA and starch was formed, which showed great ability for cavitation and vested large-scaled plastic deformation to PLA matrix. Further mechanical properties tests indicated the formation of interphase layer significantly increase the elongation at break from 10.2 to 254.5%, and notched impact strength from 1.56 to 2.37?kJ/m² for PLA/PEG/starch ternary composites. The influence of PEG component, ethanol extraction and annealing was also investigated.     

Novel Tough Crystalline Blends of Polylactide with Ethylene Glycol Derivative of POSS

Blending of polylactide (PLA) with low stereoregularity and polyhedral oligomeric silsesquioxane grafted with arms of poly(ethylene glycol) methyl ether, acting as a plasticizer, allowed us previously to obtain a novel stable elastomeric-like material. The present contribution focuses on the properties of semi-crystalline PLA plasticized with this compound. Melt blends of PLA with 5–15 wt% of the plasticizer, were compression molded, quenched and annealed, which enabled cold-crystallization. The glass transition temperature of the blends and their drawability depended on their crystallinity and plasticizer content. The best ductility was reached at the plasticizer content of 15 wt%; the achieved strain at break was 6.5 (650%) and 1.3 (130%), for the quenched and annealed material, respectively. The latter value exceeded 20 times the strain at break of neat crystalline PLA. The tensile toughness of the annealed 15 wt% blend was 12 times larger than that of crystalline PLA. Moreover, annealing of 15 wt% blend improved its yield strength by 40%. Despite the two peaks of the loss modulus, indicating the two glass transitions in this blend, no heterogeneities were found by scanning electron microscopy, indicating that the plasticizer enriched phase formed instead of distinct inclusions of the plasticizer.     

Effect of Poly(Vinyl Acetate) on Mechanical Properties and Characteristics of Poly(Lactic Acid)/Natural Rubber Blends

Natural rubber grafted with poly(vinyl acetate) copolymer (NR-g-PVAc) was synthesized by emulsion polymerization. Three graft copolymers were prepared with different PVAc contents: 1 % (G1), 5 % (G5) and 12 % (G12). Poly(lactic acid) (PLA) was melt blended with natural rubber (NR) and/or NR-g-PVAc in a twin screw extruder. The blends contained 10–20 wt% rubber. The notched Izod impact strength and tensile properties were determined from the compression molded specimens. The effect of NR mastication on the mechanical properties of the PLA/NR/NR-g-PVAc blend was evaluated. Characterization by DMTA and DSC showed an enhancement in miscibility of the PLA/NR-g-PVAc blend. The temperature of the maximum tan δ of the PLA decreased with increasing PVAc content in the graft copolymer, i.e., from 71 °C (pure PLA) to 63 °C (the blend containing 10 % G12). The increase in miscibility brought about a reduction in the rubber particle diameter. These changes were attributed to the enhancement of toughness and ductility of PLA after blending with NR-g-PVAc. Therefore, NR-g-PVAc could be used as a toughening agent of PLA and as a compatibilizer of the PLA/NR blend. NR mastication was an efficient method for increasing the toughness and ductility of the blends which depended on the blend composition and the number of mastications.     

Degradation of Polylactic Acid by Irradiation

Polylactic acid (PLA) waste has various treatment methods, such as natural decomposition, composting, incineration, and hydrolysis. Degradation of PLA waste by gamma ray and pulsed light irradiation is an efficient, safe and innovative method that also protects the environment. The focus of this study was on the development of an alternative, green technology for solving the PLA waste disposal problem of PLA, rather than using incineration or the landfill method. We used a novel approach to identify the thermal decomposition and heat properties of crystalline poly lactic acid, non-crystalline polylactic acid, and blend polylactic acid. The approach involved the degradation of the materials with gamma ray and pulsed light irradiation followed by thermogravimetric analysis (TGA). We also developed a novel approach to the heat effect, including heat reactivity properties by TGA tests and thermal mass loss simulation for proper application, processing, and waste treatment conditions. The data from this study can be used to improve the design of operation and waste treatment protocols for PLA, which will benefit the environment.     

Double-Melting Behavior of Bamboo Fiber/Talc/Poly (Lactic Acid) Composites

The melting and crystallization behavior of pure poly (lactic acid) (PLA) and PLA composites (1% Bamboo Fiber (BF)/PLA, 1% Talc/PLA, 1% BF/1% Talc/PLA) were studied with differential scanning calorimetry (DSC). DSC curves for PLA composites were obtained at various cooling rates, the crystallization temperature and heat of crystallization of PLA composites decreased almost linearly with increasing of log (cooling rate). Moreover, BF has minor effect and talc has the great effect on the crystallization temperature in the PLA composites. With increasing of cooling rate, the main melting temperature of PLA composites decreased. In pure PLA and 1% BF/PLA, the double-melting behavior appeared in the heating curves after slow rate of cooling, and there was the opposite phenomenon of double-melting behavior in other two PLA composites. BF promotes forming the imperfect crystal in the PLA composites during heating process. With increasing of heating rate, the main melting temperature of PLA composites increased except the 1% BF/PLA. At various heating rates, the defects of BF structure promoted the melt-recrystallization and talc promoted forming the small crystals. At last, the recrystallization model was given.     

Study of Thermo-Mechanical and Morphological Behaviour of Biodegradable PLA/PBAT/Layered Silicate Blend Nanocomposites

Poly (lactic acid) (PLA) and poly (butylene adipate-co-terephthalate) (PBAT) blend nanocomposites were prepared using melt blending technique followed by compression moulding. The blend nanocomposites were prepared with a variation of PBAT loading along with maleic anhydride and benzoyl peroxide ranging from 5 to 20 wt% along with two different commercially available nanoclays cloisite 93A and cloisite 30B (C30B) at 3 wt% loading. The maleic anhydride and benzoyl peroxide were used during the melt blending of the blend nanocomposites as a compatibilizer and as an accelerator respectively. Maleic anhydride used to enhance the compatibility of the PLA/PBAT blend and as well as the uniform adhesion of the nanoclays with them. The properties and characterizations of PLA matrix and the PLA/PBAT blend nanocomposites have been studied. The tensile strength, % elongation and impact strength increased with the preparation of PLA/PBAT blend nanocomposites as compared with PLA matrix. PLA/PBAT/C30B blend nanocomposites exhibited optimum tensile strength at 15 wt% of PBAT loading. Differential scanning calorimetry and thermogravimetric analysis also showed improved thermal properties as compared with virgin PLA. The wide angle X-ray diffraction studies indicated an increase in d-spacing in PLA/PBAT/C30B blend nanocomposite thus revealing intercalated morphology.     

Study on the Effect of Dicumyl Peroxide on Structure and Properties of Poly(Lactic Acid)/Natural Rubber Blend

In attempt to enhance the compatibility of NR in PLA matrix, and furthermore to enhance mechanical properties of PLA, PLA/NR blends with strong interaction were prepared in Haake internal mixer, using dicumyl peroxide (DCP) as cross-linker. The effects of dicumyl peroxide on morphology, thermal properties, mechanical properties and rheological properties of PLA and PLA/NR blends were studied. The results indicated that dicumyl peroxide could increase the compatibility of poly(lactic acid) and natural rubber. With small amount of dicumyl peroxide, the effect on NR toughening PLA was enhanced and the tensile toughness of PLA/NR blends was improved. When the DCP content was up to 0.2 wt%, the PLA/NR blend reached the maximum elongation at break (26.21 %) which was 2.5 times of that of neat PLA (the elongation at break of neat PLA was 10.7 %). Meanwhile, with introducing 2 wt% DCP into PLA/NR blend, the maximum Charpy impact strength (7.36 kJ/m²) could be achieved which was 1.8 times of that of neat PLA (4.18 kJ/m²). Moreover, adding adequate amount of DCP could improve the processing properties of blends: the viscosity of PLA/NR blend decreased significantly and the lowest viscosity of the blends could be achieved when the DCP content was 0.5 wt%.     

Effect of Nucleation of Tricalcium Phosphate and Isothermal Annealing on the Crystallization of Poly(l-lactide-co-glycolide)

We investigated the effect of nucleation and isothermal annealing on the crystallization behavior of a random copolymer, poly(l-lactide-co-glycolide) (PLLGA), with monomer molar ratios of 85/15 (PLLGA85/15) by scanning electron microscopy, polarizing optical microscopy, differential scanning calorimetry, and X-ray diffraction, and examination of the tensile properties of the resultant product. The effect of heterogeneous nucleation was assessed by the addition of tricalcium phosphate (TCP) as a nucleating agent. Nucleation and isothermal annealing of PLLGA at 130 °C were conducted to improve the degree of crystallinity of the copolymer. The fracture surfaces of the TCP/PLLGA85/15 composite bar showed a considerable number of spherulites with TCP as their nucleus. Addition of TCP and subsequent annealing improved the degree of crystallinity. After annealing, the TCP/PLLGA85/15 composite samples gained nearly the same strength that the pure PLLGA85/15 samples possessed. It is believed that this method will enhance the practical application of this nucleating agent in the processing of polymers.     

Melt Flow Behavior and Processability of Polylactic Acid/Polystyrene (PLA/PS) Polymer Blends

The present investigation dealt with the flow behavior and processability of polylactic acid/polystyrene (PLA/PS) polymer blends using a capillary rheometer. For this purpose, PLA/PS blends with different ratios of the concentrations were prepared using a single screw extruder. The shear viscosity, shear stress, shear rate, power-law index, viscous activation energy at a constant shear stress, and elongational stress were determined. PLA/PS blends exhibited a typical shear-thinning behavior over the entire range of shear rates tested, and the viscosity values of the blends would tend to decrease with increasing amount of PLA. In addition, the polymer blend of 70 % PLA and 30 % PS was found to be relatively less sensitive to the processing temperature, implying that the extrusion process was more desirable for fabrication of PLA/PS polymer blend than the injection process.     

Mechanical Property Characterization of Plasticized Sugar Beet Pulp and Poly(Lactic Acid) Green Composites Using Acoustic Emission and Confocal Microscopy

Sorbitol and glycerol were used to plasticize sugar beet pulp-poly(lactic acid) green composites. The plasticizer was incorporated into sugar beet pulp (SBP) at 0%, 10%, 20%, 30% and 40% w/w at low temperature and shear and then compounded with poly(lactic acid) (PLA) using twin-screw extrusion and injection molding. The SBP:PLA ratio was maintained at 30:70. As expected, tensile strength decreased by 25% and the elongation increased. Acoustic emission (AE) showed correlated debonding and fracture mechanisms for up to 20% w/w plasticizer and uncorrelated debonding and fracture for 30–40% sorbitol and 30% glycerol content in SBP–PLA composites. All samples had a well dispersed SBP phase with some aggregation in the PLA matrix. However, at 40% glycerol plasticized SBP–PLA composites exhibited unique AE behavior and confocal microscopy revealed the plasticized SBP and PLA formed a co-continuous two phase system.

Flammability Properties of Virgin and Recycled Polycarbonate (PC) and Acrylonitrile–Butadiene–Styrene (ABS) Recovered from End-of-Life Electronics

Acrylonitrile–Butadiene–Styrene (ABS), Polycarbonate (PC) and their alloys are widely used in automotive industry, computer and equipment housings. With increasing disposal of end-of-life electronic equipment, there is also an increased demand for recycling of these materials so that they do not pose environmental challenge as solid waste. One of the recycling approaches is mechanical recycling of these thermoplastics where recycled plastic is melt blended with virgin materials to obtain a high quality product. Besides obtaining desirable mechanical properties, such blends should also conform to fire safety standards. In this work, a series of blends were prepared using PC and ABS recovered from discarded computers and virgin materials using a twin-screw extruder. Their flammability properties were evaluated using burner flammability tests and Ohio State University (OSU) release rate tests. It was found that the extinguishing time, burning extent and weight loss appears to progressively decrease with the addition of both virgin or recycled PC to virgin or recycled ABS. It was also seen that the addition of the 70% of PC, virgin or recycled, to ABS virgin or recycled, appears to significantly decrease heat release and smoke evolution. The results of this study indicate that recycled polycarbonate can be used as an additive for virgin or recycled ABS, as a means of giving flame resistance to ABS in high-value applications. This result is significant when related to the result obtained by a separate study indicating that up to 25% of recycled material can be used without degradation of mechanical properties in the presence of 15% short glass fiber reinforcement.     

Preparation and Properties of Biodegradable Poly(lactic acid)/Poly(butylene adipate-co-terephthalate) Blend with Epoxy-Functional Styrene Acrylic Copolymer as Reactive Agent

Poly (lactic acid) (PLA) and poly (butylene adipate-co-terephthalate) (PBAT) are biodegradable polyesters and can be blended by twin-screw extrusion. Epoxy-functional styrene acrylic copolymer (ESA) was used as reactive agent for PLA/PBAT blends and the mechanical properties, phase morphology, thermal properties, melt properties, and melt rheological behaviors of the blends were investigated. During thermal extrusion, ESA was mainly a chain extender for the PLA matrix but had no evident reaction with PBAT. The great improvement in the toughness of PLA based blends was achieved by the addition of PBAT of no less than 15 wt% and that of ESA of no more than 0.5 wt%. Although SEM micrographs and the reduced deviation of the terminal slope of G′ and G″ indicated better compatibility and adhesion between the two phases, the blend with ESA was still a two-phase system as indicated in DSC curves. Rheological results reveal that the addition of ESA increased the storage modulus (G′), loss modulus (G″) and complex viscosity of the blend at nearly all frequencies. The melt strength and melt elasticity of the blend are improved by addition of ESA.     

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.     

Fabrication of Admicelled Natural Rubber by Polycaprolactone for Toughening Poly(lactic acid)

Natural rubber (NR) with polycaprolactone (PCL) core–shell (NR-ad-PCL), synthesized by admicellar polymerization, was acted as an impact modifier for poly(lactic acid) (PLA). PLA and NR-ad-PCL were melt-blended using a co-rotating twin screw extruder. The morphology of PLA/NR-ad-PCL blends showed good adhesion as smooth boundary around rubber particles and PLA matrix. Only 5 wt% of rubber phase, NR-ad-PCL was more effective than NR to enhance toughness and mechanical properties of PLA. The contents of the NR-ad-PCL were varied from 5, 10, 15 and 20 wt%. From thermal results, the incorporation of the NR-ad-PCL decreased the glass transition temperature and slightly increased degree of crystallinity of PLA. Mechanical properties of the PLA/NR-ad-PCL blends were investigated by dynamic mechanical analyser, pendulum impact tester and universal testing machine for tension and flexural properties. The increasing NR-ad-PCL contents led to decreasing Young’s and storage moduli but increasing loss modulus. Impact strength and elongation at break of the PLA/NR-ad-PCL blends increased with increasing NR-ad-PCL content up to 15 wt% where the maximum impact strength was about three times higher than that of pure PLA and the elongation at break increased to 79%.     

Processing and Characterization of Short-Fiber Reinforced Jute/Poly Butylene Succinate Biodegradable Composites: The Effect of Weld-Line

Fabrication of complex injection molded parts often involves the use of multiple gates. In such situations, polymer melts from different gates meld to form the molded part (weld line). This paper reports on the fabrication and characterization of the mechanical and morphological properties of short fiber reinforced jute/poly butylene succinate (PBS) biodegradable composites. The effect of a dual gated mold in the fabrication of welded specimens was a key focus of the investigation. It was observed that incorporation of jute fiber (10 wt%) conferred drastic changes on the stress–strain properties of the matrix as the elongation at break (EB), dropped from 160% in the matrix to just 10% in the composite. The tensile strength of the composite was lower than that of the matrix. However, it is noteworthy that the tensile modulus of the composite increased. Bending test also revealed that both bending strength and modulus increased with the incorporation of jute. Morphological studies of the tensile fracture surface using SEM revealed two types of failure mode. Ductile failure was indicated by plastic deformation at the initiation of fracture followed by brittle failure. The good interfacial bonding indicated between jute and PBS was attributed to positive interaction between the two polar polymers. A comparison of the non-weld and weld-line samples revealed that the weld-line composites have better mechanical integrity than the corresponding polymer matrix with weld line. The results also revealed that elongation at break and toughness are most sensitive to the presence of the weld-line whereas flexural properties are least sensitive.