Rheology,Morphology, Crystallization Behaviors,Mechanical and Thermal Properties of Poly(lactic acid)/Polypropylene/Maleic Anhydride-Grafted Polypropylene Blends

The rheologies, morphologies, crystallization behaviors, mechanical and thermal properties of poly(lactic acid) (PLA)/polypropylene (PP) blends and PLA/PP/maleic anhydride-grafted PP (MAPP) blends were investigated. The results showed that the complex viscosities of PLA/PP blends were between those of neat PLA and neat PP, and MAPP had a thinning effect on those of the blends. PLA/PP blends exhibited the distinct phase separation morphologies due to the limited partial miscibility of the blend components. MAPP slightly improved the miscibility between PLA and PP. Both the cold crystallization of PLA component and melt crystallization of PP component were enhanced, probably because PLA and PP were reciprocal nucleating agents. The tensile strength and flexural modulus decreased, while the tensile strain at break and heat deflection temperature (HDT) increased with the increasing PP content. MAPP had the positive effects on the notched impact strength and HDT of PLA-rich blends and also increased the flexural modulus of the binary blends. The thermal stability of the blend was improved by PP, and the incorporation of MAPP further enhanced the thermal stability.     

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.     

Study of Effects of Processing Aids on Properties of Poly(lactic acid)/Soy Protein Blends

In this work, two processing aids, acetyl tri-n-butyl citrate and an alkene bis fatty amide (wax), were investigated for their effects on rheological properties, morphology, thermal transition temperatures, and mechanical properties of the poly(lactic acid) (PLA)/soy protein concentrate blends. Acetyl tri-n-butyl citrate and alkene bis fatty amide played different roles in improving the processability of the blends, with the former functioning as a plasticizer for PLA and the latter as an internal/external lubricant. The amide wax was more effective in reducing blend melt viscosity through its dual functions of internal and external lubrication. Acetyl tri-n-butyl citrate displayed a stronger effect in facilitating PLA nucleation than the amide wax. Both processing aids decreased tensile strength and modulus of the blends and increased break strain and impact strength.     

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%.     

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.     

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.     

Biodegradable Poly(butylene succinate) and Poly(butylene adipate-co-terephthalate) Blends: Reactive Extrusion and Performance Evaluation

Two biodegradable polyesters, poly(butylene adipate-co-terephthalate) (PBAT) and poly(butylene succinate) (PBS) were melt-compounded in a twin screw extruder to fabricate a novel PBS/PBAT blend. The compatibility of the blend was attributed to the transesterification reaction that was confirmed by Fourier transform infrared spectroscopy. The Gibbs free energy equation was applied to explain the miscibility of the resulting blend. Dynamic mechanical analysis of the blends exhibits an intermediate tanδ peak compared to the individual components which suggests that the blend achieved compatibility. One of the key findings is that the tensile strength of the optimized blend is higher than each of the blended partner. Rheological properties revealed a strong shear-thinning tendency of the blend by the addition of PBAT into PBS. The phase morphology of the blends was observed through scanning electron microscopy, which revealed that phase separation occurred in the blends. The spherulite growth in the blends was highly influenced by the crystallization temperature and composition. In addition, the presence of a dispersed amorphous phase was found to be a hindrance to the spherulite growth, which was confirmed by polarizing optical microscopy. Furthermore, the increased crystallization ability of PBAT in the blend systems gives the blend a balanced thermal resistance property.     

The Properties of PLA/Oxidized Soybean Oil Polymer Blends

Novel polymer blends based on completely renewable polymers were reported. Polymer blends based on polylactic acid (PLA) and oxidized and hydroxylated soya bean oil polymers were prepared. Plasticization and mechanical strength effect of the soya bean oil polymers on the PLA were observed. Fracture surface analysis of the polymer blends was carried out by using scanning electron microscopy. The PLA blends showed more amorphous morphologies compared to pure PLA. The blends had better elongation at break in view of the stress–strain measurement. Blend of PLA with the hydroxylated polymeric soya bean oil indicated the slightly antibacterial properties.     

Tensile Properties of Polylactide/Poly(ethylene glycol) Blends

The blends of polylactide (PLA) and poly(ethylene glycol) (PEG) with different contents (0, 5, 10, 15, and 20 wt%) and molecular weights (\( \overline{M}_{w} \) 6000, 10,000 and 20,000, called respectively as PEG 6000, PEG 10,000, and PEG 20,000) were prepared by means of melt blending method. The effects of tensile speed, content and molecular weight of the PEG on the tensile properties of the PLA/PEG blends were investigated using a universal testing machine at 24 °C. With increasing tensile speed, the tensile modulus, strength and stress at break of the PLA/PEG blends marginally increased, while the tensile modulus and stress at break declined non-linearly, and the tensile strength dropped nearly linearly with increasing PEG 10,000 content. When the PEG 10,000 content was 5–15 wt%, the tensile strain at break of the PLA/PEG 10,000 blend markedly increased, and then decreased as the PEG 10,000 content exceeded 15 wt%. With increasing the molecular weight of PEG, tensile modulus and strength increased, whereas the tensile strain at break decreased. This showed that the application of right amount of lower molecular weight PEG was more conducive to improving the tensile toughness of the PLA/PEG blends, which was attributed to its better miscibility with PLA and increased mobility of PLA molecular chains.     

Effects of Diisocyanate and Polymeric Epoxidized Chain Extenders on the Properties of Recycled Poly(Lactic Acid)

Increasing demand in the use of poly(lactic acid) (PLA) leads to a debate about using potential foodstuffs for plastic production and a moral issue when starvation problem is taken into account. One of the solutions is recycling of PLA; however, recycling results in property losses during melt processing due to low thermal stability of PLA. This study focuses on using chain extenders to offset thermal degradation of recycled PLA. The effects of a diisocyanate and a polymeric epoxidized chain extender on the properties of the recycled poly(lactic acid) were investigated. In order to mimic the recycling process, PLA was subjected to thermo-mechanical degradation using a laboratory scale compounder. Chain extender type, loading and mixing time were investigated. On-line rheology and intrinsic viscosity measurements of PLA before and after chain extension confirmed that the molecular weight increased. Dynamic mechanical analysis, rheology and tensile tests revealed that the chain extenders led to a significant increase in modulus, strength and melt-viscosity. It was found that diisocyanate had slightly higher and faster chain extension reactivity than polymeric extender. Differential scanning calorimetry results showed an increase in the crystallization temperature due to the branched and extended chain structure.     

Poly(Lactic Acid) Blended with Cellulolytic Enzyme Lignin: Mechanical and Thermal Properties and Morphology Evaluation

“Green”/bio-based blends of poly(lactic acid) (PLA) and cellulolytic enzyme lignin (CEL) were prepared by twin-screw extrusion blending. The mechanical and thermal properties and the morphology of the blends were investigated. It was found that the Young’s modulus of the PLA/CEL blends is significantly higher than that of the neat PLA and the Shore hardness is also somewhat improved. However, the tensile strength, the elongation at break, and the impact strength are slightly decreased. Thermogravimetric analysis (TGA) shows that the thermal stability of the PLA is not significantly affected by the incorporation of the CEL, even with 40 wt% CEL. The results of FT-IR and SEM reveal that the CEL and the PLA are miscible and there are efficient interactions at the interfaces between them. These findings show that the CEL is a kind of feasible filler for the PLA-based blends.     

Mechanical and Barrier Properties of Biodegradable Films Made from Chitosan and Poly (Lactic Acid) Blends

Biodegradable film blends of chitosan with poly(lactic acid) (PLA) were prepared by solution mixing and film casting. The main goal of these blends is to improve the water vapor barrier of chitosan by blending it with a hydrophobic biodegradable polymer from renewable resources. Mechanical properties of obtained films were assessed by tensile test. Thermal properties, water barrier properties, and water sensitivity were studied by differential scanning calorimeter analysis, water vapor permeability measurements, and surface-angle contact tests, respectively. The incorporation of PLA to chitosan improved the water barrier properties and decreased the water sensitivity of chitosan film. However, the tensile strength and elastic modulus of chitosan decreased with the addition of PLA. Mechanical and thermal properties revealed that chitosan and PLA blends are incompatible, consistent with the results of Fourier transform infrared (FTIR) analysis that showed the absence of specific interaction between chitosan and PLA.     

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.     

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.     

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.     

Biodegradable Poly(lactic acid) Blends with Chemically Modified Polyhydroxyoctanoate Through Chain Extension

Poly(lactic acid) (PLA) was blended with chemically modified Polyhydroxyoctanoate (mPHO) using a Haake twin-screw mixer. Due to the melt viscosity disparity between the two components, PHO was reacted with Hexamethylene diisocyanate (HDI) used as a chain extender to produce high molecular weight for improving compatibility and processability with PLA. The number average and weight average molecular weight of the PHO, reacted with 0.55 wt% HDI, were increased 314 and 275%, respectively, compared with those of the unmodified PHO. The blends were characterized for rheological, thermal, and mechanical properties. Infrared spectra confirmed the formation of the urethane linkages in mPHO. The shear viscosity, as a function of shear rate or shear stress, decreased with an increase in mPHO content, indicating that the PLA/mPHO blends show shear-thinning behavior along with the power-law model. DSC thermograms showed that the two components in the blends were found with two crystalline phases and two amorphous phases confirming the coexistence of two immiscible components. Tensile results indicated that tensile strength for blends decreased with increasing mPHO content up to 80%. A decrease in elastic modulus, as well as an increase in elongation at break, was seen as a function of mPHO content. Results of aging tests showed that the mechanical properties of the blends also dropped more at a higher PLA level when compared with those of the unaged samples.     

Effect of Hexadecyl Lactate as Plasticizer on the Properties of Poly(<Emphasis Type="SmallCaps">l</Emphasis>-lactide) Films for Food Packaging Applications

In this study, poly(l-lactide) (PLA) films were fabricated by melt processing and the plasticizing effect of hexadecyl lactate (HL) (0, 5, 7.5, 10, and 12.5 wt% on PLA were investigated by scanning electron microscopy (SEM), differential scanning calorimetry, thermogravimetric analysis, tensile, transparency, and water vapor permeability tests. The SEM analysis revealed that PLA with 10 wt% HL appeared uniform with extra small bumps, confirmed the interaction between PLA and HL. The thermal analysis revealed a glass transition temperature of 57.4 °C for neat PLA film, but the addition of HL elicited a decrease in the temperature of the peak (43.8 °C). The incorporation of plasticizer into PLA resulted in the increase of elongation at break, as well as the decrease of tensile strength and tensile modulus. Even though a decrease in transparency was recorded, the PLA/HL blend films appeared transparent by visually observation. The water vapor permeability of PLA/HL blend films increased with the increase of HL. The PLA/HL blend films could effectively extend the shelf-life of fresh-cut pears as the commercial low density polyethylene films. The results indicated that the properties of PLA films can be modified with the addition of HL and PLA/HL blend films could serve as an alternative as food packaging materials to reduce environmental problems associated with synthetic packaging films.     

Improvement of Impact Toughness of Biodegradable Poly(butylene succinate) by Melt Blending with Sustainable Biobased Glycerol Elastomers

Poly(butylene succinate) (PBS) was melt blended with glycerol based polyesters (PGS) synthesized from pure and technical glycerol aiming to improve the impact strength of PBS. It was found that after addition of 30 wt% PGS to PBS its impact strength was significantly increased by 344% (from 31.9 to 110 J/m) and its elongation at break was maintained at 220%. Infrared spectra of the blends showed the presence of hydroxyl groups from the PGS phase suggesting that hydrogen bonding between the phases could be responsible for a good stress transfer and an efficient toughening in the PBS/PGS blends. Scanning electron microscopy imaging showed a good dispersion of PGS phase into PBS with a PGS particle size of 10 μm and less and no agglomeration. Addition of PGS to PBS was shown to be an effective strategy for improvement of PBS impact resistance without serious detrimental effects on its thermal and rheological properties.     

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.     

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.