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.     

Life Cycle Analysis of Extruded Films Based on Poly(lactic acid)/Cellulose Nanocrystal/Limonene: A Comparative Study with ATBC Plasticized PLA/OMMT Systems

Life cycle analysis (LCA) of limonene plasticized poly(lactic acid) (PLA) films containing cellulose nanocrystals (CNC) extracted, by acid hydrolysis, from Phormium tenax leaf fibres, was assessed and compared with the results of acetyl tributyl citrate (ATBC) plasticized PLA films, having equivalent mechanical properties, containing organo-modified montmorillonite (OMMT). Eco-Indicator 99 tool has been adopted as the main method for life cycle assessment. Results indicated that, despite CNC are biobased fillers obtained by natural sources, the related chemical extraction leads to a large environmental footprint and a relatively relevant energy expense. LCA characterization of these films demonstrated that the environmental impact of PLA/limonene film reinforced with 1% in weight of CNC (PLA/CNC/limonene) is comparable to the environmental impact of polylactic acid films reinforced with OMMT and plasticized with a petroleum based plasticizer (ATBC) (PLA/OMTT/ATBC). A “cradle to gate” approach has been considered for both the film typologies.     

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.     

Tensile Strength, Elongation, Hardness, and Tensile and Flexural Moduli of PLA Filled with Glycerol-Plasticized DDGS

Rapid growth of the biofuel industry is generating large amounts of coproducts such as distillers dried grains with solubles (DDGS) from ethanol production and glycerol from biodiesel. Currently these coproducts are undervalued, but they have application in the plastics industry as property modifiers. The objective of this research effort is to quantify the effects on mechanical properties of adding DDGS and glycerol to polylactic acid (PLA). The methodology was to physically mix DDGS, as filler, with PLA pellets and injection mold the blends into test bars using glycerol as a plasticizer. The bars were subject to mechanical testing procedures to obtain tensile strength, tensile and flexural moduli, elongation to break, and surface hardness of blends from 0 to 90?%, by weight, of plasticized filler. Blends were typically relatively brittle with little or no yielding prior to fracture, and the addition of glycerol enabled molding of blends with high levels of DDGS but did not increase strength. Any presence of filler decreased the tensile strength of the PLA, and 20?C30?% filler reduced strength by 60?%. The 35?C50?% filled PLA had about one-fifth the value for pure PLA; at 60?C65?% filler level, about 10?% tensile strength remained; and over 80?% filler, 95?% of the strength was lost. Over 20?% filler, the tensile modulus decreased. The 35?% plasticized, filled blend yielded about one-half the stiffness as the pure PLA case; flexural modulus trended in the same manner but demonstrated a greater loss of stiffness. Most blends had less than 3?% elongation to break while surface hardness measurements indicated that up to 60?% filler reduced Shore D hardness by less than 20?%. The tensile strength and modulus data are consistent with the findings of other researchers and indicate that the type of filler and amount and sequence of plasticization are secondary effects, and the total PLA displaced is the dominant factor in determining the mechanical strength of the PLA and DDGS blends. Up to 65?% plasticized DDGS filler can be injection molded, and sufficient mechanical strength exists to create a variety of products. Such a novel material provides higher-value utilization of the biofuel coproducts of glycerol and DDGS and maintains the biodegradable and biocompatible nature of PLA.     

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.     

Novative Biomaterials Based on Chitosan and Poly(ε-Caprolactone): Elaboration of Porous Structures

The swelling capability of chitosan was explored in order to use water both, as volatile plasticizer and as pore-forming agent. Chitosan powder was swelled in acidic aqueous solution and melt blended with poly(ε-caprolactone) (PCL). After stabilization at 57% RH and 25 °C, samples suffered a water mass loss of around 30 wt% without dimensions variation. Despite the low miscibility of these biopolymers, quite homogeneous dispersion of chitosan within the polyester matrix was obtained. Some interactions between both biopolymers could be observed. To obtain chitosan phase with a thermoplastic-like behaviour, the plasticization effect was also studied by the addition of 25 wt% glycerol as non volatile plasticizer. The equilibrium moisture content of samples increased with the incorporation of glycerol due to its hydrophilic nature. Morphology, thermal and mechanical properties of the blends were determined after stabilization. The preparation of rich PCL blends allowed the formation of macroporous structures since samples were not contracted after water loss and stabilization. These biomaterials with such a porous structure could be used for biomedical applications.     

Novel Biodegradable Cast Film from Carbon Dioxide Based Copolymer and Poly(Lactic Acid)

Poly(lactic acid) (PLA) and poly(propylene carbonate) (PPC) blends with different levels of chain extender were prepared and cast into films. The effect of chain extender on the mechanical, thermal and barrier properties of the films were investigated. With the inclusion of the chain extender, the compatibility and interfacial adhesion between the two polymer phases were significantly improved by a mean of forming a PLA–chain extender–PPC copolymer. Reactions between the chain extender, PLA and PPC were observed through FTIR study. SEM study also confirmed the improved compatibility and interfacial adhesion. The elongation at break of the compatibilized film with optimal amount of chain extender showed dramatic increase by up to 1940 %. DSC studies revealed that chain extender hindered the crystallization of the film which explained the decrease in both water and oxygen barrier when adding chain extender. PLA was found to be able to enhance both oxygen and water barrier of the blend as compared to neat PPC, while in the case of the blend with chain extender, oxygen and water barrier properties exhibited reduction at the beginning. However, when increasing chain extender concentration, these two barrier performance exhibited an upward trend. It was found that PLA/PPC blend showed much better oxygen barrier property than both parent polymers, which can be ascribed to the acceleration effect of PPC on the crystallization of PLA.     

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%.     

Organic–Inorganic Hybrid Coatings for the Modification of Barrier Properties of Poly(lactic acid) Films for Food Packaging Applications

Organic–inorganic hybrid coatings based on poly(ε-caprolactone), poly(ethylene oxide) or poly(lactic acid) as organic phase and silica from tetraethoxysilane as inorganic phase were prepared by the sol–gel approach. Coatings were applied onto poly(lactic acid) films for food packaging in order to improve its barrier properties towards oxygen and water vapour. All the prepared coatings were dense, homogeneous layers characterized by a good adhesion to the substrate. The permeance of the coating layers resulted one order of magnitude lower than that of the uncoated poly(lactic acid) (PLA) film. The hydrophilic character of the coating did not permit to gain a significant decrease in the water vapour permeance. The perfect visual transparency of the coatings allows their application without worsening of the esthetical properties of the substrate PLA film.     

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.     

A Biobased Blend of Cellulose Diacetate with Starch

Two bio-based polymers, cellulose diacetate (CDA) and starch, were used to prepare blends with reasonable properties and low cost. Due to the poor processing properties, starch was modified in the presence of glycerol and epoxidized soybean oil (ESO), and CDA was plasticized by triacetin (TA) and ESO, respectively. The morphologies of the blends with different amounts of modified starch (MST) were studied by scanning electron microscope (SEM), and the physical properties of the blends, including thermal stability, mechanical property, water and moisture resistance, were investigated. The equilibrium moisture absorption rates of the blends containing 30 and 50 wt% MST at 100 % of relative humidity(RH) were 9.4 and 15.0 %, respectively. SEM and DMA results demonstrated that CDA and MST had a certain extent of compatibility. Due to the partial plasticization of starch, the tensile strength of the blends was nearly not affected by the amount of MST. Even if 50 wt% MST was added, the tensile strength of the blend was as high as 24.7 MPa. The obtained blend containing 30 wt% MST can keep good mechanical properties at 50 % RH, and its tensile strength and elongation at break are 30.2 MPa and 3.6 %, respectively. All the results show that the CDA/MST blends have a potential as an environmental friendly material.     

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%.     

Biodegradation of Polylactide and Gelatinized Starch Blend Films Under Controlled Soil Burial Conditions

The biodegradability of polylactide (PLA) and gelatinized starches (GS) blend films in the presence of compatibilizer was investigated under controlled soil burial conditions. Various contents (0–40 wt%) of corn and tapioca starches were added as fillers; whereas, different amounts of methylenediphenyl diisocyanate (MDI) (0–2.5 wt%) and 10 wt% based on PLA content of polyethylene glycol 400 (PEG400) were used as a compatibilizer and a plasticizer, respectively. The biodegradation process was followed by measuring changes in the physical appearance, weight loss, morphological studies, and tensile properties of the blend films. The results showed that the presence of small amount of MDI significantly increased the tensile properties of the blends compared with the uncompatibilized blends. This is attributed to an improvement of the interfacial interaction between PLA and GS phases, as evidenced by the morphological results. For soil burial testing, PLA/GS films with lower levels (1.25 wt%) of MDI had less degradation; in contrast, at high level of MDI, their changes of physical appearance and weight loss tended to increase. These effects are in agreement with their water absorption results. Furthermore, biodegradation rates of the films were enhanced with increasing starch contents, while mechanical performances were decreased.     

Environmentally Friendly Oil-Modified Polyesters as Polymeric Plasticizers for Poly(vinyl chloride)

Oil-modified polyesters were synthesized to serve as polymeric plasticizers for PVC. A total of four polymeric plasticizers with different average molecular weights were prepared. Characterizations were done using Fourier-transformed infrared spectroscopy, proton nuclear magnetic resonance spectroscopy, and gel permeation chromatography. Some of the tests conducted on PVC films include thermal stability test using thermogravimetric analyser, determination of glass transition temperature (T_g), plasticizer migration and leaching resistance test, morphology study of plasticized PVC films using field emission scanning microscope, toxicity test, and tensile test. Owing to the plasticizing effect of the palm oil-based compound, T_g of the plasticized PVC has decreased to an average of 65 °C at 20 wt% loading. The polymeric plasticizer is also able to contribute positively to the thermal stability and mechanical properties of the PVC films. Some of the advantages of incorporating polymeric plasticizer with high molecular weight includes lower rate of leaching from plastic, and improved tensile strength and elongation at break. Besides, thermal stability of the plastic studied using Kissinger’s and Flynn–Wall–Ozawa’s approaches shows that PVC blended with high molecular weight oil-modified polyester is more thermally stable, evidenced by the increase in the activation energy of decomposition, E_d. Toxicity test using brine shrimp egg shows encouraging results, where the oil-based plasticizer is considerably less toxic compared to some of the commercial plasticizers.     

Preparation and Properties of Propylene Glycol Plasticized Wheat Protein Isolate Novel Green Films

Novel bio-based green films were prepared using wheat protein isolate (WPI) by solution casting method using Propylene Glycol as a plasticizer for packaging applications. The effect of the plasticizer content (10, 15, 20 and 25 wt%) on mechanical properties (tensile strength, young’s modulus and  % of elongation) was investigated. A thermal degradation and phase transition of the prepared WPI was assessed by means of TGA and DSC analysis. The results showed that the tensile strength and young’s modulus decreased and  % of elongation increased with increasing PG content. The ATR-FTIR and SEM were used for structural characterization and morphology of the films, respectively. FTIR studies reveals that the intensity of the bands corresponding to the amide groups increases with increasing PG content tending to increase protein–PG interactions. Further, the glass transition temperature was decreased and the thermal stability of the WPI was found to be increased by plasticization. The overall thermal stability of the films was improved and is attributed to the increase in mobility of the polymer chains.     

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.

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.     

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.     

Mechanical Properties of Poly (Lactic Acid)/Hemp Fiber Composites Prepared with a Novel Method

This research dealt with a novel method of fabricating green composites with biodegradable poly (lactic acid) (PLA) and natural hemp fiber. The new preparation method was that hemp fibers were firstly blending-spun with a small amount of PLA fibers to form compound fiber pellets, and then the traditional twin-screw extruding and injection-molding method were applied for preparing the composites containing 10–40 wt% hemp fibers with PLA pellets and compound fiber pellets. This method was very effective to control the feeding and dispersing of fibers uniformly in the matrix thus much powerful for improving the mechanical properties. The tensile strength and modulus were improved by 39 and 92 %, respectively without a significant decrease in elongation at break, and the corresponding flexural strength and modulus of composites were also improved by 62 and 90 %, respectively, when the hemp fiber content was 40 wt%. The impact strength of composite with 20 wt% hemp fiber was improved nearly 68 % compared with the neat PLA. The application of the silane coupling agent promoted further the mechanical properties of composites attributed to the improvement of interaction between fiber and resin matrix.     

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.