Starch, Poly(lactic acid), and Poly(vinyl alcohol) Blends

Research on biodegradable materials has been stimulated due to concern regarding the persistence of plastic wastes. Blending starch with poly(lactic acid) (PLA) is one of the most promising efforts because starch is an abundant and cheap biopolymer and PLA is biodegradable with good mechanical properties. Poly(vinyl alcohol) (PVOH) contains unhydrolytic residual groups of poly(vinyl acetate) and also has good compatibility with starch. It was added to a starch and PLA blend (50:50, w/w) to enhance compatibility and improve mechanical properties. PVOH (M_W 6,000) at 10%, 20%, 30%, 40%, 50% (by weight) based on the total weight of starch and PLA, and 30% PVOH at various molecular weights (M_W 6,000, 25,000, 78,000, and 125,000 dalton) were added to starch/PLA blends. PVOH interacted with starch. At proportions greater than 30%, PVOH form a continuous phase with starch. Tensile strength of the starch/PLA blends increased as PVOH concentration increased up to 40% and decreased as PVOH molecular weight increased. The increasing molecular weight of PVOH slightly affected water absorption, but increasing PVOH concentration to 40% or 50% increased water absorption. Effects of moisture content on the starch/PLA/PVOH blend also were explored. The blend containing gelatinized starch had higher tensile strength. However, gelatinized starch also resulted in increased water absorption.     

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.     

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.     

Effects of Compatibilizer and Thermoplastic Starch (TPS) Concentration on Morphological,Rheological, Tensile,Thermal and Moisture Sorption Properties of Plasticized Polylactic Acid/TPS Blends

The blends of polylactic acid plasticized with acetyl tributyl citrate (P-PLA) and thermoplastic wheat starch (TPS) were prepared by a co-rotating twin screw extruder and the effect of maleic anhydride grafted PLA (PLA-g-MA) content as reactive compatibilizer on blends compatibility through morphological, rheological and tensile properties of the blends was investigated. Considerable improvement in properties of P-PLA/TPS (70/30 w/w) blend with incorporating the optimum PLA-g-MA content of 4 phr was achieved as this blend exhibited better morphological and rheological properties with an increase by 158 and 276% in tensile strength and elongation at break, respectively, compared to the uncompatibilized blend. Also the thermal stability and moisture sorption properties of the blends as effected by TPS content were studied. Decreasing in thermal stability and increasing in equilibrium moisture content of the blends were observed with progressively increasing of TPS content. For prediction the moisture sorption behaviour of blends with various TPS contents at different relative humidity, the moisture sorption isotherm data were modeled by GAB (Guggenheim–Anderson–de Boer) model.     

Effect of Orientation on the Morphology and Mechanical Properties of PLA/Starch Composite Filaments

Polylactic acid (PLA)/starch fibers were produced by twin screw extrusion of PLA with granular or gelatinized starch/glycerol followed by drawing through a set of winders with an intermediate oven. At 30% starch, fibers drawn 2–5x were highly flexible (elongation 20–100%) while undrawn filaments were brittle (elongation 2–9%). Tensile strength and moduli increased with increasing draw ratio but decreased with increasing starch content. Mechanical properties were better for composites made with gelatinized starch/glycerol than granular starch. In conclusion, orientation greatly increases the flexibility of PLA/starch composites and this may be useful not only in fibers but also possibly in molded articles. Other advantages of starch addition could include fiber softness without added plasticizer, moisture/odor absorbency and as a carrier for active compounds.     

Biodegradable Blends Based on Starch and Poly(Lactic Acid): Comparison of Different Strategies and Estimate of Compatibilization

Finding plastic substitutes based on sustainability, especially for short-term packaging and disposable applications has aroused scientific interest for many years. Starch may be a substitute for petroleum based plastics but it shows severe limitations due to its water sensitivity and rather low mechanical properties. To overcome these weaknesses and to maintain the material biodegradability, one option is to blend plasticized starch with another biodegradable polymer. To improve both the compatibility between the main phases and the performance of the final blend, different compatibilization strategies are reported in literature. However, the relative efficiency of each strategy is not widely reported. This paper presents three different strategies: in situ (i) formation of urethane linkages; (ii) coupling with peroxide between starch and PLA, and (iiii) the addition of PLA-grafted amylose (A-g-PLA) which has been elaborated ex situ and carefully analyzed before blending. This study compares the effect of each compatibilization strategy by investigating mechanical and thermal properties of each blend. Compatibilizing behavior of the A-g-PLA is demonstrated, with a significant increase (up to 60%) in tensile strength of starch/PLA blend with no decrease in elongation at failure.     

Grafting of Glycidyl Methacrylate onto Poly(lactide) and Properties of PLA/Starch Blends Compatibilized by the Grafted Copolymer

Poly(lactide)-graft-glycidyl methacrylate (PLA-g-GMA) copolymer was prepared by grafting GMA onto PLA in a batch mixer using benzoyl peroxide as an initiator. The graft content was determined with the ¹H-NMR spectroscopy by calculating the relative area of the characteristic peaks of PLA and GMA. The result shows that the graft content increases from 1.8 to 11.0 wt% as the GMA concentration in the feed varies from 5 to 20 wt%. The PLA/starch blends were prepared by the PLA-g-GMA copolymer as a compatibilizer, and the structure and properties of PLA/starch blends with or without the PLA-g-GMA copolymer were characterized by SEM, DSC, tensile test and medium resistance test. The result shows that the PLA/starch blends without the PLA-g-GMA copolymer show a poor interfacial adhesion and the starch granules are clearly observed, nevertheless the starch granules are better dispersed and covered by PLA when the PLA-g-GMA copolymer as a compatibilizer. The mechanical properties of the PLA/starch blends with the PLA-g-GMA copolymer are obviously improved, such as tensile strength at break increasing from 18.6 ± 3.8 MPa to 29.3 ± 5.8 MPa, tensile modulus from 510 ± 62 MPa to 901 ± 62 MPa and elongation at break from 1.8 ± 0.4 % to 3.4 ± 0.6 %, respectively, for without the PLA-g-GMA copolymer. In addition, the medium resistance of PLA/starch blends with the PLA-g-GMA copolymer was much better than PLA/starch blends.     

Effects of Incorporating Polycaprolactone and Flax Fiber into Glycerol-Plasticized Pea Starch

This study focused on improving the material properties of pea thermoplastic starch (TPS) with polycaprolactone (PCL) and flax fiber. Accordingly, composites of glycerol-plasticized pea starch, polycaprolactone, and flax fiber were prepared through solid-phase compounding and compression-molding. The specimens were characterized through scanning electron microscopy, tensile test, moisture absorption test, and differential scanning calorimetry. Morphological studies of the tensile fracture surfaces revealed poor TPS-PCL interfacial interaction and limited TPS-flax fiber interfacial bonding. The composites showed significant improvements in tensile strength with reduced moisture absorption capability essentially due to the hydrophobicity of PCL. Individual components of the composites retained their respective thermal properties, an indication of thermodynamic immiscibility.     

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.     

A Novel Packaging Film from Cassava Starch and Natural Rubber

Currently, there is an environmental pollution problem generated in part by packaging materials produced from non-biodegradable synthetic polymers made from petroleum. However, these can be replaced with biodegradable materials made from cassava starch (CS) and natural rubber (NR). In the work described, a novel biopolymer film was obtained from the CS and NR using glycerol (GE) as a plasticizer in a water-based system. The physical properties of an 95/5 CS/NR blend films with the addition of NR and with varying GE contents were studied based on their swelling ratio, moisture content, moisture absorption, mechanical properties and biodegradability in soil. The results showed that the moisture content and moisture absorption tended to be directly proportional to the GE content, while the moisture content and moisture absorption of the sample decreased as a function of the NR content. The swelling ratio of the 95/5 CS/NR blend slightly decreased as a function of the NR and GE content. Surprisingly, the best swelling ratio of 350% was found at 10% NR. The elongation at break of the CS/NR blend was improved by the addition of GE. The contact angle of the 95/5 CS/NR blend decreased as a function of the GE. With increased NR in the composite, an increasing, trend in the contact angle was found. Further, the 95/5 CS/NR blend exhibited good transparency when it was applied as a coating to delay the ripening of bananas, the results were positive. Moreover, the film showed decomposition well in natural soil.     

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.     

Thermoplastic Starch (TPS)/Polylactic Acid (PLA) Blending Methodologies: A Review

Polylactic acid (PLA) and thermoplastic starch (TPS) are biodegradable polymers of biological origin, and the mixture of these polymers has been studied due to the desirable mechanical properties of PLA and the low processing cost of TPS. However, the TPS/PLA combination is thermodynamically immiscible due to the poor interfacial interaction between the hydrophilic starch granules and the hydrophobic PLA. To overcome these limitations, researchers studied the modification, processing, and properties of the mixtures as a strategy to increase the compatibility between phases. This review highlights recent developments, current results, and trends in the field of TPS/PLA-based compounds during the last two decades, with the main focus of improving the adhesion between the two components. The TPS/PLA blends were classified as plasticized, compatible, reinforced and with nanocomposites. This article presents, based on published research, TPS/PLA combinations, considering different methods with significant improvements in mechanical properties, with promising developments for applications in food packaging and biomedicine.

     

The Effect of Polymeric Chain Extenders on Physical Properties of Thermoplastic Starch and Polylactic Acid Blends

The effects of a polymeric chain extender on the properties of bioplastic film made from blends of plasticized polylactic acid (p-PLA) and thermoplastic starch (TPS) were studied. Joncryl^? ADR 4370S, a polymeric chain extender, was blended with TPS and p-PLA at a level of 1% (w/w). A co-rotating twin-screw extrusion process was used to prepare films with various ratios of TPS and p-PLA. Mechanical and physical properties of films, including film tensile properties, surface energy, moisture content, hydrophilicity, moisture sorption behaviour and thermal mechanical properties were determined. During extrusion, films enhanced by 1% Joncryl addition demonstrated more desirable and consistent qualities, such as smoother film edge and surface. Addition of Joncryl significantly improved film tensile strength, 0.2% offset yield strength, and elongation, especially evident with the 250% elongation of 70/30 (TPS/p-PLA) film. Total surface energy of films was not significantly influenced by addition of Joncryl. However, the polar contribution to the total surface energy of 70/30 (TPS/p-PLA) film increased after the addition of Joncryl. The study showed that blending TPS with p-PLA transformed TPS film from being highly hydrophilic to highly hydrophobic. On the other hand, addition of Joncryl had limited effects on moisture content, water solubility, glass transition temperature and moisture sorption behaviour of TPS/p-PLA blend films.     

Lightweight Concrete Containing an Alkaline Resistant Starch-Based Aquagel

Starch aquagel-based lightweight concrete has properties similar to those of other lightweight concrete products. However, starch aquagels are unstable in the strongly alkaline conditions typical of Portland Cement-based concrete and may interfere with the setting process. The effect of alkali treatments on the physical, mechanical, and functional properties of starch aquagels and aquagels from starch/polymer blends was investigated. Starch was blended at 100–115°C in a twin-screw extruder with five different polymers to determine whether the blends improved alkaline resistance. Polymer blends containing 5%, 15%, and 30% of the polymer hydrated and formed aquagels when equilibrated in water for 24 h. However, equilibrium moisture content was lower for the blends compared to the starch control. Aquagels equilibrated in 0.15 N NaOH swelled, lost compressive strength and had greater than 90% moisture. The blend of starch and 30% PVOH absorbed less moisture and was more resistant to alkaline dissolution in 1 N NaOH than the other blends tested making it a more suitable material for aquagel-based concrete. The moisture content of starch-based aquagels and mixing time were critical factors in determining setting times. The size of aquagel blends had a minor effect on density and compressive strength.     

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.     

A Comparison Study of Wheat Gluten Composites Filled with Dialdehyde Starch and Native Starch

Environmentally friendly green composites were prepared by blending Wheat gluten (WG) as matrix, dialdehyde starch (DAS) as filler and glycerol as plasticizer followed by compression molding of the mixture at 110 °C. The properties of the WG/DAS composite are compared with those of the WG/native wheat starch (NWS) composites. While tensile strength and strain at break decrease with increasing NWS content in the WG/NWS composites, a small content of DAS could improve tensile strength and strain at break simultaneously in the WG/DAS composites. The WG/DAS composites exhibit reduced moisture absorption in comparison with the WG/NEW composites. Formation of chemical bonding between DAS and WG is beneficial for the dispersion of DAS in the WG matrix and WG/DAS composites exhibit improved mechanical properties and reduced moisture absorption over the WG/NWS composites.     

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%.     

Properties of Starch/PVA Blend Films Containing Citric Acid as Additive

Starch/polyvinyl alcohol (PVA) blend films were prepared successfully by using starch, polyvinyl alcohol (PVA), glycerol (GL) sorbitol (SO) and citric acid (CA) for the mixing process. The influence of mixing time, additional materials and drying temperature of films on the properties of the films was investigated. With increase in mixing time, the tensile strength (TS), elongation (%E), degree of swelling (DS) and solubility (S) of the film were equilibrated. The equilibrium for TS, %E, DS and S value was 20.12 MPa, 36.98%, 2.4 and 0.19, respectively. The mixing time of equilibrium was 50 min. TS, %E, DS and S of starch/PVA blend film were examined adding glycerol (GL), sorbitol (SO) and citric acid (CA) as additives. At all measurement results, except for DS, the film adding CA was better than GL or SO because hydrogen bonding at the presence of CA with hydroxyl group and carboxyl group increased the inter/intramolecular interaction between starch, PVA and additives. Citric acid improves the properties of starch/PVA blend film compared to glycerol and sobitol. When the film was dried at low temperature, the properties of the films were clearly improved because the hydrogen bonding was activated at low temperature.     

Modification of Aliphatic Polyesters and Their Reactive Blends with Starch

Modified polycaprolactone was synthesized by melt reaction of PCL and reactive monomers such as glycidyl methacrylate (GMA) and maleic anhydride (MAH) in the presence of benzoyl peroxide in Brabender mixer. MAH showed a different grafting phenomenon compared to GMA. The reaction mechanism was discussed with different reactive monomers. Reactive blends of the PCL-g-GMA and the gelatinized starch with glycerin were prepared and their mechanical properties and biodegradabilities were investigated. Reactive blends of PCL-g-GMA and starch showed well-dispersed starch domain in the matrix and better mechanical strength than the unmodified PCL/starch blend. However, the reaction between PCL-g-GMA and starch induced a crosslinking during the reactive blending and this crosslinking in the blend lowered the biodegradation of the blend during the composting test. The biodegradability was investigated by the weight loss and surface morphology change of the blend in the composting medium.     

Effect of Glycerin and Starch Crosslinking on Molecular Compatibility of Biodegradable Poly(lactic acid)-Starch Composites

Poly(lactic acid) (PLA) is a biodegradable material. However, PLA is relatively cost effective. Blending starch with PLA is one of the promising efforts because starch is a widely distributed and inexpensive product. PLA and starch were blended using a rheometer to form composites in this report. Glycerin was added into the blends to make the mixture molecular compatible and more homogeneous. The starch was crosslinked using epichlorohydrin to improve the compatibility of starch with PLA. Two series of composite were fabricated. One was PLA and the crosslinked starch containing 32 wt% glycerin. In this group, the crosslinking degree of the modified starch was varied. The second group was PLA and non-crosslinked starch with varied amount of glycerin added. Micro-structure of the blending composites was observed using a SEM to view the homogeneity of the mixture. The SEM pictures indicated that the compatibility of PLA and starch molecules was poor. The addition of glycerin can change the compatibility of PLA and starch. The higher the glycerin content in the composites, the better the compatibility between PLA and starch. Furthermore, when the starch was crosslinked by epichlorohydrin, the compatibility of PLA and starch can be greatly improved. The compatibility increases with the increase of crosslinking degree. This is due to the change of hydrophilicity of starch because the hydroxyl groups on the starch molecules were crosslinked into ether groups by the epichlorohydrin molecules.