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.     

Thermal and mechanical properties of poly(lactic Acid) and poly(ethylene/butylene Succinate) blends

In this study, blends of poly (lactic acid) (PLA) with poly(ethylene/butylene succinate) (Bionolle) have been investigated for their thermal and mechanical properties as a function of the concentration of Bionolle. Differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), and tensile tests were used to characterize the blends. From the results of the DMA and DSC, it was found that this blend system was not miscible within the compositions studied. DSC results showed that adding Bionolle aids in crystallization of PLA. It was observed that increasing the Bionolle concentration led to a slight increase in the strain-at-break of the blends but a decrease in the Young’s modulus and ultimate tensile strength. Biaxially oriented films showed an increase in tensile strength, modulus, and strain-at-break.     

The influence of degree of substitution on blend miscibility and biodegradation of cellulose acetate blends

In this account, we report our findings on blends of cellulose acetate having a degree of substitution (DS) of 2.49 (CA2.5) with a cellulose acetate having a DS of 2.06 (CA2.0). This blend system was examined over the composition range of 0–100% CA2.0 employing both solvent casting of films (no plasticizer) and thermal processing (melt-compressed films and injection molding) using poly(ethylene glycol) as a common plasticizer. All thermally processed blends were optically clear and showed no loss in optical quality after storage for several months. Thermal analysis and measurement of physical properties indicate that blends in the middle composition range are partially miscible, while those at the ends of the composition range are miscible. We suggest that the miscibility of these cellulose acetate blends is influenced primarily by the monomer composition of the copolymers. Bench-scale simulated municipal composting confirmed the biodestructability of these blends and indicated that incorporation of a plasticizer accelerated the composting rates of the blends.In vitro aerobic biodegradation testing involving radiochemical labeling conclusively demonstrated that both the lower DS CA2.0 and the plasticizer significantly enhanced the biodegradation of the more highly substituted CA2.5.While this work was in progress, Robert Gardner was struck with cancer and died on June 6, 1995. This paper is dedicated to his memory and to his contributions as a friend and colleague.     

The Effect of Gamma and Electron Beam Irradiation on the Biodegradability of PLA Films

Biodegradation of poly(lactic) acid (PLA) has been studied extensively, but there is only limited knowledge about the effect of irradiation sterilization on its biodegradability. The aim of this work was to examine the aerobic biodegradation of gamma and electron beam irradiated PLA films along with the effects of aging (3, 6, and 9 months of storage) using a direct measurement respirometric system. Commercial PLA film was exposed to a simulated aerobic compost environment, and its mineralization was 96 % at day 85. Gamma and electron beam irradiation affected the biodegradation of the post-irradiated PLA film. Aging irradiated PLA had some potential to increase the biodegradation rate, as the average value of mineralization after 9 months of storage was higher than for the non-irradiated PLA. Comparison of the effect of storage time on the biodegradability of PLA showed a significant increase in biodegradation of the gamma irradiated PLA after 3 months (70 %) and 9 months of storage (130 %). Similarly, there was a significant difference in the biodegradation of electron beam irradiated PLA between 3 months (68 %) and 9 months of storage (120 %). Due to the priming effect, the percent mineralization of gamma irradiated and E-beam irradiated PLA after 9 months of storage was greater than 100 %. Both non-irradiated and irradiated PLA films can be considered biodegradable plastics since they showed mineralization percentage larger than 90 % of that of the positive control at the end of the test period.     

Anaerobic Biodegradation of Poly (Lactic Acid) Film in Anaerobic Sludge

The anaerobic biodegradation rates of four different sizes of poly (lactic acid) (PLA) films (thickness 25???m) in anaerobic sludge at 55?°C were examined. The anaerobic biodegradation rates of small pieces of PLA film were slower than for large pieces of PLA film. We also examined whether PLA film could also be used as a reference material in the anaerobic biodegradation test in addition to PLA powder. The anaerobic biodegradation rate of PLA film became slower with lower activity sludge, but the rate of decrease was gradual, and the anaerobic biodegradation rate of PLA film was faster than the PLA powder (125?C250???m). The anaerobic biodegradation rate of the PLA powder (125?C250???m) reflected the plastic anaerobic biodegradation activity of the sludge more accurately than the thin PLA film (thickness 25???m). Consequently, PLA powder (125?C250???m) is more suitable than thin PLA film (thickness?<?25???m) for use as a reference material to assess the plastic anaerobic biodegradation activity of the sludge in an anaerobic biodegradation test at 55?°C.     

Biodegradation of γ Irradiated Poly 3-hydroxybutyrate (PHB) Films Blended with Poly(Ethyleneglycol)

Poly(3-hydroxybutyrate) (PHB) was evaluated in blends with poly(ethyleneglycol) (PEG) of different weight average molecular weight (Mw = 300, 600, 1,000 and 6,000). Irradiation of the PHB/PEG films was carried out to different levels of irradiation doses (5 and 10 kGy) and the effects were investigated talking into consideration: thermal properties by differential scanning calorimetry (DSC), perforation resistance, water vapor transmission rate and biodegradation in simulated soil. The addition of plasticizer alters thermal stability and crystallinity of the blends. The improvement in perforation resistance due to irradiation was regarded to be a result of the crosslinking effect. Also, biodegradation assays resulted in mass retention improvements with increases in PEG molar masses, PEG concentration and irradiation dose. The irradiation process was shown to hamper the biodegradation mechanism.     

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.     

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 Epoxy and MF Modified Polyurethane Films Derived from a Sustainable Resource

Mesua ferrea L. seed oil (MFLSO) modified polyurethanes blends with epoxy and melamine formaldehyde (MF) resins have been studied for biodegradation with two techniques, namely microbial degradation (broth culture technique) and natural soil burial degradation. In the former technique, rate of increase in bacterial growth in polymer matrix was monitored for 12 days via a visible spectrophotometer at the wavelength of 600 nm using McFarland turbidity as the standard. The soil burial method was performed using three different soils under ambient conditions over a period of 6 months to correlate with natural degradation. Microorganism attack after the soil burial biodegradation of 180 days was realized by the measurement of loss of weight and mechanical properties. Biodegradation of the films was also evidenced by SEM, TGA and FTIR spectroscopic studies. The loss in intensity of the bands at ca. 1735 cm⁻¹ and ca. 1050 cm⁻¹ for ester linkages indicates biodegradation of the blends through degradation of ester group. Both microbial and soil burial studies showed polyurethane/epoxy blends to be more biodegradable than polyurethane/MF blends. Further almost one step degradation in TG analysis suggests degradation for both the blends to occur by breakage of ester links. The biodegradation of the blends were further confirmed by SEM analyses. The study reveals that the modified MFLSO based polyurethane blends deserve the potential to be applicable as “green binders” for polymer composite and surface coating applications.     

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.     

Temperature Effects on Soil Mineralization of Polylactic Acid Plastic in Laboratory Respirometers

A respirometric system was used to analyze the biodegradation of high molecular weight (120,000 to 200,000 g mol^–1) polylactic acid (PLA) plastic films in soil under laboratory conditions. The respirometric system consisted of air-conditioning pretraps, a soil reactor, and a carbon dioxide (CO₂) posttrap. A 200-g homogeneous soil mixture of all-purpose potting soil : manure soil : sand [1 : 1 : 1 (w/w)] and 1.5 g of PLA plastic films in 1 × 1-cm² squares was added to each bottle. The respirometers were placed in a 28, 40, or 55°C water bath for 182 days. Treatments (three replicates) included native corn starch (positive control), polyethylene (Glad Cling Wrap; negative control), and three PLA films: Ca-I (Cargill Dow Polymers LLC, monolayer), GII (Cargill Dow Polymers LLC, Generation II), and Ch-I (Chronopol; monolayer). The degree of polymer mineralization was indicated by the cumulative CO₂ liberated from each respirometer. The initial average mineralization rate and total percentage mineralized of the PLA plastic films at 28, 40, and 55°C was 24.3, 41.5, and 76.9 mg/day with a 27, 45, and 70% carbon loss, respectively. No decrease in soil pH was observed after 182 days of mineralization. Hence, increase in soil temperature drastically enhanced the biodegradation of PLA plastic films in soil under laboratory conditions (P < 0.0001).     

The Effect of Acetylation on the Hydrolytic Degradation of PLA/Clay Nanocomposites

In this study, the hydrolytic degradation of Poly(lactic acid) (PLA) and acetylated PLA (PLA-Ac)–clay nanocomposites were investigated. The organo clay was obtained by ion exchange reaction using cetyl tri methyl ammonium bromide (CTAB). Nanocomposites containing 2, 5 and 8% mass ratio of organo clay (CTAB-O) were prepared. PLA and its organo clay nanocomposites were characterized by scanning electron microscope (SEM), thermo gravimetric analysis (TGA) and X-ray diffraction (XRD) to determine the morphology before and after hydrolytic degradation. Fourier transform infrared (FTIR) analyses of PLA and PLA-Ac were also obtained. The hydrolytic degradation of polymers and their composites were investigated in the phosphate buffered saline solution (PBS). The results showed that controlled hydrolytic degradation was observed in the samples with end group modification of PLA. While weight loss of PLA films was 28%, that of PLA-Ac films was 18% after 60 days degradation time. The weight loss was obtained as 29.5 and 25.5% for PLA-5 wt% organo clay (PLA/5CTAB-O) and PLA-Ac-5 wt% organo clay (PLA-Ac/5CTAB-O) nanocomposites films, respectively. It was also observed that thermal degradation of PLA-Ac was much more than that of PLA. Hydrolytic degradation increased depending on organo clay content. The end group modificated PLA results in controlled hydrolytic degradation. While hydrolytic degradation in polymer films occurred as surface erosion, bulk erosion was observed in composite films.     

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%.     

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.     

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.     

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%.     

Degradation of Polylactic Acid (PLA) Plastic in Costa Rican Soil and Iowa State University Compost Rows

In this study the degradation of polylactic acid (PLA) plastic films in Costa Rican soil and in a leaf composting environment was investigated. Three types of PLA films were used: Ch-I, (PLA monolayer plastic films from Chronopol, Golden, CO), GII (PLA trilayer plastic films from Cargill Dow Polymers LLC, Minnetonka, MN), and Ca-I (PLA monolayer plastic films from Cargill Dow Polymers LLC). The average soil temperature and moisture content in Costa Rica were 27°C and 80%, respectively. The average degradation rate of PLA plastic films in the soil of the banana field was 7675 M _w/week. Two compost rows were set up at the Iowa State University (ISU) (Ames) compost site. Temperature and relative humidity of the compost rows were kept at 55 ± 5°C and 50 ± 10% RH, respectively. The degradation rates of GII and Ca-I in the compost rows were 113,290 and 71,283 M _w/week, respectively. Therefore, it was estimated that in Costa Rican soil and in compost rows, PLA would be visibly degraded in 6 months and in 3 weeks, respectively.     

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.     

Anaerobic Biodegradation of Blends Based on Polyvinyl Alcohol

The presented work deals with blends composed of polyvinyl alcohol (PVA) and biopolymers (protein hydrolysate, starch, lignin). PVA does not belong to biologically inert plastics but its degradation rate (particularly under anaerobic conditions) is low. A potential solution to the issue problem lies in preparation of blends with readily degradable substrates. We studied degradation of blow-molded films made of commercial PVA and mentioned biopolymers in an aqueous anaerobic environment employing inoculation with digested activated sludge from the municipal wastewater treatment plant. Films prepared in the first experimental series were to be used for comparing biodegradation of blends modified with native or plasticized starch; in this case effect of plasticization was not proved. The degree of PVA degradation after modification with native or plasticized starch increases in a striking and practically same manner already at a starch level as low as approximately 5 wt.%. Films of the second experimental series were prepared as additionally modified with protein hydrolysate and lignin. Only lignin-modified samples exhibited a somewhat lower degree of biodegradation but regarding the measure of lignin present in blend this circumstance is not essential. Level of biodegradation with all discussed films differed only slightly—within range of experimental error.     

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.