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.     

Synthesis,Characterization and Nanocomposite Formation of Poly(glycerol succinate-co-maleate) with Nanocrystalline Cellulose

A novel biodegradable polymer based on glycerol, succinic anhydride and maleic anhydride, poly(glycerol succinate-co-maleate), poly(GlySAMA), was synthesized by melt polycondensation and tested as a matrix for composites with nanocrystalline cellulose. This glycerol-based polymer is thermally stable as a consequence of its targeted cross-linked structure. To broaden its range of properties, it was specifically formulated with nanocrystalline cellulose (NCC) at concentrations of 1, 2 and 4 wt%, and showed improved mechanical properties with NCC. Specifically, the effect of reinforcement on mechanical properties, thermal stability, structure, and biodegradability was evaluated, respectively, by tensile tests and thermogravimetric analyses, X-ray diffraction and respirometry. The neat poly(GlySAMA) polymer proved flexible, exhibiting an elongation-to-break of 8.8 % while the addition of nanowhiskers (at 4 wt%) caused tensile strength and Young’s modulus to increase, 20 and 40 %, respectively. Stiffness improved without significantly decreasing thermal stability as measured by thermogravimetric analysis. Biodegradation tests indicated that all samples were degradable but NCC reduced the rate of biodegradation.     

Biodegradability and biodegradation rate of poly(caprolactone)-starch blend and poly(butylene succinate) biodegradable polymer under aerobic and anaerobic environment

The biodegradability and the biodegradation rate of two kinds biodegradable polymers; poly(caprolactone) (PCL)-starch blend and poly(butylene succinate) (PBS), were investigated under both aerobic and anaerobic conditions. PCL-starch blend was easily degraded, with 88% biodegradability in 44 days under aerobic conditions, and showed a biodegradation rate of 0.07 day⁻¹, whereas the biodegradability of PBS was only 31% in 80 days under the same conditions, with a biodegradation rate of 0.01 day⁻¹. Anaerobic bacteria degraded well PCL-starch blend (i.e., 83% biodegradability for 139 days); however, its biodegradation rate was relatively slow (6.1 mL CH₄/g-VS day) compared to that of cellulose (13.5 mL CH₄/g-VS day), which was used as a reference material. The PBS was barely degraded under anaerobic conditions, with only 2% biodegradability in 100 days. These results were consistent with the visual changes and FE-SEM images of the two biodegradable polymers after the landfill burial test, showing that only PCL-starch blend had various sized pinholes on the surface due to attack by microorganisms. This result may be use in deciding suitable final disposal approaches of different types of biodegradable polymers in the future.     

Biodegradability and Mechanical Properties of Poly(vinyl alcohol)-Based Blend Plastics Prepared Through Extrusion Method

Plastic blend materials consisting of poly(vinyl alcohol), glycerol and xanthan or gellan were prepared through laboratory extrusion. Their base mechanical properties were compared with the properties of poly(vinyl alcohol) foil and their biodegradability in soil, compost and both activated and anaerobic sludge were assessed. In samples with lower polysaccharide content (10–21 %w/w) the tensile strength of 15–20 MPa was found; the elongation at break of all blends was relatively close to the parameter of poly(vinyl alcohol) foil. The biodegradability levels of the blends tested corresponded to the content of natural components, and the mineralization of the samples with the highest carbohydrate proportion (42 %) reached 50–78 %, depending on the type of the environment. Complete biodegradation of all samples occurred in activated sludge.     

Biodegradability and Biodegradation of Polyesters

A variety of biodegradable plastics have been developed in order to obtain useful materials that do not cause harm to the environment. Among the biodegradable plastics, aliphatic polyesters such as: poly(3-hydroxybutyrate) (PHB), poly(ε-caprolactone) (PCL), poly(butylene succinate) (PBS), and poly(l-lactide) (PLA) have become the focus of interest because of their inherent biodegradability. However, before their widespread applications, comprehensive studies on the biodegradability and biodegradation mechanisms of these polyesters are necessary. Thus, this paper describes the degradation mechanisms and the effects of various factors on the degradation of polyesters. The distribution of polymer-degrading microorganisms in the environment, different microorganisms and enzymes involved in the degradation of various polyesters are also discussed.     

Determination of Mark-Houwink Parameters and Absolute Molecular Weight of Medium-Chain-Length Poly(3-Hydroxyalkanoates)

Absolute molecular weight distributions were determined for different medium-chain-length poly(3-hydroxyalkanoates) (MCL PHAs) with predominantly 3-hydroxyoctanoate (PHO), 3-hydroxynonanoate (PHN) or 3-hydroxydodecanoate content. This is the first study to estimate the Mark-Houwink constants of these polymers in the commonly employed GPC carrier solvent tetrahydrofuran (THF). The absolute molecular weight averages were determined via triple-detector size exclusion chromatography and combined with analyses using various detectors. Unlike with the short-chain-length poly(3-hydroxybutyrate), PHB, uncorrected polystyrene calibration in THF provided a good estimate (within 10 %) of absolute MW values for these MCL PHAs, irrespective of side chain length. Weight-average MW values ranged from 172,000 Da for PHO to 18,200 for PHN with 30 mol% 3-hydroxyheptanoate, and dispersities of all samples were close to two. Melt viscosity data suggested an entanglement molecular weight around 8 × 10⁴ Da, significantly higher than most polymers.     

Preparation and Characterization of Polyhydroxyalkanoate Bioplastic-Based Green Renewable Composites from Rice Husk

The biodegradability, morphology, and mechanical properties of composite materials consisting of acrylic acid-grafted poly(hydroxyalkanoate) (PHA-g-AA) and rice husk (RH) were evaluated. Composites containing PHA-g-AA (PHA-g-AA/RH) exhibited noticeably superior mechanical properties compared with those of PHA/RH because of greater compatibility with RH. The dispersion of RH in the PHA-g-AA matrix was homogeneous because of ester formation and the consequent creation of branched and crosslinked macromolecules, between the carboxyl groups of PHA-g-AA and hydroxyl groups in RH. The water resistance of PHA-g-AA/RH was higher than that of PHA/RH, although the weight loss of composites buried in soil compost indicated that both were biodegradable, especially at high levels of RH substitution. After 60 days, the weight loss of the PHA-g-AA/RH (40 wt%) composite was greater than 90 %. PHA/RH exhibited a weight loss of approximately 4–8 wt% more than PHA-g-AA/RH. The PHA/RH and PHA-g-AA/RH composites were more biodegradable than pure PHA, which implies a strong connection between RH content and biodegradability.     

Novel Biodegradable Thermoplastic Elastomer Based on Poly(butylene succinate) and Epoxidized Natural Rubber Simple Blends

Novel biodegradable thermoplastic elastomer based on epoxidized natural rubber (ENR) and poly(butylene succinate) (PBS) blend was prepared by a simple blend technique. Influence of blend ratios of ENR and PBS on morphological, mechanical, thermal and biodegradable properties were investigated. In addition, chemical interaction between ENR and PBS molecules was evaluated by means of the rheological properties and infrared spectroscopy. Furthermore, the phase inversion behavior of ENR/PBS blend was predicted by different empirical and semi-empirical models including Utracki, Paul and Barlow, Steinmann and Gergen models. It was found that the co-continuous phase morphology was observed in the blend with ENR/PBS about 58/42 wt% which is in good agreement with the model of Steinmann. This correlates well to morphological and mechanical properties together with degree of crystallinity of PBS in the blends. In addition, the biodegradability was characterized by soil burial test after 1, 3 and 9 months and found that the biodegradable ENR/PBS blends with optimum mechanical and biodegradability were successfully prepared.     

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.     

Optimization of Poly(<Emphasis Type="SmallCaps">dl</Emphasis>-Lactic Acid) Degradation and Evaluation of Biological Re-polymerization

Poly(dl-lactic acid) or PLA is a biodegradable polymer. It has received much attention since it plays an important role in resolving the global warming problem. The protease produced by Actinomadura keratinilytica strain T16-1 was previously reported as having PLA depolymerase potential and being applicable to PLA biodegradation, which was used in this work. Therefore, this research demonstrates the important basic knowledge on the biological degradation process by the crude PLA-degrading enzyme from strain T16-1. Its re-polymerization was evaluated. The optimization of PLA degradation by statistical methods based on central composite design was determined. Approximately 6700 mg/l PLA powder was degraded by the crude enzyme under optimized conditions: an initial enzyme activity of 200 U/ml, incubated at 60 °C for 24 h released 6843 mg/l lactic acid with 82% conversion, which was similar to the commercial enzyme proteinase K (81%). The degradable products were re-polymerized repeatedly by using commercial lipase as a catalyst under a nitrogen atmosphere for 6 h. A PLA oligomer was achieved with a molecular weight of 378 Da (n = 5). This is the first report to demonstrate the high efficiency of the enzyme to degrade 100% of PLA powder and to show the biological recycling process of PLA, which is promising for the treatment and utilization of biodegradable plastic wastes in the future.     

The Effects of Additives on the Biodegradation of Polycaprolactone Composites

Because environmental pollution caused by plastic waste is a major problem investigations concerning biodegradable packaging are important and required. In this study, the biodegradation of PCL composite films with organic (glycerol monooleate and oleic acid) and inorganic additives (organo nano clay) was investigated to understand which additive and the amount of additive was more effective for biodegradation. The relationship between the degree of crystallinity and the effect of additives on the biodegradability of polycaprolactone (PCL) was examined. PCL composite films were prepared using organo nano clay (0.1–0.4–1–3 wt%) and oleic acid (1–3–5 wt%) or GMO (1–3–5 wt%). The 35 films prepared with PCL (P), clay (C), oleic acid (O), or glycerol monooleate (G) are coded as P_C#wt%_O (or G)#wt%. The composite films, P_C0.4_O5 contains 0.4 wt% clay and 5 wt% oleic acid and the P_C3_G1 contains 3 wt% clay and 1 wt% glycerol monooleate. The biodegradation of PCL films in simulated soil was studied for 36 months. The films were periodically removed from the simulated soil and film thicknesses, weight losses, visual changes, crystal structures, and a functional group analyses were performed. PCL composite films are separated into three groups, depending on degradation time, (1) films that degraded before 8 months (fast degradation), (2) films that degraded around 24 months (similar to neat PCL), and (3) films that take longer to degrade (slow degradation). The films in the first group are PCL films with 1 and 3 wt% clay additive and they begin to biodegrade at the 5th month. However, a composite film of PCL with only 0.4 wt% clay and 5 wt% GMO addition has the shortest degradation time and degraded in 5 months. The films in the last group are; P_G3, P_G5, P_C0.1, P_C0.1_O1, and P_C0.1_O5 and they took around 30 months for biodegradation. It was observed that increasing the organo nanoclay additive increases the biodegradability by disrupting the crystal structure and causing a defective crystal formation. The addition of GMO with organo nano clay also accelerates biodegradation. The addition of organo nano clay in an amount as small as 0.1 wt% acts as the nucleating agent, increases the degree of crystallinity of the PCL composites, and slows the biodegradation period by increasing the time.     

Biodegradation Behaviors of Poly(p-dioxanone) in Different Environment Media

This work was aimed at researching the aerobic biodegradation of poly(p-dioxanone) (PPDO), a novel kind of degradable polymer material, by simulating real-life conditions in a laboratory-scale test, specified by the standard methods based on two biodegradation environments, composting and aqueous media. To measure and describe the biodegradability of PPDO, not only had carbon dioxide produced by respiratory metabolism of microorganism been measured, which determines the ultimate aerobic biodegradability of chemical compounds, but also the detailed results of biodegradation were further characterized by monitoring physical, chemical and thermal properties changes of test materials at different incubation times in the two media, confirmed by using the appropriate analytical techniques. Scanning electron microscopy was used to observe the surface morphology, and the thermal performance of PPDO was characterized by differential scanning calorimetry. The changes of molecular weight were detected by intrinsic viscosity ([η]) and gel permeation chromatography, and the variations of the molecular structure were monitored by the nuclear magnetic resonance and FT-IR. The results show that PPDO has outstanding character of biodegradation and may be more adapted for biodegrading in liquid medium than in composting.     

Characterization of Urea Encapsulated by Biodegradable Starch-PVA-Glycerol

The influence of the blending ratio of biodegradable starch/polyvinyl alcohol (PVA)/glycerol in encapsulating urea has been investigated. It is found that water absorption capacity increased approximately 135 % as the amounts of starch, PVA and glycerol in the composite film increase. Therefore, the swell ability of the composite film is increased and the urea is released from the composite film in the wet environment. The FTIR shows that the urea had been encapsulated successfully in the composite films. Moreover, the soil burial biodegradation results indicated that the biodegradability of the starch/PVA/glycerol/urea composite film strongly depended on the PVA proportion in the composite film matrix. The DSC results show that the higher the amount of PVA in the composite film, the less change of the melting enthalpy value. The crystalline region of PVA remains after biodegradation.     

Aliphatic Polyester-Based Green Renewable Eco-composites from Agricultural Residues: Characterization and Assessment of Mechanical Properties

The biodegradability, morphology, and mechanical properties of composite materials consisting of maleic anhydride-grafted poly(butylene succinate adipate) (PBSA-g-MA) and agricultural residues (wheat bran, WB) were evaluated. Composites containing maleic anhydride-grafted PBSA (PBSA-g-MA/WB) exhibited noticeably superior mechanical properties compared with those of PBSA/WB because of greater compatibility with WB. PBSA/WB exhibited a tensile strength at break of approximately 2–15 MPa more than PBSA-g-MA/WB. The dispersion of WB in the PBSA-g-MA matrix was highly homogeneous as a result of ester formation and the subsequent creation of branched and cross-linked macromolecules between the anhydride carboxyl groups of PBSA-g-MA and hydroxyl groups in WB. Additionally, the PBSA-g-MA/WB composites were more easily processed due to their lower melt viscosity. Water resistance of PBSA-g-MA/WB was higher than that of PBSA/WB, although weight loss of composites buried in Azospirillum brasilense BCRC 12270 liquid culture medium compost indicated that both were biodegradable, especially at high levels of WB substitution. After 60 days, the weight loss of the PBSA-g-MA/WB (40 wt%) composite was greater than 90 %. PBSA/WB exhibited a weight loss of approximately 4–8 wt% more than PBSA-g-MA/WB. The PBSA/WB and PBSA-g-MA/WB composites were more biodegradable than pure PBSA, which implies a strong connection between WB content and biodegradability.     

Transfer of Graphene CVD to Surface of Low Density Polyethylene (LDPE) and Poly(butylene adipate-co-terephthalate) (PBAT) Films: Effect on Biodegradation Process

Here, the influence of graphene as a coating on the biodegradation process for two different polymers is investigated, poly(butylene adipate-co-terephthalate) (PBAT) (biodegradable) and low-density polyethylene (LDPE) (non-biodegradable). Chemical vapor deposition graphene was transferred to the surface of two types of polymers using the Direct Dry Transfer technique. Polymer films, coated and uncoated with graphene, were buried in a maturated soil for up to 180 days. The films were analyzed before and after exposure to microorganisms in order to obtain information about the integrity of the graphene (Raman Spectroscopy), the biodegradation mechanism of the polymer (molecular weight and loss of weight), and surface changes of the films (atomic force microscopy and contact angle). The results prove that the graphene coating acted as a material to control the biodegradation process the PBAT underwent, while the LDPE covered by graphene only had changes in the surface properties of the film due to the accumulation of solid particles. Polymer films coated with graphene may allow the production of a material that can control the microbiological degradation, opening new possibilities in biodegradable polymer packaging. Regarding the possibility of graphene functionalization, the coating can also be selective for specific microorganisms attached to the surface.     

Influence of aeration rate and biodegradability fractionation on composting kinetics

The influences of aeration rate and biodegradability fractionation on biodegradation kinetics during composting were studied. The first step was the design of a suitable lab-reactor that enabled the simulation of composting. The second step comprised of composting trials of six blends of sludge (originating from a food processing effluent) with wood chips using aeration rates of 1.69, 3.62, 3.25, 8.48, 11.98 and 16.63 L/h/kg DM of mixture. Biodegradation was evaluated by respiration measurements and from the analysis of the substrate (dry matter, organic matter, total carbon and chemical oxygen demand removal). Continuous measurement of oxygen consumption was coupled with the analysis of initial substrate and composted product for chemical oxygen demand (in the soluble and non-soluble fractions), which enabled an evaluation of the organic matter biodegradability. Oxygen requirements to remove both the easily and slowly biodegradable fractions were determined. Dividing the substrate into different parts according to biodegradability allowed explanation of the influence of aeration rate on stabilization kinetics. Considering that the biodegradation kinetics were of the first-order, the kinetic constants of the easily and slowly biodegradable fractions were calculated as a function of temperature. The methodology presented here allows the comparison of organic wastes in terms of their content of easily and slowly biodegradable fractions and the respective biodegradation kinetics.     

Toughening of Polyvinyl Alcohol Hydrogel Through Co-Crosslinking and its Wastewater Treatment Performance by Immobilizing with Microorganism

In order to improve the hydraulic impact resistance of the polyvinyl alcohol (PVA) hydrogel as microorganism immobilization carrier and meet the requirements of long-time aeration of sewage treatment, the toughening PVA hydrogel beads were prepared by co-crosslinking with polyoxypropylene triol (PPG) through the boric acid (H₃BO₃)-chemical crosslinking method. It was found that PPG could increase the consumption of H₃BO₃, participated and accelerated the crosslinking reaction of PVA, and the pore size of the surface layer and core layer of the hydrogel beads can be controlled. With increasing PPG content, the shear storage modulus (G’) and the effective network density (ν_e) increased first, reached maximum in presence of 2 wt% PPG, and decreased afterwards. A relatively low content of PPG could promote the formation of relatively uniform and dense network structure in PVA hydrogel, resulting in an improvement of the mechanical property and long-term hydraulic stability of the gel beads. By addition of PPG, the capillary water absorption capacity of PVA hydrogel can be enhanced and the high permeability can be kept well. When applying in waste water treatment, the value of the oxygen uptake rate (OUR) and COD removal rate of the PVA hydrogel immobilized with activated sludge had no obvious difference with addition of PPG, and a high microbial activity can be maintained.     

Biodegradable Soy-Based Plastics: Opportunities and Challenges

Today's plastics are designed with little consideration for their ultimate disposability or the effect of the resources (feedstocks) used in making them. This has resulted in mounting worldwide concerns over the environmental consequences of such materials when they enter the mainstream after their intended uses. This led to the concept of designing and engineering new biodegradable materials–materials that have the performance characteristics of today's materials but that undergo biodegradation along with other organic waste to soil humic materials. Hence, the production of biodegradable materials from annually renewable agricultural feedstocks has attracted attention in recent years. Agricultural materials such as starches and proteins are biodegradable and environmentally friendly. Soybean is a good candidate for manufacturing a large number of chemicals, including biodegradable plastics, as it is abundantly available and cheap. Soy protein concentrate, isolate, or flakes could be compounded with synthetic biodegradable plastics such as polycaprolactone or poly (lactic acid) to make molded products or edible films or shopping bags and make the environment cleaner and greener.     

Soil Biodegradation of PHBV/Peach Palm Particles Biocomposites

There is great interest in developing eco-friendly green biocomposites from plant-derived natural fibers and crop-derived bioplastics attributable to their renewable resource-based origin and biodegradable nature. Fully biodegradable composites, made from both biodegradable polymeric matrices and natural fibers, should be advantageous in some applications, such as one way packaging. Polyhydroxyalkanoates (PHAs) are naturally occurring biodegradable polymers produced from a wide range of microorganisms, with poly(3-hydroxybutyrate) P(3HB) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) being important examples of PHAs. In this work, biocomposites of PHBV consisting of a PHBV matrix incorporating peach palm particles (PPp), [i.e., 100/0, 90/10, 80/20 and 75/25 (%w/w) PHBV/PPp] were processed by injection molding at 160 °C. The effect of PPp loading on the thermal and the mechanical properties, as well as on the morphological behavior of the PHBV/PPp biocomposites was investigated. Soil biodegradation tests were carried out by burying specimen beakers containing aged soil and kept under controlled temperature and humidity in accordance with ASTM G160-98. Degradation of the biocomposites was evaluated by visual analysis, scanning electron microscopy (SEM) and thermogravimetric analysis (TGA) following test exposures of up to 5 months. The addition of PPp reduced the maximum strength and the elongation at break of the biocomposites. On the other hand, the Young’s modulus improved with the PPp content. Micrographs of the fracture surfaces following tensile strength testing revealed a large distance between the PHBV matrix and PPp particles although a low interaction is expected. Where measured, these distances tended increase as the PPp content of the biocomposites increased. Soil biodegradation tests indicated that the biocomposites degraded faster than the neat polymer due to the presence of cavities that resulted from introduction of the PPp and that degradation increased with increasing PPp content. These voids allowed for enhanced water adsorption and greater internal access to the soil-borne degrader microorganisms.     

Exploring the Biodegradation Potential of Polyethylene Through a Simple Chemical Test Method

Oxidatively degradable polyethylene is finding widespread use, particularly in applications such as single use packaging and agriculture. However, the key question which still remains unanswered is the ultimate fate and biodegradability of these polymers. During a short-time frame only the oxidized low molecular weight fraction will be amenable to significant biodegradation. The short-time frame biodegradation potential of different LDPE-transition metal formulations was, thus, explored through a simple chemical extraction of oxidized fraction. In addition the effectiveness of different transitions metals was evaluated by comparing the extractable fractions. Blown LDPE films modified with different transition metal based pro-oxidants were thermo-oxidized at 60 °C over extended periods. The structural changes occurring in the polymer were monitored and the oxidized degradation products formed as a result of the aging process were estimated by extractions with water and acetone. The extractable fraction first increased to approximately 22 % as a result of thermo-oxidative aging and then leveled off. The extractable fraction was approximately two times higher after acetone extraction compared to extraction with water and as expected, it was higher for the samples containing pro-oxidants. Based on our results in combination with existing literature we propose that acetone extractable fraction gives an estimation of the maximum short-term biodegradation potential of the material, while water extractable fraction indicates the part that is easily accessible to microorganisms and rapidly assimilated. The final level of biodegradation under real environmental conditions will of course be highly dependent on the specific environment, material history and degradation time.