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.     

A review of the biodegradability and utility of poly(caprolactone)

Since the early 1970s, it has been known that exposure of poly(caprolactone) (PCL) to a variety of microorganisms results in biodegradation of this polymer. Besides the ability of PCL to be utilized as a carbon source for microorganisms, it has been demonstrated that, during degradation, carbon dioxide is generated. Soil burial and compost experiments have shown that chain scission of the PCL backbone occurs, mechanical properties of articles prepared from PCL are reduced rapidly, and significant weight loss occurs in a short time period. This inherent biodegradability of PCL, in combination with its ability to be converted by conventional extrusion equipment, allows for the preparation of biodegradable articles that have utility.Paper presented at the Bio/Environmentally Degradable Polymer Society—Third National Meeting, June 6–8, 1994, Boston, Massachusetts.     

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.     

Process,Characterization and Biodegradability of Aliphatic Aromatic Polyester/Sisal Fiber Composites

The biodegradability, morphology, and mechanical properties of composite materials made of Poly(butylene adipate-co-terephthalate) (PBAT) and sisal fiber (SF) were evaluated. Composites containing acrylic acid-grafted PBAT (PBAT-g-AA/SF) exhibited noticeably superior mechanical properties due to greater compatibility between the two components. The dispersion of SF in the PBAT-g-AA matrix was highly homogeneous as a result of ester formation between the carboxyl groups of PBAT-g-AA and hydroxyl groups in SF and the consequent creation of branched and cross-linked macromolecules. Each composite was subjected to biodegradation tests in Rhizopus oryzae compost. Morphological observations indicated severe disruption of film structure after 60 days of incubation, and both the PBAT and the PBAT-g-AA/SF composite films were eventually completely degraded. Water resistance of PBAT-g-AA/SF was higher than that of PBAT/SF, although weight loss of composites buried in Rhizopus oryzae compost indicated that both were biodegradable, even at high levels of SF substitution. The PBAT-g-AA/SF films were more biodegradable than those made of PBAT, implying a strong connection between these characteristics and biodegradability.     

Enhanced Mineralization of PLA Meltblown Materials Due to Plasticization

Polylactic acid (PLA) is one of the important biodegradable polymers. It is widely used in many industrial applications such as films and fibers. Its biodegradability is based on data derived mostly from composting processes. For a broad application of the PLA material in personal care products, an understanding of anaerobic biodegradability is essential because soiled personal care products are usually disposed of in sanitary landfills, where biodegradability mechanisms are predominately in anaerobic conditions. Extensive laboratory results are acquired to elucidate the effects of the temperature on the PLA anaerobic sludge biodegradation. When the temperature is higher than PLA glass transition temperature (T_g), anaerobic degradation is accelerated. A plausible mechanism to explain this observation is that amorphous part of the polymer is easily accessible by microorganisms. When the degrading temperature is below PLA glass transition temperature, sample mineralization under anaerobic conditions is apparently slowed. The mechanisms elucidated by T_g modification can be utilized to control the rate of PLA biodegradation for sustainable waste management.     

Studies on enhanced degradable plastics. III. The effect of weathering of polyethylene and (ethylene-carbon monoxide) copolymers on moisture and carbon dioxide permeability

Two enhanced-photodegradable polyethylenes were studied to determine the effect of photooxidative degradation upon transport properties. Water vapor permeability of LDPE films containing metal compound prooxidants, weathered to different extents under outdoor exposure was studied. A film made of LDPE blended with 20 wt% of polycaprolactone was also examined to determine if biodegradation over a 40-day period resulted in a measurable change in its water vapor transport characteristics. A gravimetric technique was used to study the effects of outdoor and weather-ometer exposures on the permeability of carbon dioxide of both the LDPE film and (ethylene-carbon monoxide) copolymer films. Generally, photooxidative degradation was seen to be accompanied by a change in transport characteristics of the polymer films.     

Fungal Degradation of Poly(Butylene Adipate-Co-Terephthalate) in Soil and in Compost

The present work mainly dedicated to fungal degradation of poly(butylene adipate-co-terephthalate) [PBAT], to enclose the role of fungi in a real process of biodegradation, the degree of degradation, and to understand the kinetics of PBAT biodegradation. Respirometer tests were realized in soil at 30 °C, and in compost at 30 and 58 °C. Results have shown that temperature is one of the essential parameters governing the fungal degradation of PBAT. Moreover, the final rates of PBAT biodegradation in an inoculated compost with fungi and in a real compost were found comparable, which means that the selected fungi were efficient as much as a mixture of bacteria and fungi. The curves of PBAT biodegradation were modeled by Hill sigmoid. Fungal degradation was completed by investigating the physical and the chemical properties of the polymer during the process of degradation using several analytical methods such as matrix assisted laser desorption ionization-time of fly spectroscopy, size exclusion chromatography, and differential scanning calorimetry. These experiments led to a better understanding of the various stages of fungal degradation of PBAT: hydrolysis as well as mineralization. Furthermore, the analysis of metabolizing products was investigated also.     

Aromatic Copolyester-based Nano-biocomposites: Elaboration, Structural Characterization and Properties

Biodegradable polymers are one of the most promising ways to replace non-degradable polymers. But, to be a real alternative to classical synthetic polymers and find applications, biopolymer (biodegradable polymer) properties have to be enhanced. Nano-biocomposites, which are obtained by incorporation of nanofillers into a biomatrix, are an interesting way to achieve these improvements. Modified and unmodified montmorillonites have been introduced into a biodegradable aromatic copolyester, poly(butylene adipate-co-terephthalate) (PBAT). Structural characterization, thermal and mechanical tests have been carried out to understand better the relations between the nanofillers structuring and the final nano-biocomposite properties. Main results show that clay incorporation and the obtained intercalated structures improve PBAT properties (enhanced thermal stability, increased stiffness) and thus may increase the attractiveness of this biopolymer.     

Topographical imaging as a means of monitoring biodegradation of poly(hydroxyalkanoate) films

Poly(hydroxyalkanoates) (PHAs) are a class of bacterially-derived polymers that are naturally biodegradable through the action of extracellular depolymerase enzymes secreted by a number of different bacteria and fungi. In this paper we describe the development of topographical imaging protocols (by both scanning electron microscopy; SEM, and confocal microscopy; CM) as a means of monitoring the biodegradation of solution cast films of poly(3-hydroxybutanoate-co-3-hydroxyhexanoate) (P3HB/3HHx) and medium-chain-length (mcl-) PHA. Pseudomonas lemoignei and Comamonas P37C were used as sources for PHA depolymerase enzymes as these bacteria are known to degrade at least one of the polymers in question. SEM revealed the bacterial colonization of the film surfaces while CM permitted the comparative assessment of the roughness of the film surfaces upon exposure to the two bacterial strains. By dividing the total surface area of the film (A′) by the total area of the scan (A) it was possible to monitor biodegradation by observing differences in the topography of the film surface. Prior to inoculation, P3HB/3HHx films had an A′/A ratio of 1.06. A 24-h incubation with P. lemoignei increased the A′/A ratio to 1.47 while a 48- and 120-h incubation with Comamonas resulted in A′/A ratios of 1.16 and 1.33, respectively. These increases in the A′/A ratios over time demonstrated an increase in the irregularity of the film surface, indicative of PHA polymer breakdown. Mention of trade names or commercial products in this publication is solely for the purpose of providing specific information and does not imply recommendation or endorsement by the U.S. Department of Agriculture.     

Electron Microscope Observation of Biodegradation of Polymers

Biodegradable polymers generally decompose in the various media in our environments. These environments contain soils, seawater, and activated sludge. If biodegradable materials waste is discarded, they decompose in these media. The biodegradation process of biodegradable polymers was investigated by scanning electron microscopy. Polycaprolactone, polybutylene succinate, and P(3HB-co-3HV) were tested. The shapes of holes on the decomposing surfaces are different according to the biodegradation media. Semispherical holes are observed on the surfaces of polybutylene succinate films degraded in activated sludge and cracks are observed on the surfaces of polycaprolactone films degraded in soil.     

Biodegradation of pretreated polyethylene film by Pseudomonas aeruginosa AMB-CD-1

A comparative study evaluated the acid, alkali, and heat-treated polyethylene biodegradation efficiency of Pseudomonas aeruginosa AMB-CD-1. The polyethylene (PE) pieces were separately treated with heat (50°C), acid (1N HCl), and alkali (1N NaOH) and then washed with water before use. All the treated samples were analyzed through thermogravimetric analysis. In addition, weight and temperature changes during the decomposition reactions were also measured and determined. In these treatments, the PE films of heat-treated and acid-treated low-density polyethylene (LDPE) indicated more significant weight loss at 120°C (48.99% and 40.75%, respectively) as compared to their control or untreated PE and alkali-treated LDPE (21.84% and 24.68%, respectively). A biodegradation assay was then conducted with treated and untreated LDPE films with P. aeruginosa AMB-CD-1 strain. Fourier transform infrared spectroscopy analysis revealed that the heat or acid-pretreated samples with isolate AMB-CD-1 displayed peaks at 2922.84, 2923.97, and 1450.31, 874.22 cm⁻¹ for C–H stretching deformation vibration, CH₂ scissoring vibration, –CHO stretching, and strong alkyl structure, respectively. Furthermore, the new peaks with a significant difference at 2500–2000 cm⁻¹ (O═C═O, O–H stretching vibration: carboxylic acid) and 1500–1000 cm⁻¹ (–CHO and C═O stretching) were noticed in the infrared spectral range of LDPE degradation. Modifications in the functional group provided evidence that biodegradation had impacted the chemical structure of the LDPE film. Additionally, it was demonstrated that pretreating LDPE films with heat or acid could speed up their biodegradation.     

Formulation and Characterization of Biodegradable Packaging Film Derived from Potato Starch &; LDPE Grafted with Maleic Anhydride—LDPE Composition

There is a paradigm shift from non renewal resources to renewable resources in view of problems of disposal of plastic products after their life cycle. This paper deals with the approach, preparation and product properties of polymer prepared by using polysaccharide based biodegradable polymer. Basic material has been prepared by mixing LDPE, LDPE-g-mA (LDPE grafted with (0.5%) maleic anhydride (1:1)) containing a polar group in the LDPE backbone. Prepared basic material has been compounded in twin screw extruder with 0, 2.5, 5.0, 7.5, 10.0, 12.5 & 15% of Potato Starch. Thereafter, after conditioning blown film samples were prepared using extrusion film blowing technique, under temperature profile ranging from 120 to 160 °C. Packaging films have been prepared with maximum 15% potato starch contents and have been characterized by FTIR, DSC, TGA, and XRD techniques to ascertain its impact on some structural and thermal properties like thermal stability, flexibility, crystallinity, crystal size etc.     

Evaluation of Biodegradable Films Made of Waste Mycelium and Poly (Vinyl Alcohol) on the Yield of Pak-Choi

Novel biodegradable films were prepared via blending of poly (vinyl alcohol) and waste mycelium from sauce residue and citric acid fermentation residue, respectively. The performance of these two types of films when used as alternative covers for pak-choi growth under semi-arid climatic conditions was evaluated via field test towards their abilities for water retention and biodegradation, together with the impact on the yield and nutritional quality of pak-choi. Experimental results showed that the use of these films could result in 50% higher water retention than a blank control film after 96-h treatment at 40?°C. Films were biodegraded within 14?weeks under natural conditions, leading to a significant mineralization, progressively releasing over 56% of K⁺, NO₃ ^?, Mg²⁺ and organics, beneficial for plant growth as fertilizer. The yield of pak-choi was increased by 80% in weight when using these films compared with the unmulched control. Compared to those treated with traditional LDPE mulching film, the average contents of chlorophyll, crude protein and soluble sugar in pak-choi were increased by 52.9, 7.2, 80.7% (blends of sauce residue) and 26.7, 11.4, 10.8% (blends of citric acid fermentation residue), respectively.     

Comparative Biodegradation in Soil Behaviour of two Biodegradable Polymers Based on Renewable Resources

This work presents the last phase of long-term experimental studies on the biodegradation in soil behaviour of polymers destined for agricultural applications. The paper focuses on comparative studies between the biodegradation in soil behaviour of two important biodegradable polymers based on renewable resources: poly(lactic acid) (PLA) versus polyhydroxyalkanoates (PHA). Full-scale experiments were carried out during the period June 2008–January 2009. Different methods of exposure were applied in the case of polyhydroxyalkanoates, simulating the agricultural biodegradable mulching films use and their fate in soil after the end of their useful lifetime. The field results were compared with the results of biodegradation under controlled laboratory conditions simulating biodegradation in soil, using soil from the experimental field. Further, the field results were compared against the results of biodegradation under farm composting conditions.     

Biodegradation of Agricultural Plastic Films: A Critical Review

The growing use of plastics in agriculture has enabled farmers to increase their crop production. One major drawback of most polymers used in agriculture is the problem with their disposal, following their useful life-time. Non-degradable polymers, being resistive to degradation (depending on the polymer, additives, conditions etc) tend to accumulate as plastic waste, creating a serious problem of plastic waste management. In cases such plastic waste ends-up in landfills or it is buried in soil, questions are raised about their possible effects on the environment, whether they biodegrade at all, and if they do, what is the rate of (bio?)degradation and what effect the products of (bio?)degradation have on the environment, including the effects of the additives used. Possible degradation of agricultural plastic waste should not result in contamination of the soil and pollution of the environment (including aesthetic pollution or problems with the agricultural products safety). Ideally, a degradable polymer should be fully biodegradable leaving no harmful substances in the environment. Most experts and acceptable standards define a fully biodegradable polymer as a polymer that is completely converted by microorganisms to carbon dioxide, water, mineral and biomass, with no negative environmental impact or ecotoxicity. However, part of the ongoing debate concerns the question of what is an acceptable period of time for the biodegradation to occur and how this is measured. Many polymers that are claimed to be ‘biodegradable’ are in fact ‘bioerodable’, ‘hydrobiodegradable’, ‘photodegradable’, controlled degradable or just partially biodegradable. This review paper attempts to delineate the definition of degradability of polymers used in agriculture. Emphasis is placed on the controversial issues regarding biodegradability of some of these polymers.     

Biodegradability of a Selected Range of Polymers and Polymer Blends and Standard Methods for Assessment of Biodegradation

Synthetic polymers are important to the packaging industry but their use raises aesthetic and environmental concerns, particularly with regard to solid waste accumulation problems and the threat to wildlife. Some concerns are addressed by attention to problems associated with source reduction, incineration, recycling and landfill. Others are addressed by the development of new biodegradable polymers either alone or in blends. Materials used for biodegradable polymers include various forms of starch and products derived from it, biopolyesters and some synthetic polymers. Starch is rapidly metabolised and is an excellent base material for polymer blends or for infill of more environmentally inert polymers where it is metabolised to leave less residual polymer on biodegradation. This should help to improve the environmental impact of waste disposal. A number of standard methods have been developed to estimate the extent of biodegradability of polymers under various conditions and with a variety of organisms. They tend to be used mainly in the countries where they were developed but there is much overlap between the standards of different countries and wide scope for development of consistent and international standards.     

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.     

A New Biodegradable Injection Moulded Bioplastic from Modified Soy Meal and Poly (butylene adipate-co-terephthalate): Effect of Plasticizer and Denaturant

Soy meal, a co-product of the soy oil-based biodiesel industry, has up to 50 % protein content. The main aim of this work was to develop value-added application for soy meal. Soy meal was plasticized by glycerol and water, denatured by the addition of guanidine hydrochloride (GHCl), and then blended with poly (butylene adipate-co-terephthalate) (PBAT), petroleum based tough biodegradable polymer. Characterization by FTIR spectroscopy confirmed that soy meal was plasticized and denatured. The blends of PBAT/soy meal (SM), PBAT/plasticized soy meal and PBAT/GHCl modified plasticized soy meal (mPSM) were fabricated by industry prevalent extrusion and injection molding process. The developed bioblends were characterized by thermal and mechanical testing. One of the important outcomes of this research was that elongation of the bioblend was found to increase by 80 % after plasticization and denaturation of soy meal. Scanning electron microscope analysis showed that PBAT/mPSM blends have smoother surfaces and better internal structures than the other two.     

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.     

Biodegradability of Poly (lactic acid), Preparation and Characterization of PLA/Gum Arabic Blends

In this study, the biodegradation of PLA films using microorganisms from Lake Bogoria (Kenya) were investigated. The biodegradation tests done using certain strains of thermophilic bacteria showed faster biodegradation rates and demonstrated temperature dependency. The biodegradation of the PLA films was studied using Gel Permeation Chromatography (GPC) and light microscopy. The biodegradation of PLA was demonstrated by decrease in molecular weight. The preparation and characterization of PLA/Gum Arabic blends were also investigated using DSC, TGA, TMA and NMR. In summary, the results obtained in this research show that PLA films undergo fast biodegradation using thermophiles isolated from Lake Bogoria. The PLA/GA blends studies show it is possible to prepare films of varying hydrophobic–hydrophilic properties for various applications.