Synthesis of3H- polyethylene and its use for fate studies on degradable plastics

Determining the fate of xenobiotic materials in the environment can be aided by the use of radioactive isotope technology. Previous research on the degradation of polymers such as polyethylene (PE) was aided by the utilization of radiotracers. In order to study the environmental fate of degradable (PE/starch) plastics, we synthesized³H-labeled PE. Results of soil incubation studies indicate that only minimal degradation of the PE component, as indicated by the production of water-soluble metabolites, occurred during 2 years of incubation in soil. Despite the minimal degradation, the³H label did not allow for detection of the degradation products. In addition, the³H-PE was particularly useful for tracing the fate of degradable plastics after consumption by terrestrial isopods. The detection of aqueous-soluble radioactivity in isopod frass was used to indicate degradation of the plastic film.     

Degradation studies of novel degradable starch-polyethylene plastics containing oxidized polyethylene and prooxidant

Linear low-density polyethylene films were prepared that contained native corn starch (7, 14, or 28%), low or high molecular weight oxidized polyethylene (15%), and a prooxidant mixture (18% POLYCLEAN II) that contains manganese and vegetable oil. For each mixture all components were first mixed at high temperatures in a twin-screw extruder and pelletized. The pellets were cast into films using a single-screw extruder. Oxidized-polyethylene addition did not impair the transparency and thickness of the films and did not reduce the percentage elongation, whereas significant reductions in film mechanical properties were observed. Thermal and photodegradation properties of each film were evaluated by 70°C forced-air oven treatment (20 days), by high-temperature, high-humidity treatment in a steam chamber (20 days), and by exposure to ultraviolet light (365 nm; 4 weeks). Changes in the mechanical properties of the films were determined by an Instron Universal Test Machine; in the carbonyl index, Fourier transform infrared spectroscopy; and in molecular weight, by high-temperature gel-permeation chromatography (HT-GPC). The addition of oxidized polyethylene, especially high molecular weight oxidized polyethylene, and up to 14% starch to the films significantly increased the rate of thermal and photodegradation.Journal Paper No. J-15363 of the Iowa Agriculture and Home Economics Experiment Station, Ames. Project No. 0178 and 2889.     

Biodegradability of chitin- and chitosan-containing films in soil environment

The biodegradation of polyethylene-chitin (PE-chitin) and polyethylene-chitosan (PE-chitosan) films, containing 10% by weight chitin or chitosan, by pure microbial cultures and in a soil environment was studied. Three soil-inhabited organsims,Serratia marcescens, Pseudomonas aeruginosa, andBeauveria bassiana were able to utilize chitin and chitosan in prepared PE-chitin and PE-chitosan films after eight weeks of incubation at 25°C in a basal medium containing no source of carbon or nitrogen. In a soil environment, the biodegradation of those films was studied and compared with a commercial biodegradable film containing 6% by the weight of corn starch. In soil placed in the lab, 73.4% of the chitosan and 84.7% of the chitin in the films were degraded, while 46.5% of the starch in the commercial film was degraded after six months of incubation. In an open field, 100% of the chitin and 100% of the chitosan in the films were degraded, but only 85% of the starch in the commercial film was degraded after six months of incubation. The weight of controls, (polyethylene films), remained mainly stable during the incubation period. Both PE-chitin and PE-chitosan films degraded at a higher rate than the commercial starch-based film in a soil environment indicating the potential use of chitin-based films for the manufacturing of biodegradable packaging materials.     

Effect of Oxidized Starch on Morphology,Rheological and Tensile Properties of Low-Density Polyethylene/Linear Low-Density Polyethylene/Thermoplastic Oxidized Starch Blends

In this work, morphology, rheological and tensile properties of low-density polyethylene/linear low-density polyethylene/thermoplastic oxidized starch (LDPE/LLDPE/TPOS) blends are studied. The blends of LDPE/LLDPE (70/30, w/w) containing 0–20 wt% TPOS in the presence of 3 wt% of PE-grafted maleic anhydride (PE-g-MA) as a compatibilizer are prepared by a twin screw extruder and then converted to appropriate thin films using an extrusion film blowing machine. Scanning electron microscopic images show that there is a relative good dispersion of oxidized starch particles in PE matrices. However, as TPOS content in the blends increases, the starch particle size increases too. The rheological analyses indicate that TPOS can decrease the elasticity and viscosity of the blends. The LDPE/LLDPE/TPOS blends show power-law behavior and as the TPOS content increases the power-law exponent (n) and consistency index (K) decrease. The ultimate tensile strength and elongation at break of the final blend films reduce, when TPOS content increases from 5 to 20 wt%. However, the required mechanical properties for packaging applications are achieved when 10 wt% oxidized starch is added, according to ASTM D4635.     

Preparation and Optimization of Starch/Poly Vinyl Alcohol/ZnO Nanocomposite Films Applicable for Food Packaging

Pollution and destruction of the environment due to the accumulation of non-degradable plastics are some of the most important concerns in the world. A significant amount of this waste is related to the polymers used in food packaging. Therefore, experts in the food industry have been looking for suitable biodegradable alternatives to synthetic polymers. Preparing biocompatible and biodegradable films based on starch is a good choice. In this study, various factors affecting films of starch/polyvinyl alcohol (PVA)/containing ZnO nanoparticles such as the amount of starch, PVA, glycerol, and ZnO were evaluated by response surface methodology (RSM). Film formation by solvent casting method, mechanical properties, swelling, solubility, and water vapor permeability (WVP) were selected as responses of RSM. The results showed that hydrogen bonding interactions between polyvinyl alcohol and starch improved the film formation. The effect of glycerol and PVA content on the mechanical strength was contrary to each other. As the amount of PVA increased, the tensile strength first decreased and then increased. The value of WVP was for all Runs from 0 to 6.77?×?10^??8 g m^??1 s^??1 Pa^??1. Finally, films with high film formation, maximum tensile strength, and high elongation at break, minimum solubility, permeability, and swelling were optimized.

     

Dialdehyde starch and zein plastic: Mechanical properties and biodegradability

Dialdehyde starch (DAS) and zein, a hydrophobic corn protein, were investigated to produce biodegradable plastics with improved water resistance and mechanical properties. In the study, dialdehyde starch and zein ratio, plasticizers, and degree of starch oxidation were examined. Increased molding temperature and level of starch oxidation decreased water absorption of the plastic. Tensile strength and Young's modulus increased with starch oxidation. The biodegradation of starting materials and ground plastic specimens was studied in aerobic soil reactors maintained at 25°C for 180 days. Biodegradation of corn starch, zein, and dialdehyde starch for 180 days produced CO₂ equivalent to 64, 63, and 10% of theoretical carbon, respectively. Specimens of molded DAS and zein (3 : 1) plastic showed accelerated CO₂ evolution compared to DAS and other raw materials alone. By 180 days, specimens made with starch of low oxidation (1 and 5% oxidized) demonstrated a 60% biodegradation, and specimens with highly oxidized starch (90% oxidized) achieved 37% biodegradation.Paper presented at the Bio/Environmentally Degradable Polymer Society—Third National Meeting, June 6–8, 1994, Boston, Massachusetts.Journal Paper J-15927 of the Iowa Agriculture and Home Economics Experiment Station, Ames, Project No. 3258.     

Performance and Environmental Impact of Biodegradable Films in Agriculture: A Field Study on Protected Cultivation

The performance, the degradability in soil and the environmental impact of biodegradable starch-based soil mulching and low tunnel films were assessed by means of field and laboratory tests. The lifetime of the biodegradable mulches was 9 months and of the biodegradable low-tunnel films 6 months. The radiometric properties of the biodegradable films influenced positively the microclimate: air temperature under the biodegradable low tunnel films was 2 °C higher than under the low density polyethylene films, resulting in an up to 20% higher yield of strawberries. At the end of the cultivation period, the biodegradable mulches were broken up and buried in the field soil together with the plant residues. One year after burial, less than 4% of the initial weight of the biodegradable film was found in the soil. According to ecotoxicity tests, the kinetic luminescent bacteria test with Vibrio fischeri and the Enchytraeus albidus ISO/CD 16387 reproduction potential, there was no evidence of ecotoxicity in the soil during the biodegradation process. Furthermore, there was no change in the diversity of ammonia-oxidizing bacteria in the soil determined on the basis of the appearance of amoA gene diversity in denaturing gradient gel electrophoresis.     

Characterization of Biodegradable Polymer Blends of Acetylated and Hydroxypropylated Sago Starch and Natural Rubber

Development of biodegradable polymers from absolute environmental friendly materials has attracted increasing research interest due to public awareness of waste disposal problems caused by low degradable conventional plastics. In this study, the potential of incorporating natural rubber latex (NRL) into chemically modified sago starch for the making biodegradable polymer blends was assessed. Native sago starch was acetylated and hydroxypropylated before gelatinization in preparing starch thermoplastic using glycerol. They were than casted with NRL into biopolymer films according to the ratios of 100.00/0.00, 99.75/1.25, 98.50/2.50, 95.00/5.00, 90.00/10.00 and 80.00/20.00 wt/wt, via solution spreading technique. Water absorption, thermal, mechanical, morphological and biodegradable properties of the product films were evaluated by differential scanning calorimetry (DSC), universal testing machine (UTM), scanning electron microscopy (SEM) and fourier transform infrared spectroscopy. Results showed that acetylation promoted the incorporating behavior of NRL in sago starch by demonstrating a good adhesion characteristic and giving a uniform, homogenous micro-structured surface under SEM observation. However, the thin biopolymer films did not exhibit any remarkable trend in their DSC thermal profile and UTM mechanical properties. The occurrence of NRL suppressed water adsorption capacity and delayed the biodegradability of the biopolymer films in the natural environment. Despite the depletion in water adsorption capacity, all of the product films degraded 50 % within 12 weeks. This study concluded that biopolymers with desirable properties could be formulated by choosing an appropriate casting ratio of the sago starch to NRL with suitable chemical substitution modes.     

Biodegradable kinetics of plastics under controlled composting conditions

This study models and evaluates the kinetics of C-CO₂ evolution during biodegradation of plastic materials including Polyethylene (PE), PE/starch blend (PE/starch), microcrystalline cellulose (MCE), and Polylactic acid (PLA). The aerobic biodegradation under controlled composting conditions was monitorated according to ISO 14855-1, 2004. The kinetics model was based on first order reaction in series with a flat lag phase. A non-linear regression technique was used to analyze the experimental data. SEM studies of the morphology of the samples before and after biodegradation testing were used to confirm the biodegradability of plastics and the accuracy of the model. The work showed that MCE and PLA produced the high amounts of C-CO₂ evolution, which gave readily hydrolysable carbon values of 55.49% and 40.17%, respectively with readily hydrolysis rates of 0.338 day⁻¹ and 0.025 day⁻¹, respectively. Whereas, a lower amount of C-CO₂ evolution was found in PE/starch, which had a high concentration of moderately hydrolysable carbon of 97.74% and a moderate hydrolysis rate of 0.00098 day⁻¹. The mineralization rate of PLA was 0.500 day⁻¹ as a lag phase was observed at the beginning of the biodegradability test. No lag phase was observed in the biodegradability testing of the PE/starch and MCE. The mineralization rates of the PE/starch and MCE were found to be 1.000 day⁻¹, and 1.234 day⁻¹, respectively. No C-CO₂ evolution was observed during biodegradability testing of PE, which was used for reference as a non-biodegradable plastics sample.     

Influence for Soil Environment by Continuing use of Biodegradable Plastic

The influence on soil environment by continuing use of the biodegradable plastic films (biodegradable mulching films) in farmland was investigated. The difference was not seen in the amount of soil bacteria between mulching film plowing sections and non-plowing sections. The total bacteria amount did not increase by the effect of plowing the biodegradable mulching film. Poly-(butylene succinate and adipate) (PBSA) and poly-(ε-caprolactone) (PCL) decomposing bacteria did not increase in PBSA and PCL mulching film plowing sections comparing polyethylene covering section (PE) and no-film section. Polylactic acid (PLA) decomposing bacteria were not detected in all sections. Total denaturing gradient gel electrophoresis (DGGE) band patterns did not show a clear transition of the bacterial community structure in both the cultivating and promoting sections. In usual usage condition of the biodegradable plastic films, it was hardly influence to the soil environment such as bacterial community structure in farmland.     

Degradation of Polyethylene Designed for Agricultural Purposes

For many years now, scientific articles have been published on the potential biodegradability of polyethylene. Polyethylene (PE) with peroxidant additives, in the form of agricultural films, is sold by various suppliers as biodegradable mulch. Even though, the photo-chemical and thermal degradation of these products under artificial laboratory conditions is highlighted, several extrapolation on the biodegradation and, moreover, on the neutral environmental impact of PE are made. In this study, three different commercial mulch films have been submitted to standardised biodegradation tests and the results are discussed. The first conclusions are that a very low degree of biodegradation of the commercial PE films is achieved from these tests and that crosslinked PE micro-fragments are found in soil after a very long period of time.     

Physical properties and biodegradability of blends containing poly(ε-caprolactone) and tropical starches

In order to assess feasibility of tropical starches (sago and cassava starches) as biodegradable plastic materials, blending with poly(-caprolactone) (PCL), a biodegradable polymer, was carried out. It was confirmed that the physical properties (tensile strength and elongation) of PCL/sago and PCL/cassava blends were similar to those of PCL/corn blend, suggesting that sago and cassava starches can also be blended with PCL for production of biodegradable plastic. However, the properties of all PCL/starch blends were still low compared with those of polyethylene. Enzymatic degradability evaluation showed that lipase degradation of PCL and-amylase degradation of starch increased as the starch content in the blend increased. Burial test of the blends for 1, 3, and 5 months was carried out and the rate of degradation of the PCL/sago blend was confirmed to be slower than those of PCL/corn and PCL/cassava blends. Observation of the film blends structure by scanning electron microscope revealed that the starch was dispersed in a PCL continuous phase. Furthermore, changes in the film surface before and after enyzme treatments were observed.     

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.     

Morphological characteristics of waste polyethylene/polypropylene plastics during pyrolysis and representative morphological signal characterizing pyrolysis stages

In this work, the morphological characteristics of waste polyethylene (PE)/polypropylene (PP) plastics during their pyrolysis process were investigated, and based on their basic image changing patterns representative morphological signals describing the pyrolysis stages were obtained. PE and PP granules and films were used as typical plastics for testing, and influence of impurities was also investigated. During pyrolysis experiments, photographs of the testing samples were taken sequentially with a high-speed infrared camera, and the quantitative parameters that describe the morphological characteristics of these photographs were explored using the “Image Pro Plus (v6.3)” digital image processing software. The experimental results showed that plastics pyrolysis involved four stages: melting, two stages of decomposition which are characterized with bubble formation caused by volatile evaporating, and ash deposition; and each stage was characterized with its own phase changing behaviors and morphological features. Two stages of decomposition are the key step of pyrolysis since they took up half or more of the reaction time; melting step consumed another half of reaction time in experiments when raw materials were heated up from ambient temperatures; and coke-like deposition appeared as a result of decomposition completion. Two morphological signals defined from digital image processing, namely, pixel area of the interested reaction region and bubble ratio (BR) caused by volatile evaporating were found to change regularly with pyrolysis stages. In particular, for all experimental scenarios with plastics films and granules, the BR curves always exhibited a slowly drop as melting started and then a sharp increase followed by a deep decrease corresponding to the first stage of intense decomposition, afterwards a second increase – drop section corresponding to the second stage of decomposition appeared. As ash deposition happened, the BR dropped to zero or very low values. When impurities were involved, the shape of BR curves showed that intense decomposition started earlier but morphological characteristics remained the same. In addition, compared to parameters such as pressure, the BR reflects reaction stages better and its change with pyrolysis process of PE/PP plastics with or without impurities was more intrinsically process correlated; therefore it can be adopted as a signal for pyrolysis process characterization, as well as offering guide to process improvement and reactor design.     

An accelerated laboratory study evaluating the disintegration rates of plastic films in simulated aquatic environments

Six plastic films were exposed to accelerated sunlight while in simulated aquatic environments to determine the effects of chemical composition and environment on the disintegration rates. An environment of UV light/no water was used as a control to determine if the microorganisms in the aquatic systems enhanced the breakdown of the plastic films. The disintegration rate of the plastics was determined by monitoring changes in selected physical properties. The plastics included two conventional plastics commonly used in packaging (LDPE and polystyrene) and four plastics enhanced to have more rapid breakdown in the environment (2% ECO, 10% ECO, PE with ketone graft, and PE with starch). The two ECO copolymers had a significantly faster loss of physical properties than the other plastics evaluated in this study. Degradation was influenced by environmental conditions. Those plastics that showed a change in physical properties had a greater change faster in the UV light/no water than in the environments where water was present. Plastics on the surface of the water showed a more rapid loss of properties than those samples partially or completely submerged. This can be attributed to decreased light intensity and the lack of heat buildup.     

Physical Properties of Chemically Modified Starch(RS4)/PVA Blend Films—Part 1

In this paper, we report on the physical properties of films that have been synthesized by using native corn starch (NS) and chemically modified starch (RS4). NS or RS4/PVA blend films were synthesized by using the mixing process and the casting method. Glycerol (GL), sorbitol (SO), and citric acid (CA) were used as additives. The chemically modified starch (RS4) was synthesized by using sodium trimetaphosphate (STMP) and sodium tripolyphosphate (STPP) as a crosslinker. Then, the RS4 thus synthesized was confirmed by using the pancreatin-gravimetric method, swelling power and an X-ray diffractometer (XRD). Tensile strength (TS), elongation (%E), swelling behavior (SB), and solubility (S) of the films were measured. The result of the measurements indicated the RS4-added film was better than the NS-added film. Especially, the RS4/PVA blend film with CA as an additive showed the physical properties superior to other films.     

Molecular Weight Changes and Polymeric Matrix Changes Correlated with the Formation of Degradation Products in Biodegraded Polyethylene

The molecular weight changes in abiotically and biotically degraded LDPE and LDPE modified with starch and/or prooxidant were compared with the formation of degradation products. The samples were thermooxidized for 6 days at 100°C to initiate degradation and then either inoculated with Arthobacter paraffineus or kept sterile. After 3.5 years homologous series of mono- and dicarboxylic acids and ketoacids were identified by GC-MS in abiotic samples, while complete disappearance of these acids was observed in biotic environments. The molecular weights of the biotically aged samples were slightly higher than the molecular weights of the corresponding abiotically aged samples, which is exemplified by the increase in from 5200 g/mol for a sterile sample with the highest amount of prooxidant to 6000 g/mol for the corresponding biodegraded sample. The higher molecular weight in the biotic environment is explained by the assimilation of carboxylic acids and low molecular weight polyethylene chains by microorganisms. Assimilation of the low molecular weight products is further confirmed by the absence of carboxylic acids in the biotic samples. Fewer carbonyls and more double bonds were seen by FTIR in the biodegraded samples, which is in agreement with the biodegradation mechanism of polyethylene.     

Biodegradation and Ecotoxicity of Polyethylene Films Containing Pro-Oxidant Additive

The worldwide accumulation of non-degradable plastic materials, such as plastic bags, is one of the most important environmental concerns nowadays. The use of degradable materials is an option to mitigate the environmental impact generated by the consumption of plastics. One of the technologies used for the manufacture and use of degradable plastics is the use of pro-degradant additives that are incorporated in conventional plastics to promote their degradation under certain conditions. The aim of this study is to evaluate the process of oxidation, biodegradation and potential ecotoxicity of polyethylene films containing an oxo-degradable additive, according to the standard ASTM D-6954. This method establishes a procedure in which the samples are subjected to consecutive steps of accelerated oxidation, biodegradation by composting and ecotoxicity assessment. Furthermore, the effect of the presence of printing ink in the polyethylene samples with oxo-degradable additive was evaluated, and the results were compared with those obtained for samples of conventional polyethylene and polylactic acid. After 180 days of laboratory controlled composting, the samples reached the following percentages of biodegradation: polylactic acid, 41 %; printed oxo-degradable polyethylene, 32.24 %; oxo-degradable polyethylene, 25.84 %; printed polyethylene, 18.23 % and polyethylene, 13.48 %. The cellulose sample used as a control was mineralized in 58.45 %. Ecotoxicity assessment showed that the products of biodegradation of the samples tested, did not generate a negative effect on germination or development of the vegetal species studied. Under proper waste management conditions, these plastics can be used as an option to decrease the environmental impact of plastic films.     

Processing and mechanical properties of biodegradable Poly(hydroxybutyrate-co-valerate)-starch compositions

Poly(hydroxybutyrate-co-valerate) (PHBV) is a completely biodegradable thermoplastic polyester produced by microbial fermentation. The current market price of PHBV is significantly higher than that of commodity plastics such as polyethylene and polystyrene. It is therefore desirable to develop low-cost PHBV based materials to improve market opportunities for PHBV. We have produced low-cost environmentally compatible materials by blending PHBV with granular starch and environmentally benign CaCO₃. Such materials can be used for specific applications where product biodegradability is a key factor and where certain mechanical properties can be compromised at the expense of lower cost. The inclusion of granular starch (25 wt%) and CaCO₃ (10 wt%) in a PHBV matrix (8% HV, 5% plasticizer) reduces the cost by approximately 40% and has a tensile strength of 16 MPa and flexural modulus of 2.0 Gpa, while the unfilled PHBV/plasticizer matrix has a tensile strength of 27 MPa and a flexural modulus of 1.6 GPa.Paper presented at the Bio/Environmentally Degradable Polymer Society—Third National Meeting, June 6–8, 1994, Boston, Massachusetts.The mention of firm names or trade products does not imply that they are endorsed or recommended by the U.S. Department of Agriculture over other firms or similar products not mentioned.     

Effect of the Incorporation of Lysozyme on the Properties of Jackfruit Starch Films

Jackfruit starch based biodegradable films containing lysozyme were characterized for their antimicrobial activity, thickness, solubility, water vapor permeability and mechanical properties. The biodegradable films had good appearance and antimicrobial activity against Micrococcus lysodeikticus. The thickness of the biodegradable films were not affected by the variation in pH, but the addition of lysozyme increased the thickness, the thickest films being those with the highest lysozyme concentrations. The variation in pH of the filmogenic solutions affected the solubility of the biodegradable films, water solubility being greatest at pH 7.0 and with the highest lysozyme concentration. The permeability of the biodegradable films was increased by incorporating lysozyme. The lysozyme concentration and pH variation caused changes in the mechanical properties. The addition of 8% lysozyme increased the tensile strength and Young’s modulus for all the pH values studied. With respect to the release of antimicrobial activity, the diffusion of lysozyme was shown to follow Fickian transport mechanism.