Structure-biodegradation relationships of polymeric materials. 1. Effect of degree of oxidation on biodegradability of carbohydrate polymers

The biodegradability of oxidized starch and inulin has been studied in relation to the degree of periodate oxidation to dialdehyde derivatives, by measuring oxygen consumption and mineralization to carbon dioxide. A higher degree of oxidation of dialdehyde starch and dialdchyde inulin results in a lower rate at which the polymers are biodegraded. It is demonstrated that the biodegradation rate of dialdehyde inulin derivatives decreases more than that of equivalent starch derivatives. The differences in biodegradation behavior between dialdehyde starch and dialdehyde inulin, resulting from comparable modifications, are discussed in terms of conformational structure.     

Storage stability of injection-molded starch-zein plastics under dry and humid conditions

Corn starch and zein mixtures (4 : 1 dry weight) were extruded and injection-molded in the presence of plasticizers (glycerol and water). Tensile strength and percentage elongation of the molded plastics were measured before and after 1 week of storage under a dry or humid condition (11 or 93% RH). With 10–12% glycerol and 6–8% water, injection-molded plastics had relatively good tensile properties (20- to 25-MPa tensile strength and 3.5–4.7% elongation). But while exposed to dry conditions (11% RH), the molded plastics lost weight (0.5–1.5% in 7 days) and became very brittle, with significant decreases in tensile strength and elongation. Partial replacement (5–10%) of starch with a maltodextrin (average DE 5) reduced the glass transition and melting temperatures of the starch-zein mixture as well as the dry storage stability. Using potato starch instead of corn starch significantly improved the dry storage stability of the injection-molded starch-zein plastics (18- vs 11-MPa tensile strength). Anionic corn starches with a maleate or succinate group (DS<0.01) produced injection-molded plastics with improved tensile properties and storage stability. Plastics prepared from the starch maleate and zein mixture retained the strength during 1 week of dry storage without a significant change (26-MPa tensile strength and 3.7% elongation after 1 week of storage).Paper presented at the Bio/Environmentally Degradable Polymer Society—Second National Meeting, August 19–21, 1993, Chicago, Illinois.Journal paper No. J-15561 of the Iowa Agriculture and Home Economics Experiment Station, Ames, Iowa, Project No. 2863.     

Biodegradation of Coproducts from Industrially Processed Corn in a Compost Environment

Information pertaining to biodegradability of renewable polymeric material is critical for the design and development of single-use biodegradable consumer products. The rate and extent of biodegradation of corn fiber, corn zein, cornstarch, distillers grain, and corn gluten meal were evaluated in compost environments under variable temperature, pH, and moisture conditions. Generally, composts with higher temperature (40°C), neutral pH (7.0), and 50%–60% moisture appeared to be ideal for corn coproduct biodegradation, particularly for corn gluten meal and corn zein. Low moisture conditions slowed biodegradation considerably, but degradation rates improved when moisture content increased up to 60%. Thereafter, increased moisture particularly slowed the degradation of corn gluten meal and corn zein, whereas cornstarch degradation remained unaffected. At low pH (4.0) and high pH (11.0) the rate of degradation of most coproducts was slowed somewhat. Cornstarch degradation was slower at pH 7.0, but degradation improved with increased temperatures. Increase in compost temperature from 25 to 40°C (in 5°C increments) also improved biodegradation of corn fiber and distillers grain. Addition of 1% urea to compost as a nitrogen source decreased the extent of biodegradation nearly 40% for corn gluten meal and corn zein, and 20% for cornstarch samples. Treatment of compost with 0.02% azide inhibited biodegradation of all coproducts, suggesting that the presence of metabolically active microbial cells is required for effective degradation of biobased materials in a compost environment.     

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).     

Photodegradation and Biodegradation Study of a Starch and Poly(Lactic Acid) Coextruded Material

To simulate the behavior of agricultural mulch coextruded poly(lactic acid)(PLA)/starch films, two stages were carried out. The first was an ultraviolet treatment (UV) at 315 nm, during which glass transition temperature T_g, weight, and molecular weight (MW) decreased and a separation between PLA and starch phase was observed. For the second stage, the mineralization of the carbon of the material was followed using the ASTM (D 5209–92 and 5338–92) and ISO/CEN (14852 and 14855) standard procedures. To measure the biodegradability of polymer material, the assessment of the carbon balance allowed determination of the distribution between the carbon rate used to the biomass synthesis or the respiration process (released CO₂), as well as the dissolved organic carbon into the culture medium and the carbon in the residual insoluble material. The influence of the nature of the medium and the standardized procedures on the final rate of biodegradation was investigated. Whatever the standardized method, the biodegradation percentage was significantly stronger in liquid medium (92.4–93.4) than on inert medium (80–83%). In the case of the compost process, only released CO₂ was measured and corresponded to 79.1–80.3%.     

Microbial biomass yield and turnover in soil biodegradation tests: carbon substrate effects

Most of the standardized biodegradation tests used to assess the ultimate biodegradation of environmentally degradable polymers are based solely on the determination of net evolved carbon dioxide. However, under aerobic conditions, it has to be considered that heterotrophic microbial consortia metabolize carbon substrates both to carbon dioxide and in the production of new cell biomass. It is generally accepted that in the relatively short term, 50% of the carbon content of most organic substrates is converted to CO₂, with the remaining carbon being assimilated as biomass or incorporated into humus. The latter is particularly important when the metabolism of the organic matter occurs in a soil environment. A straightforward relationship between the free-energy content of a carbon substrate (expressed as the standard free-energy of combustion) and its propensity for conversion to new microbial biomass rather than mineralization to CO₂ has been established. This can potentially lead to underestimation of biodegradation levels of test compounds, especially when they consist of carbon in a fairly low formal oxidation state and relatively high free-energy content. In the present work, the metabolism of different kind of carbon substrates, especially in soil, is reviewed and compared with our own experimental results from respirometric tests. The results show that conversion of highly oxidized materials, such as the commonly used reference materials, cellulose or starch, to CO₂ may be significantly overestimated. The addition of glucosidic material to soil leads to greatly increased respiration and is accompanied by a very low conversion to biomass or humic substances. In contrast, relatively less oxidized substrates metabolize more slowly to give both CO₂ and biomass to an extent which may be significantly underestimated if glucosidic materials are used as the reference. The need for an overall carbon balance taking into account both the carbon immobilized as biomass and that volatized as CO₂ must be considered in standard respirometric procedures for assessing the biodegradability of slowly degrading macromolecules.     

Evaluation of the Biodegradation of Starch and Cellulose Under Controlled Composting Conditions

In order to verify the response of the controlled composting test method (i.e., the ISO/DIS 14855:1997, the ASTM D 5338-92, or the CEN counterpart) to starch at different concentrations, the maximum amount prescribed by the test method (100 g) and lower amounts (60 and 30 g), as if starch were a coingredient in a blend, were tested. After 44 days of incubation (at a constant temperature of 58°C) the biodegradation curves were in a plateau phase, displaying the following final values (referred to a nominal starch initial amount of 100 g): starch 100 g, 97.5%; starch 60 g, 63.7%; and starch 30 g, 32.5%. The data show a CO₂ evolution roughly equal, in each case, to the theoretical maximum, indicating a complete starch mineralization. We cannot discern whether the deviations found at lower concentrations are caused by a priming effect. In any case, the extent of the deviations is not high and is acceptable in biodegradation studies. The average biodegradation of cellulose, obtained gathering four independent experiments with 11 biodegradation curves, turned out to be 96.8 ± 6.7% (SD) after 47 ± 1 days. The data indicate that the controlled composting is a reliable test method also for starch and cellulose and, consequently, for starch-based and cellulose-based materials.     

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.     

Increased biodegradation of a low-density polyethylene (LDPE) matrix in starch-filled LDPE materials

Preheated¹⁴C-labeled LDPE-films with 15% corn starch and a proxidant formulation [masterbatch (MB)] incubated in aqueous solutions with fungi at ambient temperature are about three times more susceptible to biodegradation than the corresponding preheated pure LDPE as observed by liquid scintillation counting (LSC). The inbuilt induction time before autoxidation commences can be shortened by initial heating. Preheated LDPE-MB materials biodegrade about five times faster than nonheated ones. After 1 year of biodegradation of nonheated LDPE-MB, sporadic increases in the evolution of¹⁴CO₂ have been noted, showing that the induction time may be running toward and end.     

Aging properties of extruded high-amylose starch

The structural and mechanical properties of extruded high-amylose and normal cornstarch were studied as a function of time and humidity to determine the suitability of high-amylose cornstarch for use in biodegradable plastic materials. After extrusion at 170°C and 20–30% moisture, high-amylose starch was mostly amorphous, with small amounts of V- and A-type crystal structures. Tensile strengths for the extruded high-amylose starch ribbons were rather stable with time (65, 50, and 35 MPa at 20, 50, and 80% RH) and were higher than those for normal cornstarch (25, 40, and 15 MPa after 84 days at 20, 50, and 80% RH). Elongations at break declined gradually with time for high-amylose starch (6, 11, and 11% after 84 days at 20, 50, and 80% RH), while rapid declines were seen for normal cornstarch at higher humidities (3, 9, and 3% after 84 days at 20, 50, and 80% RH). Differential scanning calorimetry revealed that normal cornstarch aged at a high humidity had much larger sub-T _g endotherms than high-amylose cornstarch. These endotherms reflect decreases in enthalpy and free volume which occur in amorphous polymers due to structural relaxation. It appears, therefore, that plastic materials prepared from gelatinized or melted high-amylose cornstarch should have greater strength and flexibility and slower physical aging than those prepared from gelatinized normal cornstarch.Paper presented at the Bio/Environmentally Degradable Polymer Society—Second National Meeting, August 19–21, 1993, Chicago, Illinois.Product names are necessary to report factually on available data; however, the USDA neither guarantees nor warrants the standard of the product, and the use of the name by the USDA implies no approval of the product to the exclusion of others that may also be suitable.     

Biodegradation of Compostable Plastics in Green Yard-Waste Compost Environment

Compostable plastic materials, produced from polylactic acid (PLA), corn starch, or sugarcane, degraded in a green yard-waste compost environment. The compostable plastics claim to meet ASTM D6400 standards for biodegradation, sustainable plant growth, and eco-toxicity. Biodegradation was measured by disintegration studies over 20 weeks. The commercially available compostable products, made from PLA, sugarcane, or corn starch, biodegraded while in a commercial compost facility with other common yard waste compostable items. The PLA container, cup, and knife completely degraded in 7 weeks at a rate similar to the Avicell micro-cellulose control. The corn starch-based trash bag and sugarcane plate degraded at a similar rate as the Kraft paper control. The three materials degraded between 80% and 90% after 20 weeks.     

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.     

Biodegradable Corn Starch Loose-Fill. II. The Effect of Storage at Different Relative Humidities on the Physical Properties of Loose-Fill

The physical properties of corn starch loose-fill were examined at various relative humidities (r.h.). After 48 h of storage at both 25 and 50% r.h., only a slight change in the dimension and physical properties of the corn starch loose-fill was apparent. A wet environment (75% r.h. for 48 h), however, caused significant shrinkage and the loss of physical properties. The tensile properties, particularly tensile modulus, sharply increased, while the resilience gradually decreased with storage time. Amorphous X-ray diffraction patterns of corn starch loose-fills were transformed into crystalline patterns due to aging at 75% r.h. after 48 h. These changes were attributed to the structural relaxation, which was accelerated by moisture gain. The T _g of corn starch loose-fill decreased with increasing the moisture content in expanded starch. Our proposed model based on Avrami equation was able to describe the time-dependent recrystallization of corn starch by modifying the time-dependent tensile modulus. The growth parameter (n) and time constant (k) for the recrystallization process of corn starch loose-fill were about 3.2 and 8.87 × 10^–18 s^–1, respectively. If the growth parameter of 3.2 is considered, spherulitic growth of crystallization occurred in the corn starch loose-fill in the wet environment.     

Biodegradable packing materials from hydrolysates of collagen waste proteins

Enzymatic hydrolysates of waste collagen proteins (H), from current industrial manufacture (leather, edible meat product casings, etc.) of mean molecular mass 20-30 kDa by a reaction with dialdehyde starch (DAS), produces hydrogels applicable as biodegradable (or even edible) packaging materials for food, cosmetic and pharmaceutical products. Thermo-reversibility of prepared hydrogels is given by concentrations of H and DAS in a reaction mixture. At concentrations of H 25-30% (w/w) and that of DAS 15-20% (related to weight of hydrolysate), thermo-reversible hydrogels arise, which can be processed into packaging materials by a technique similar to that of soft gelatin capsules (SGC). Exceeding the limit of 20% DAS leads to hydrogels that are thermo-reversible only in part, a further increase in DAS concentration then leads to thermo-irreversible gels whose processing into biodegradable packaging materials necessitates employment of other procedures.     

A New Test Method for Determining Biodegradation of Plastic Material Under Controlled Aerobic Conditions in a Soil-Simulation Solid Environment

A new test method is described for assessing biodegradation of plastic material under simulated soil conditions. An inert substrate can be activated with soil extract and nutrient and used in place of soil in biodegradation tests. The biodegradation level is evaluated by determining the carbon dioxide (CO₂) production released by the test reactors. Effects of substrate nature, solution pH, nutrient composition, soil extract concentration, and activation duration on CO₂ production were investigated, and the experimental conditions were optimized. Results obtained with cellulose showed a biodegradation rate of 80% within 28 days. Moreover, with this kind of substrate, reaction products and residues can be easily extracted and analysed.     

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.     

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

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

不同碳源对微生物修复石油污染土壤的促进作用

为解决石油污染土壤中以石油为唯一碳源的土著微生物生长缓慢的问题,研究了分别添加玉米淀粉、玉米粉、可溶性淀粉和葡萄糖4种碳源对土样细菌总量和石油烃降解率的影响。研究结果表明：玉米淀粉作为碳源时土样TN和TP的下降幅度均最大;添加玉米淀粉和玉米粉比添加可溶性淀粉和葡萄糖更有利于细菌的生长繁殖;细菌对直链烷烃化合物均具有较好的降解效果,但对较为复杂的芳香烃化合物降解效果较差。降解反应第40天时,分别添加玉米淀粉、玉米粉、可溶性淀粉和葡萄糖的石油烃降解率分别为67.25%、48.60%、46.30%和28.57%。     

Biodegradation by Composting of Surface Modified Starch and PVA Blended Films

Several starch/PVA/glycerol polymer blends were prepared by a solution casting technique and examined for biodegradation by composting over 45 days. Within this time frame, the starch and glycerol components were fully degraded, leaving the PVA component essentially intact. The lowest PVA content film (20%) was selected as a polymer with enough PVA to impart important physical characteristics, but also enough starch to be considered biodegradable. The film characteristics were further improved by surface modification with chitosan. This modification did not interfere with the biodegradation of the starch component. Furthermore, there was slight evidence that PVA biodegradation had been initiated in composted, surface modified starch/PVA blends.     

Progress in the genetic manipulation of crops aimed at changing starch structure and increasing starch accumulation

The starch content and its composition have important consequences for the yield of the harvested crop and the materials extracted from it. The functional properties of the foods or other processed materials derived from these crops are also affected by the structure and composition of the starch. Recently, genetic engineering has been used to produce plants with an elevated starch content, achieved by transforming the plant with a mutated bacterial gene coding for an ADPglucose pyrophosphorylase that is active in the presence of metabolites which inhibit the plant enzyme. Besides the practical implications of these results, this experiment provided direct evidence for the regulatory role of the ADPglucose pyrophosphorylase in starch synthesis. Other bacterial enzymes, such as glycogen synthase and branching enzyme, could be introduced in order to modify starch structure. However, a more elegant (but longer-term) approach would be to learn enough about the structure-function relationships of the plant enzymes so that the product of their action could be changed. To achieve this objective, much more will have to be learned about the enzymes involved in the biosynthesis of starch than is presently known. Here, the basic properties of starch and the current research approaches to understanding its biosynthesis are described, together with a perspective of how genetic manipulation of starch structure may be achieved.Paper presented at the Bio/Environmentally Degradable Polymer Society—Third National Meeting, June 6–8, 1994, Boston, Massachusetts.