A carbon-13 method for evaluating degradation of starch-based polymers

A new method for evaluating biodegradability of starch-based and certain other polymer blends uses the pre- and postexposure stable carbon isotope composition of material coupled with weight loss data to determine which components have degraded. The naturally occurring stable isotope of carbon.¹³C, is enriched in corn starch (¹³C, approx. –11) compared to petroleum-derived synthetic polymers (¹³C, approx. –32). Results on starch-synthetic polymer blends indicate that the ¹³C signatures of these blends are near-linear mixtures of their component ¹³C. Values of a ¹³C for starch-synthetic polymer blends exposed to biologically active laboratory soil and artificial seawater conditions are depleted in¹³C compared to unexposed samples, suggesting loss of the starch component. Combined with weight loss data for the exposed samples, the ¹³C values are statistically consistent with models requiring loss of the soluble component glycerin, followed by loss of starch, then petrochemical polymer, or simultaneous loss of starch and petrochemical polymer. Replicate ¹³C analyses of starch-synthetic polymer blends increase the statistical power of this relatively inexpensive, accessible technique to discriminate between degrading components.     

Evaluation of the Biodegradability of Polyvinyl Alcohol/Starch Blends: A Methodological Comparison of Environmentally Friendly Materials

Polyvinyl alcohol (PVA) and starch are both biodegradable polymers. These two polymers can be prepared as biodegradable plastics that are emerging as one of the environmental friendly materials available now. In this study, after reacting with sodium trimetaphosphate (STMP), modified corn starch was blended with PVA in different ratios by a barbender. Test samples were prepared for mechanical and thermal properties measurements. The surface roughness and morphology of fractured surface of the samples were observed by an atomic force microscopy (AFM) and scanning electron microscope (SEM) measurements. Aqueous degradation by enzyme, water absorption and biodegradability behavior were evaluated for the degradability. The biodegradability of these materials was followed by bio-reactivity kinetics models. Results showed that the addition of modified starch could enhance its water uptake. With an addition of 20 wt% of modified starch, the blend had a maximum weight loss during enzymatic degradation. It was found that the degradability was enhanced with the addition of the starch. Analyzing the results of the biodegradability based on the kinetic models, the growth rate of the microorganism was found to be increasing with the increase of the content of starch in the PVA/starch blends in the first order reaction fashion. In our biodegradability analysis, i.e., based on the China national standards (CNS) 14432 regulations, we estimated the decomposition behavior based on the mentioned first order reaction. We found that the PVA/starch blends would take 32.47, 16.20 and 12.47 years to degrade by 70% as their starch content 0, 20 and 40 wt%, respectively.     

Enzymatic Degradation of Cellulose-Based Materials

The biodegradability of cellulose-based materials was compared in the standard Sturm test and by enzymatic hydrolysis. Trichoderma reesei culture filtrate, the purified enzymes endoglucanase I and II from T. reesei, and -glucosidase from Aspergillus niger were used in the experiments. The unpurified Trichoderma reesei culture filtrate was found to contain a mixture of enzymes suitable for cellulose degradation. However, when purified enzymes were used the right balance of the individual enzymes was necessary. The addition of -glucosidase enhanced the enzymatic hydrolysis of cellulose materials when both culture filtrate and purified enzymes were used. In the Sturm test the biodegradability of most of the cellulose materials exceeded 70% carbon dioxide generation, but, in contrast, the biodegradability of the highly substituted aminated cellulose and cellulose acetate was below 10%. The results concerning enzymatic hydrolysis and biodegradability were in good agreement for kraft paper, sausage casing, aminated cellulose, and cellulose acetate. However, diverging results were obtained with cotton fabric, probably as a result of its high crystallinity.     

Biodegradability of Thermally Aged PHB,PHB-V,and PCL in Soil Compostage

The biodegradability of poly--hydroxybutyrate (PHB), poly--hydroxybutyrate-co-valerate (PHB-V) and poly--caprolactone (PCL) were examined following thermal aging in an oven for 192, 425 and 600 h. Different temperatures, 100, 120 and 140°C for PHB and PHB-V and 30, 40 and 50^oC for PCL were used to assess the influence of this parameter on biodegradation. The biodegradability tests were done in soil compostage at pH 11.0 and involved measuring the residual mass of polymer. Thermal analysis of the polymers was done using a differential scanning calorimeter (DSC). The melting temperature and crystallinity were also determined. Thermal ageing increased the biodegradability only for PHB at 120 and 140^oC, and there was no correlation between crystallinity and the biodegradation of the polymers.     

Humidity- and Age-Tolerant Starch-Based Sponge for Loose-Fill Packaging

Loose-fill packaging sponges were extruded from mixtures of 54–62% hydroxypropylated (HP 5%) amylomaize V (50% amylose) and wheat starches, 17–24% synthetic polymer, 13% water, 7% blowing agent(s), and 0.5% nucleating agent. One product made from 28% HP wheat starch, 28% HP amylomaize V starch, 12% ethylene vinyl alcohol (EVOH) copolymer, 8% polystyrene (PS), and 3% polystyrene maleic anhydride (PSMA) copolymer, plus the other raw materials, had a compressibility and resilience that matched those of expanded polystyrene (EPS), although its bulk density was four times higher. The starchy sponge showed 16% shrinkage in volume at 90% relative humidity and was 2% soluble in excess water, both at 25°C. After aging for 18 months near 25°C, the HP starchy sponge gave only a trace of fines in a simulated shipping test, compared to 20% fines from a biodegradable, starch-based, loose-fill sponge of commerce.     

Biodegradation of starch-poly(β-hydroxybutyrate-co-valerate) composites in municipal activated sludge

Injection-molded composites were prepared by blending PHBV⁵ with native cornstarch (30% and 50%) and with cornstarch precoated with PEO as a binding agent. These composites were evaluated for their biodegradability in municipal activated sludge by measuring changes in their physical and chemical properties over a period of 35 days. All composites lost weight, ranging from 45 to 78% within 35 days. Interestingly, the extent and rate of weight loss were quite similar in PHBV composites with no starch, with 30% starch, and with 50% starch. Weight loss was slowest in PHBV blends prepared with PEO-coated starch. For all samples, the weight loss was accompanied by a rapid deterioration in tensile strength and percentage elongation. The deterioration of these mechanical properties exhibited a relative rate of PHBV>starch-PHBV>PEO-coated starch-PHBV. Changes in starch/PHBV composition after biodegradation were quantified by FTIR spectroscopy. Increasing the starch content resulted in more extensive starch degradation, while the PHBV content in the blends became less susceptible to hydrolytic enzymes.The mention of firms names or trade products does not imply that they are endorsed or recommended by the U.S. Department of Agriculture over firms or similar products not mentioned. All programs and services of the U.S. Department of Agriculture are offered on a nondiscriminatory basis without regard to race, color, national origin, religion, sex, marital status, or handicap.     

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.     

Synthesis and biodegradation of poly(γ-butyrolactone-co-l-lactide)

Biodegradable polyesters were synthesized by ring-opening copolymerization of -butyrolactone (BL) and its derivatives withl-lactide (LLA). Although tetraphenyl tin was the main catalyst used, other organometallic catalysts were used as well.¹H and¹³C NMR spectra showed that poly(BL-co-LLA)s were statistical and that their number-average molecular weights were as high as 7×10⁴. The maximum BL content obtained from copolymerization BL/LLA was around 17%. TheT _m andT _g values of the copolymers showed a gradual depression with an increase in BL content. NoT _m was obtained for the copolymers containing more than 13 mol% BL. The biodegradability of the copolyesters was evaluated by enzymatic hydrolysis and nonenzymatic hydrolysis tests. The enzymatic hydrolysis was carried out at 37°C for 24 h using lipases fromRhizopus arrhizus andR. delemar. Hydrolyses by both lipases showed that an increase in BL content of the copolymer resulted in enhanced biodegradability. Nonenzymatic accelerated hydrolysis of copolymers at 70°C was found to increase proportionally to their exposure time. The hydrolysis rate of these copolymers was considerably faster than that of PLLA. The higher hydrolyzability was recorded for the BL-rich copolymers. The copolymerization of -methyl--butyrolactone (MBL) or -ethyl--butyrolactone (EBL) with LLA resulted in relatively LA-rich copolymers.     

Biodegradation of Injection Molded Starch-Poly (3-hydroxybutyrate-co-3-hydroxyvalerate) Blends in a Natural Compost Environment

Injection molded specimens were prepared by blending poly (hydroxybutyrate-co-valerate) (PHBV) with cornstarch. Blended formulations incorporated 30% or 50% starch in the presence or absence of poly-(ethylene oxide) (PEO), which enhances the adherence of starch granules to PHBV. These formulations were evaluated for their biodegradability in natural compost by measuring changes in physical and chemical properties over a period of 125 days. The degradation of plastic material, as evidenced by weight loss and deterioration in tensile properties, correlated with the amount of starch present in the blends (neat PHBV < 30% starch < 50% starch). Incorporation of PEO into starch-PHBV blends had little or no effect on the rate of weight loss. Starch in blends degraded faster than PHBV and it accelerated PHBV degradation. Also, PHBV did not retard starch degradation. After 125 days of exposure to compost, neat PHBV lost 7% of its weight (0.056% weight loss/day), while the PHBV component of a 50% starch blend lost 41% of its weight (0.328% weight loss/day). PHB and PHV moieties within the copolymer degraded at similar rates, regardless of the presence of starch, as determined by ¹H-NMR spectroscopy. GPC analyses revealed that, while the number average molecular weight (Mn) of PHBV in all exposed samples decreased, there was no significant difference in this decrease between neat PHBV as opposed to PHBV blended with starch. SEM showed homogeneously distributed starch granules embedded in a PHBV matrix, typical of a filler material. Starch granules were rapidly depleted during exposure to compost, increasing the surface area of the PHBV matrix.     

Electrical resistance characteristics of starch foams

The insulative character of expanded polystyrene loose-fill packing material supports the immobile triboelectric charge on its surface, causing static cling. One beneficial property of starch-based loose-fill is its antistatic behavior, which prevents the buildup of electrostatic charges on the foam surface, resulting in no static cling. This investigation explores the electrical resistance characteristics of plasticized starch materials such as commercial loose-fill. Electrical resistance standards used in this study to measure surface resistance and static decay properties are ASTM D 257-78, EOS/ESD S-11, and EIA 541. Following these established testing protocols, the electrical resistance of starch-based and expanded polystyrene loose-fill is quantified. Surface resistivity, measured at 12% RH, of starch-based loose-fill products is less than 1.0×10¹² per square characteristic of inherently static dissipative materials.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 be suitable.Presented at the 1995 International Chemical Congress of Pacific Basin Societies, Symposium onEnvironmental Polymer Biodegradation, December 17–22, 1995, Honolulu, Hawaii, USA.     

Effect of the composting substrate on biodegradation of solid materials under controlled composting conditions

Biodegradability under composting conditions is assessed by test methods, such as ASTM D 5338-92, based on the measurement of CO₂ released by test materials when mixed with mature compost and maintained in a controlled composting environment. However, in real composting, biodegradation occurs in fresh waste. To clarify this point, the biodegradation of paper and of a starch-based biodegradable thermoplastic material, Mater-Bi ZI01U, was followed by measuring the weight loss of samples introduced either into a mature compost or into a synthetic waste. The weight loss in mature compost was higher at the beginning but tended to decrease; in synthetic waste a first lag phase was followed by an exponential phase. Complete degradation of paper was noticed simultaneously in the two substrates (after 25 days). The bulkier Mater-Bi samples were fully degraded after 20 days in fresh waste, but after 45 days in mature compost. Therefore, the test methods using mature compost as a substrate can possibly underestimate the biodegradation rate occurring in fresh waste, i.e., in real composting plants, and have to be considered as conservative test methods. The test procedure described in this paper seems very suitable as a screening method to verify the compostability of plastic materials in a composting environment.     

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.     

Photo-/Bio-degradability of Agro Waste and Ethylene–Propylene Copolymers Composites Under Abiotic and Biotic Environments

Composites were prepared by two methods, (i) graft copolymerization (GFC) of isotactic polypropylene (PP) with maliec anhydride, (MAH) followed by esterification with coir fiber and (ii) by direct reactive mixing (DFC) of polypropylene (PP) and ethylene–propylene (EP) copolymers with MAH and peroxide with coir fiber. These composites, after molding in films (5×5 cm, m thickness) were examined for susceptibility to biological attack by measuring the percentage weight loss in compost upto 6 months, periodically, and fungal colonization on surface of the samples, when kept as sole carbon source for the growth of Aspergillus niger in culture medium upto 40 days. Photodegradation was evaluated by monitoring the variations in FT-IR spectrum and crack formation after successive treatment with UV light (≥290 nm) for 0, 20, 50 and 100 h at 60°C in the presence of air. Specimens of virgin PP were taken as a reference during all period of photo and biodegradation studies. Significant changes were observed depending on the preparation methods during photodegradation and biodisintegration of composites. DFCs samples were disintegrated faster than GFCs during the composting whereas, in culture, GFCs were covered highly in well uniform way by fungi. It was observed that photo-oxidative ageing directly enhanced the biodegradability of composites as the increase in fungal growth rate and decrease in weight during composting were found. It was concluded that extent of compatibilization had a profound effect on photo-oxidation and biodisintegration of composite material; consequently ester bonds were main units during fungal consumption. Composition of monomers in copolymers was also showing significant effect on the degradability which decreased with increasing content of ethylene in ethylene–propylene (EP) copolymers.     

Degradation of poly(β-hydroxyalkanoates) and polyolefin blends in a municipal wastewater treatment facility

Six types of plastics and plastic blends, the latter composed at least partially of biodegradable material, were exposed to aerobically treated wastewater (activated sludge) to ascertain their biodegradability. In one study, duplicate samples of 6% starch in polypropylene, 12% starch in linear low-density polyethylene, 30% polycaprolactone in linear low-density polyethylene, and poly(-hydroxybutyrate-co-hydroxyvalerate) (PHB/V), a microbially produced polyester, were exposed to activated sludge for 5 months, and changes in mass, molecular weight average, and tensile properties were measured. None of the blended material showed any sign of degradation. PHB/V, however, showed a considerable loss of mass and a significant loss of tensile strength. In a second study, PHB/V degraded rapidly, but another type of microbial polymer which forms a thermoplastic elastomer, poly(-hydroxyoctanoate), did not degrade. These results illustrate the potential for disposal and degradation of PHB/V in municipal wastewater.     

New biodegradable polyester-copolymers from commodity chemicals with favorable use properties

Copolyesters composed of aliphatic and aromatic compounds were synthesized by the polycondensation of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, sebacic acid, adipic acid, and terephthalic acid. By applying an appropriate ratio of aliphatic to aromatic acids, the synthesized materials proved to be biodegradable, as was verified by several degradation test methods such as aqueous polymer suspension inoculated by a soil eluate (Sturm test), a soil burial test (at ambient temperature), and a composting simulation test at 60°C. The degradability of the polyester-copolymers (measured as weight loss) was investigated with respect to the aliphatic monomer components and the fraction of terephthalic acid. Excellent biodegradability was observed even for copolymers with a content of terephthalic acid up to 56 mol% (of the acid fraction) and melting points in the range up to 140°C. Degradation by chemical hydrolysis of the polyesters was determined independently and was found to facilitate microbial attack significantly only at higher temperatures. The findings demonstrate that biodegradable polymers with advantageous usage properties can easily be manufactured by conventional techniques from commodity chemicals (adipic acid, terephthalic acid, and ethylene glycol or 1,4-butanediol).Dedicated to Prof. J. Klein's 60th birthday.     

Physical state and biodegradation behavior of starch-polycaprolactone systems

The biodegradation behavior of insoluble crystalline polymers depends on both chemical structure and physical state. The physical state is strongly affected by the molding conditions; moreover the presence of natural hydrophylic substances such as starch can further influence the biodegradation process. This paper examines the biotic and abiotic degradation of thick injection-molded parts, made of pure poly--caprolactone (PCL) at different molecular weights, and of PCL in the presence of starch in the case of a commercial grade of Mater-Bi, produced by Novamont. The abiotic degradation was studied at 25 and 50°C, whereas the biotic degradation was followed in conditions of SCAS (semicontinuous activated sludges) at 25 and 50°C, soil burial, and controlled composting. The physical-chemical modifications provoked at the surface and in the bulk of the samples by the different types of degradation were determined by differential scanning calorimetry, viscometric and gravimetric analysis, scanning electron microscopy, and dynamic mechanical analysis. The mechanical modifications induced by the different environments were followed by tensile tests. It was demonstrated that the presence of starch significantly increases the apparent biodegradation rate of PCL, making even thick parts of ZI01U compatible with the composting process.Paper presented at the Bio/Environmentally Degradable Polymer Society—Third National Meeting, June 6–8, 1994, Boston, Massachusetts.     

Thermal Properties and Biodegradability Studies of Poly(3-hydroxybutyrate-co-3-hydroxyvalerate)

For investigating the relationship between thermal properties and biodegradability of poly (3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), several films of PHBV containing different polyhydroxyvalerate (HV) fractions were subjected to degradation in different conditions for up to 49 days. Differential scanning calorimetry (DSC), thermogravimetry (TG), specimen weight loss and scanning electron microscopy (SEM) were performed to characterize the thermal properties and enzymatic biodegradability of PHBV. The experimental results suggest that the degradation rates of PHBV films increase with decreasing crystallinity; the degradability of PHBV occurring from the surface is very significant under enzymatic hydrolysis; the crystallinity of PHBV decreased with the increase of HV fraction in PHBV; and no decrease in molecular weight was observed in the partially-degraded polymer.     

Crystallization behavior of predominantly syndiotactic poly(β-hydroxybutyrate)

Predominantly syndiotactic poly(-hydroxybutyrate), syn-PHB, of variable syndioregularity (syndyad fractions 0.59, 0.62, 0.64, and 0.71) and molecular weight was prepared by the dibutyltin dimethoxide catalyzed ring opening of racemic-butyrolactone (BL). The crystallization behavior of the syn-PHB polymers was investigated by DSC and X-ray diffraction analyses. DSC of films after melting and annealing showed at least one, and often two distinct melting transitions occuring over a broad (often 40°C) temperature range. These results indicate that syn-PHB chain segments of variable syndioregularity form crystalline regions with very different thermodynamic stabilities. Maximum degrees of crystallinity for melt annealed 0.64- and 0.71-syn-PHB was observed at an annealing temperature (T _c ) of 30°C. AtT _c values at 45°C and higher, crystallization of relatively lower syndioregular chain segments was apparently excluded to variable degrees dependent onT _c and sample syndiotactic dyad content. After crystallization of syn-PHB samples at elevated temperatures, ambient temperature annealing resulted in an observed lower temperature melting transition at 50°C. This result showed little to no dependence on syn-PHB syndio-regularity andT _c . Both solution precipitated 0.62-syn-PHB and 0.71-syn-PHB have WAXS patterns with poorly resolved crystalline reflections superimposed on amorphous haloes indicating low levels of crystallinity (17% and 25%, respectively) and poorly formed crystals. Isothermal crystallization monitored by DSC showed that the syn- and natural origin PHB showed fastest crystallization rates at temperatures between 50°C and 70°C and 60°C and 90°C, respectively. From the dependence of the higher melting transition onT _c it was determined that the equilibrium melting temperatures for 0.62-syn-PHB (M _n =83,700 g/mol) and a 0.64-syn-PHB (M _n =11,900 g/mol) were 157 and 154°C, respectively. An Avrami analysis of syn-PHB yielded results similar to that found for natural origin PHB indicating that crystal growth occurs by a two-dimensional mechanism.Guest Editor: Dr. Graham Swift, Rohm & Haas.     

Evaluation of the biodegradability of copolyesters containing aromatic compounds by investigations of model oligomers

Model oligo esters of terephthalic acid with 1,2-ethanediol, 1,3-propanediol, and 1,4-butanediol have been investigated with regard to their biodegradability in different biological environments. Well-characterized oligomers with weight-average molar masses of from 600 to 2600 g/mol exhibit biodegradation in aqueous systems, soil, and compost at 60°C. SEC investigations showed a fast biological degradation of the oligomer fraction consisting of 1 or 2 repeating units, independent of the diol component used for polycondensation, while polyester oligomers with degrees of polymerization higher than 2 were stable against microbial attack at room temperature in a time frame of 2 months. At 60°C in a compost environment chemical hydrolysis also degrades chains longer than two repeating units, resulting in enhanced degradability of the oligomers. Metabolization of the monomers and the dimers as well by the microorganisms could be confirmed by comparing SEC measurements and carbon balances in a Sturm test experiment. Based on these results degradation characteristics of potential oligomer intermediates resulting from a primary chain scission from copolyesters consisting of aromatic and aliphatic dicarbonic acids can be predicted depending on their composition. These results will have an evident influence on the evaluation of the biodegradability of commercially interesting copolyesters and lead to new ways of tailor-made designing of new biodegradable materials as well.     

Pure-culture and enzymatic assay for starch-polyethylene degradable plastic biodegradation withStreptomyces species

Eleven starch-polyethylene degradable plastic films were prepared from masterbatches from Archer Daniels Midland Inc. (ADM), EcoStar Inc. (SLS), and Fully Compounded Plastic Inc. The biodegradability of initial and 70°C heat-treated materials was determined using a pure-culture assay withStreptomyces badius 252,S. setonii 75Vi2, orS. viridosporus T7A or without bacterial culture (control). Films were treated with 10-foldS. setonii culture concentrates and compared with inactive enzyme controls. Changes in each films mechanical property, molecular weight distribution, and Fourier-transformed infrared spectrum (FT-IR) were determined, and results were evaluated for significant differences by analysis of variance. Cell mass accumulation on each film was quite pronounced. In pure-culture studies, biodegradation was demonstrated for ADM-7 and SLS-2 initial films and for ADM-6 heat-treated films, whereas after 3-week treatment with activeS. setonii culture concentrates (enzyme assay), reductions in mechanical properties and changes in FT-IR spectrum were illustrated by all the films except SLS-2. Thus the absence of biofilm formation on the film surface permitted enzymatic attack of the materials. Furthermore, inhibition of chemical oxidative degradation in the pure-culture assay was demonstrated for ADM-11, SLS-5, and SLS-10 initial materials and for ADM-4, ADM-7, SLS-8, and SLS-10 heat-treated films. These data suggest that biological and chemical degradation were directly affected by the reduction in oxygen tension on the plastic film surface due to cell mass accumulation. This same phenomenon could be the cause for slow degradation rates in nature.Journal Paper No. J-15061 of the Iowa Agriculture and Home Economics Experiment Station, Ames, Iowa. Project Nos. 0178 and 2889.