Preparation and Biodegradation of Starch/Polycaprolactone Films

Starch granules were modified with trisodium trimetaphosphate (TSTP) and characterized by P³¹-NMR, FTIR and DSC. Seventy-micron films were prepared from modified starch and polycaprolactone blends by solvent casting technique. Three different types of films—PCL (100% polycaprolactone), MOD-ST/PCL (50% modified starch and 50% polycaprolactone blend) and NONMOD-ST/PCL (50% nonmodified starch and 50% polycaprolactone blends)—were prepared, and their thermal, mechanical, and morphologic properties were investigated to show the increased performance of PCL with the addition of starch and also the effect of modification. It was observed that with the addition of starch the Young's modulus of polycaprolactone was increased and became less ductile, whereas tensile strength and elongation at break values decreased. Biodegradation of these films was inspected under different aerobic environments with the presence of Pseudomonas putida, activated sludge, and compost. It was observed that whereas P. putida had almost no effect on degradation during 90 days, with the presence of activated sludge, considerable deformation of films was observed even in the first 7 days of degradation. In a compost environment, degradation was even faster, and all polymer films were broken into pieces within first 7 days of degradation and no film remained after 15 days.     

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.     

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.     

Environmental Degradation of Blends of Atactic Poly[(R,S)-3-hydroxybutyrate] with Natural PHBV in Baltic Sea Water and Compost with Activated Sludge

Degradation of atactic poly[(R,S)-3-hydroxybutyrate] (a-PHB) binary blends with natural poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV, 12 mol% of 3HV units), has been investigated and compared with plain PHBV in the compost containing activated sludge and under marine exposure conditions in the dynamic water of the Baltic Sea. Characteristic parameters of compost and the Baltic Sea water were monitored during the incubation period (6 weeks) and their influence on the degree of biodegradation is discussed. After specified degradation times of the experiments the weight loss of the samples, surface changes, changes in molecular weight and polydispersity as well as changes of the composition and thermo-mechanical properties of the blends have been evaluated. Macroscopic observations of the samples were accompanied by investigations using optical microscopy, size-exclusion chromatography (SEC), nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC) and tensile testing. The degree of degradation of blends of a-PHB with PHBV depends on the blend composition and environmental conditions. In both environments studied the weight loss of plain PHBV was more significant than changes the molecular weight. In both environments only enzymatic degradation of the blends, which proceeds via surface erosion mechanisms, was observed during the incubation period.     

Effect of environmental parameters on the degradability of polymer films in laboratory-scale composting reactors

Previous research in our laboratory reported a convenient laboratory-scale composting test method to study the weight loss of polymer films in aerobic thermophilic (53°C) reactors maintained at a 60% moisture content. The laboratory-scale compost reactors contained the following synthetic compost mixture (percentage on dry-weight basis): tree leaves (45.0), shredded paper (16.5), food (6.7), meat (5.8), cow manure (17.5), sawdust (1.9), aluminum and steel shavings (2.4), glass beads (1.3), urea (1.9), and a compost seed (1.0) which is designated Mix-1 in this work. To simplify the laboratory-scale compost weight loss test method and better understand how compost mixture compositions and environmental parameters affect the rate of plastic degradation, a systematic variation of the synthetic mixture composition as well as the moisture content was carried out. Cellulose acetate (CA) with a degree of substitution (DS) value of 1.7 and cellophane films were chosen as test polymer substrates for this work. The extent of CA DS-1.7 and cellophane weight loss as a function of the exposure time remained unchanged when the metal and glass components of the mixture were excluded in Mix-2. Further study showed that large variations in the mixture composition such as the replacement of tree leaves, food, meat, and sawdust with steam-exploded wood and alfalfa (forming Mix-C) could be made with little or no change in the time dependence of CA DS-1.7 film weight loss. In contrast, substituting tree leaves, food, meat, cow manure, and sawdust with steam-exploded wood in combination with either Rabbit Choice (Mix-D) or starch and urea (Mix-E) resulted in a significant time increase (from 7 to 12 days) for the complete disappearance of CA DS-1.7 films. Interestingly, in this work no direct correlation was observed between the C/N ratio (which ranged from 13.9 to 61.4) and the CA DS-1.7 film weight loss. Decreasing moisture contents of the compost Mix-2 from 60 and 50 and 40% resulted in dramatic changes in polymer degradation such that CA DS-1.7 showed an increase in the time period for a complete disappearance of polymer films from 6 to 16 and 30 days, respectively.Guest Editor: Dr. Graham Swift, Rohm & Haas.Paper presented at the Bio/Environmentally Degradable Polymer Society—Second National Meeting, August 19–21, 1993, Chicago, Illinois.     

Preparation and Characterization of Xylan Derivatives and Their Blends

Although hemicellulose is found widely in nature, it is currently under-utilized as a raw material for commercial applications. It would be desirable to find new uses for hemicellulose in order to add value to this agro-based material. A common type of hemicellulose is xylan, which is found in a number of wood species and in cotton. In this work we prepared cationic and anionic xylan derivatives and characterized them by ¹³C NMR, FT-IR, size exclusion chromatography (SEC), thermal analysis, and rheology. In particular, the ¹³C NMR spectra of carboxymethyl xylan (CMX) and quaternary ammonium-adducted xylan (QAX) were fully assigned with the help of samples with different degrees of substitution. SEC indicated that the beechwood xylan showed a bimodal molecular weight distribution, but with derivatization the distribution tended to become unimodal. Thermal analysis and rheology studies did not uncover any surprises; the solution of xylan and its derivatives exhibited mostly Newtonian behavior. The blends of CMX and QAX produced a precipitate at almost all ratios, indicating the formation of a polyelectrolyte complex. When cationic and anionic xylan samples were added together to paper, the paper dry strength increased. Thus, the combination of cationic/anionic xylan may be of interest in selected applications.     

Analysis of Biodegradability of Three Biodegradable Mulching Films

The development of biodegradable mulching films is a great direction for environment protecting and oil saving problems. In this paper, it was used three kinds of biodegradable mulching films named a, b and c (different ratio between modified starch and poly-CL with pro-oxidant additives) in microorganism culture test and soil burial test was investigated under laboratory conditions. The index of degradation was assessed by visual observation, weight loss and SEM analysis from quantitative and qualitative aspect. The results of both tests showed that these biodegradable mulching films were more readily degraded than the common plastic film. The percentage weight loss was in sequence of biodegradable mulching film c > biodegradable mulching film b > biodegradable mulching film a, while common plastic film basically had no changes. Weight loss was not as obvious as the visual degradation and suggested broader types of microbial attack. SEM analysis clearly indicated that the changes of surface morphology of these samples after the soil burial exposure.     

Degradation of Polycaprolactone Modified with TPS or CaCO3 in Biotic/Abiotic Seawater

This paper is an investigation of the polymer degradation process in two types of seawater (with and without microorganisms) sourced from the Baltic Sea. The chosen polymeric materials were polycaprolactone modified with either thermoplastic starch (PCL/TPS?>?85%) or calcium carbonate (60% PCL/40% CaCO₃) compared directly against unmodified polycaprolactone. All samples were incubated for 28?weeks in seawater with and without microorganisms under laboratory conditions and analysed before and after the degradation process. Weight loss analysis, microscopic observations of polymer surfaces and tensile strength tests were used to determine the progress of polymer degradation. The experimental results obtained indicated, that in each of the experiments, degradation of tested polymeric samples occured. The process was more effective in seawater with microorganisms compared against systems without added microorganisms. The experiment in seawater demonstrated that modification of PCL with calcium carbonate did not encourage the degradation process; and in some circumstances inhibited it.     

Degradation and mineralization of cellulose acetate in simulated thermophilic compost environments

Residual cellulose acetate (CA) films with initial degree of substitution (DS) values of 1.7 and 2.5 (CA DS-1.7 and DS-2.5) were recovered from a simulated thermophilic compost exposure and characterized by gel permeation chromatography (GPC), proton nuclear magnetic resonance (¹H NMR), and scanning electron microscopy (SEM) to determine changes in polymer molecular weight and DS and to study microbial colonization and surface morphology, respectively. During the aerobic degradation of CA DS-1.7 and CA DS-2.5 films exposed for 7 and 18 days, respectively, the number-average molecular weight (M _n) of residual polymer decreased by 30.4% on day 5 and 20.3% on day 16, respectively. Furthermore, a decrease in the degree of substitution from 1.69 to 1.27 (4-day exposure) and from 2.51 to 2.18 (12-day exposure) was observed for the respective CA samples. In contrast, CA films (DS-1.7 and DS-2.5) which were exposed to abiotic control vessels for identical time periods showed no significant changes inM _n and DS. SEM photographs of CA (DS-1.7 and DS-2.5) film surfaces after compost exposures revealed severe erosion and corresponding microbial colonization. Similar exposure times for CA films in abiotic control vessels resulted in only minor changes in surface characteristics by SEM observations. The conversion of CA DS-1.7 and DS-2.5 to CO₂ was monitored by respirometry. In these studies, powdered CA was placed in a predigested compost matrix which was maintained at 53°C and 60% moisture content throughout the incubation period. A lag phase of 10- and 25-day duration for CA DS-1.7 and DS-2.5, respectively, was observed, after which the rate of degradation increased rapidly. Mineralization of exposed CA DS-1.7 and DS-2.5 powders reported as the percentage theoretical CO₂ recovered reached 72.4 and 77.6% in 24 and 60 days, respectively. The results of this study demonstrated that microbial degradation of CA films exposed to aerobic thermophilic laboratory-scale compost reactors not only results in film weight loss but also causes severe film pitting and a corresponding decrease in chainM _n and degree of substitution for the residual material. Furthermore, conversions to greater than 70% of the theoretical recovered CO₂ for CA (DS 1.7 and 2.5) substrates indicate high degrees of CA mineralization.Guest Editor: Dr. Graham Swift, Rohm & Haas.     

Mechanical Property and Biodegradability of Cast Films Prepared from Blends of Oppositely Charged Biopolymers

Biodegradable cast films of about 50 m thickness were fabricated by blending oppositely charged biopolymers such as anionic starch–chitosan, and cationic starch–pectin. The tensile strength and elongation at break (%) of films were evaluated as well as their capacity to degrade in compost. Films recovered from soil every 48 h showed consistent degradation (weight loss), diminution of the polymers characteristic peak absorbance in the carbohydrate fingerprint region of the FTIR, and changes in the surface morphology via scanning electron microscopy (SEM). Anionic starch–chitosan films had much superior tensile strength and elongation compared to cationic starch–pectin, suggesting that the ionic bonds formed between anionic-starch and positively charged groups in chitosan polymer were much more stable and stronger. Initially, both films lost about 36% weight within 96 h, which also correlated well with the loss in the characteristic absorption peaks in the region of the infrared spectrum typical of biopolymers. The total mineralization of films by microorganisms in compost soil was also measured using respirometric techniques. Though the rate of mineralization differed for two formulations, total mineralization (extent) for both films were achieved within 45 days.     

Biodegradability: An assessment of commercial polymers according to the Canadian method for anaerobic conditions

The degradation of several biodegradable polymers was measured as a result of exposure to an anaerobic medium. The polymers investigated included materials based upon polylactic acid, polylactone, and poly(hydroxy butyrate/valerate) as well as those incorporating starch-based materials. The degradation was monitored by methane and carbon dioxide evolution. In addition, the physical and chemical changes were noted as a result of exposure. These measurements included changes in mass, dimension, and molecular weight. FTIR, UV-vis, proton, and¹³C NMR spectra were also recorded prior to and after exposure. The results clearly indicated that several biological and chemical degradation processes were occurring with the biodegradable polymers studied.Paper presented at the Bio/Environmentally Degradable Polymer Society—Second National Meeting, August 19–21, 1993, Chicago, Illinois.Issued as NRCC No. 37549.     

Influence of Processing Additives on the Degradation of Melt-Pressed Films of Poly(ε-Caprolactone) and Poly(Lactic Acid)

Melt-pressed films of polycaprolactone (PCL) and poly(lactic acid) (PLA) with processing additives, CaCO₃, SiO₂, and erucamide, were subjected to pure fungal cultures Aspergillus fumigatus and Penicillium simplicissimum and to composting. The PCL films showed a rapid weight loss with a minor reduction in the molecular weight after 45 days in A. fumigatus. The addition of SiO₂ to PCL increased the rate of (bio)erosion in A. fumigatus and in compost. The use of a slip additive, erucamide, was shown to modify the properties of the film surface without decreasing the rate of bio(erosion). Both the rate of weight loss and the rate of molecular weight reduction of PCL increased with decreasing film thickness. The addition of CaCO₃ to PLA significantly reduced the thermal degradation during processing, but it also reduced the rate of the subsequent (bio)degradation in the pure fungal cultures. PLA without additives and PLA containing SiO₂ exhibited the fastest (bio)degradation, followed by PLA with CaCO₃. The degradation of the PLA films was initially governed by chemical hydrolysis, followed by an acceleration of the weight change and of the molecular weight reduction. PLA film subjected to composting exhibits a rapid decrease in molecular weight, which then remains unchanged during the measurement period, probably because of crystallization.     

Synthesis of cellulose-fatty acid esters for use as biodegradable plastics

Long-chain fatty acid carbohydrate esters (FACE) were synthesized by the acid chloride-pyridine reaction to different degrees of substitution (DS). The hydrolyzed soybean oil was used as the source of unsaturated fatty acids. High molecular weight FACE polymers are insoluble in common solvents, such as benzene, toluene, THF, etc., and are highly water resistant. However, FACE polymers of hydrolyzed cellulose (MW 180 kD) are soluble/swellable in toluene and can be cast into tough, flexible films. FACE polymer properties of tensile strength and clasticity vary with degree of substitution and polymer size.Paper presented at the Bio/Environmentally Degradable Polymer Society—Third National Meeting, June 6–8, 1994, Boston, Massachusetts.     

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.     

Adsorption/Desorption of Polyvinyl Alcohol on Solid Substrates and Relevant Biodegradation

The rates and extents of absorption and desorption of polyvinyl alcohol (PVA) samples on different solid substrates comprising montmorillonite, quartz sand, and farm soil, as well as humic acid mixture are reported. The uptake of PVA by the substrates was analyzed as a function of PVA hydrolysis (72–98%), molecular weight, and molecular weight distribution. Higher adsorption was detected on montmorillonite followed by farm soil, whereas the quartz sand did not display any specific adsorption affinity for the PVA. An increase in the hydrolysis degree of PVA increased the adsorption rate and extent whereas this feature was reversed by an increase in PVA molecular weight. The desorption of PVA samples from the different substrates was performed both under various pH conditions and in the presence of concentrated HF that was used to dissolve the silicon derivatives present in the substrates. Biodegradation experiments carried out in liquid cultures of PVA adsorbed on montmorillonite showed that the mineralization of the adsorbed PVA was much lower than that detected for the nonadsorbed PVA. This investigation suggests that irreversible adsorption of PVA on the clay component occurs in soil, thus substantially inhibiting PVA biodegradation.     

Applying metabolic fingerprinting to ecology: The use of Fourier-transform infrared spectroscopy for the rapid screening of plant responses to N deposition

The potential for metabolic fingerprinting via Fourier-transform infrared (FT-IR) spectroscopy to provide a novel approach for the detection of plant biochemical responses to N deposition is examined. An example of spectral analysis using shoot samples taken from an open top chamber (OTC) experiment simulating wet ammonium deposition is given. Sample preparation involved oven drying and homogenisation via mill grinding. Slurries of a consistent dilution were then prepared prior to FT-IR analysis. Spectra from control, 8 and 16 kg N ha^–1 yr^–1 treatments were then subjected to cross-validated discriminant function analysis. Ordination diagrams showed clear separation between the three N treatments examined. The potential for using Calluna vulgaris (L.) Hull as a bioindicator of N deposition is further evident from these results. The results also clearly demonstrate the power of FT-IR in discriminating between subtle phenotypic alterations in overall plant biochemistry as affected by ammonium pollution.     

Microbial degradation of poly(3-hydroxybutyrate) and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) in compost

The microbial degradation of tensile test pieces made of poly(3-hydroxybutyrate) [P(3HB)] or copolymers with 10% [P(3HB-co-10%3HV)] and 20% [P(3HB-co-20%3HV)] 3-hydroxyvaleric acid was studied in small household compost heaps. Degradation was measured through loss of weight (surface erosion) and changes in molecular weight and mechanical strength. It was concluded, on the basis of weight loss and loss of mechanical properties, that P(3HB) and P(3HB-co-3HV) plastics were degraded in compost by the action of microorganisms. No decrease inM _w could be detected during the degradation process. The P(3HB-co-20%3HV) copolymer was degraded much faster than the homopolymer and P(3HB-co-10%3HV). One hundred nine microbial strains capable of degrading the polymersin vitro were isolated from the samples used in the biodegradation studies, as well as from two other composts, and identified. They consisted of 61 Gram-negative bacteria (e.g.,Acidovorax facilis), 10 Gram-positive bacteria (mainlyBacillus megaterium), 35Streptomyces strains, and 3 molds.     

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 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.     

Degradation of starch-plastic composites in a municipal solid waste landfill

The rate and extent of deterioration of starch-plastic composites were determined over a 2-year period for samples buried in a municipal solid waste landfill. The deterioration of the starch-plastic composites following exposure was determined by measuring changes in tensile properties, weight loss, and starch content of samples retrieved from the landfill. Elongation decreases of 92 and 44% were measured for starch-plastic composite LDPE and LLDPE films, respectively, while elongation decreases of 54 and 21% were measured for their corresponding control films following 2 years of burial. Starch loss of 25% for LLDPE and 33% for LDPE starch-plastic composite films was measured following 2 years of landfill burial. Starch-plastic composites did not fragment or lose mass during the 2-year landfill burial. The limited degradation observed for the starch-plastic composites was attributed to the ineffectiveness of the prooxidant additive to catalyze the thermal oxidation of the polyethylene or polypropylene component of the starch-plastic composite under the environmental conditions present within the landfill.