Biodegradability and biodegradation rate of poly(caprolactone)-starch blend and poly(butylene succinate) biodegradable polymer under aerobic and anaerobic environment

The biodegradability and the biodegradation rate of two kinds biodegradable polymers; poly(caprolactone) (PCL)-starch blend and poly(butylene succinate) (PBS), were investigated under both aerobic and anaerobic conditions. PCL-starch blend was easily degraded, with 88% biodegradability in 44 days under aerobic conditions, and showed a biodegradation rate of 0.07 day⁻¹, whereas the biodegradability of PBS was only 31% in 80 days under the same conditions, with a biodegradation rate of 0.01 day⁻¹. Anaerobic bacteria degraded well PCL-starch blend (i.e., 83% biodegradability for 139 days); however, its biodegradation rate was relatively slow (6.1 mL CH₄/g-VS day) compared to that of cellulose (13.5 mL CH₄/g-VS day), which was used as a reference material. The PBS was barely degraded under anaerobic conditions, with only 2% biodegradability in 100 days. These results were consistent with the visual changes and FE-SEM images of the two biodegradable polymers after the landfill burial test, showing that only PCL-starch blend had various sized pinholes on the surface due to attack by microorganisms. This result may be use in deciding suitable final disposal approaches of different types of biodegradable polymers in the future.     

Biodegradation Behaviors of Poly(p-dioxanone) in Different Environment Media

This work was aimed at researching the aerobic biodegradation of poly(p-dioxanone) (PPDO), a novel kind of degradable polymer material, by simulating real-life conditions in a laboratory-scale test, specified by the standard methods based on two biodegradation environments, composting and aqueous media. To measure and describe the biodegradability of PPDO, not only had carbon dioxide produced by respiratory metabolism of microorganism been measured, which determines the ultimate aerobic biodegradability of chemical compounds, but also the detailed results of biodegradation were further characterized by monitoring physical, chemical and thermal properties changes of test materials at different incubation times in the two media, confirmed by using the appropriate analytical techniques. Scanning electron microscopy was used to observe the surface morphology, and the thermal performance of PPDO was characterized by differential scanning calorimetry. The changes of molecular weight were detected by intrinsic viscosity ([η]) and gel permeation chromatography, and the variations of the molecular structure were monitored by the nuclear magnetic resonance and FT-IR. The results show that PPDO has outstanding character of biodegradation and may be more adapted for biodegrading in liquid medium than in composting.     

Radiation Crosslinking of Poly(Butylene Succinate) in the Presence of Inorganic Material and Its Biodegradability

Three kinds of poly(butylene succinate)s (PBS) with different molecular weight were irradiated with electron beams in the presence of inorganic material. Fourteen kinds of inorganic materials were used in this work. The presence of inorganic material inside cross-linked PBS samples enhances the yield of gel formation. The heat stabilities of PBS samples were checked; it was found that silicon dioxide and carbon black significantly improve these properties. Enzymatic and soil burial tests were performed; the presence of these inorganic materials in cross-linked PBS accelerates the rate of biodegradation.     

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%.     

The biodegradation of lactic acid-based poly(ester-urethanes)

The biodegradability of lactic acid based poly(ester-urethanes) was studied using the headspace test method, which was performed at several elevated temperatures. The poly(ester-urethanes) were prepared using a straight two-step lactic acid polymerization process. The lactic acid is first condensation polymerized to a low molecular weight hydroxyl-terminated telechelic prepolymer and then the molecular weight is increased with a chain extender such as diisocyanate. In the biodegradation studies the effect of different stereostructures (different amounts of D-units in the polymer chain), the length of ester units, and the effect of crosslinking on the biodegradation rate were studied. The results indicate that poly(ester-urethanes) do not biodegrade at 25‡C, but at elevated temperatures they biodegrade well. The different stereostructures and crosslinking have a strong influence on the biodegradation rate. The length of ester units in the polymer chain also affects the biodegradation rate, but much less than crosslinking and stereostructure.     

Bioabsorbable Soy Protein Plastic Composites: Effect of Polyphosphate Fillers on Biodegradability

The use of biodegradable polymers made from renewable agricultural products such as soy protein isolate has been limited by the tendency of these materials to absorb moisture. A straightforward approach for controlling the inherent water absorbency of the biodegradable polymers involves blending special bioabsorbable polyphosphate fillers, biodegradable soy protein isolate, plasticizer, and adhesion promoter in a high-shear mixer followed by compression molding. The procedure yields a relatively water-resistant, biodegradable soy protein polymer composite, as previously reported. The aim of the present study is to determine the biodegradability of the new polyphosphate filler/soy protein plastic composites by monitoring the carbon dioxide released over a period of 120 days. The results suggest that the composites biodegrade satisfactorily, with the fillers having no significant effect on the depolymerization and mineralization of the soy protein plastic, processes that would otherwise result in nonbiodegradable composites. Further, the results indicate that the biodegradation and useful service life of these biocomposites may be controlled by changing the filler concentration, making the biocomposites useful in applications in which the control of water resistance and biodegradation is critical.     

Biomass Carbon Ratio of Polymer Composites Measured by Accelerator Mass Spectrometry

The evaluation method of biomass carbon ratio of polymer composite samples including organic and inorganic carbons individually was investigated. Biodegradable plastics and biobased plastics can have their mechanical properties improved by combining with inorganic fillers. Polymer composites consisting of biodegradable plastics and carbonate were prepared by two different methods. Poly(lactic acid) (PLA) composite was prepared by synthesis from l-lactide with catalyst and calcium carbonate (CaCO₃) powders from lime. Poly(butylene succinate) (PBS) composite was prepared by hot-pressing the mixture of PBS powder and CaCO₃ powders from oyster shells. The mechanical properties of composite samples were investigated by a tensile test and a compression test using an Instron type mechanical tester. Tensile test with a dumbbell shape specimen was performed for PBS composite samples and compression test with a column shape specimen for PLA composite samples. Strength, elastic modulus and fracture strain were obtained from the above tests. Biomass carbon ratio is regulated in the American Standards for Testing and Materials (ASTM). In ASTM standards on biomass carbon ratio, it is required that carbon atoms from carbonates, such as CaCO₃, are omitted. Biomass carbon ratio was evaluated by ratio of ¹⁴C to ¹²C in the samples using Accelerator Mass Spectrometry (AMS). The effect of pretreatment, such as oxidation temperature and reaction by acid, on results of biomass carbon ratio was investigated. Mechanical properties decrease with increasing CaCO₃ content. The possibility of an evaluation method of biomass carbon ratio of materials including organic and inorganic carbons was shown.     

Biodegradation of Poly(vinyl alcohol) and Bacterial Cellulose Composites by <Emphasis Type="Italic">Aspergillus niger</Emphasis>

The ability of fungal strains to attack a composite material obtained from poly(vinyl alcohol) (PVA) and bacterial cellulose (BC) is investigated. The fungal strain tested was Aspergillus niger. This fungal strain was able to change not only the polymer surface from smoother to rougher, but also to disrupt the polymer. The degradation results were confirmed by visual observations, scanning electron microscopy (SEM) analyses, X-ray diffraction analyses and FTIR spectra of the film samples. SEM micrographs confirmed the growth of fungi on the composite film surface. The degree of microbial degradation depends on culture medium and on composition of polymeric materials, especially on PVA content. The biodegradation process is accelerated by the presence of glucose in the culture medium as an easily available carbon source.     

Mechanical, Thermal and Water Absorption Properties of Kenaf-Fiber-Based Polypropylene and Poly(Butylene Succinate) Composites

The use of composites made from non-biodegradable conventional plastic materials (e.g., polypropylene, PP) is creating global environmental concern. Biodegradable plastics such as poly(butylene succinate) (PBS) are sought after to reduce plastic waste accumulation. Unfortunately, these types of plastics are very costly; therefore, natural lignocellulosic fibers are incorporated to reduce the cost. Kenaf fibers are also incorporated into PP and PBS for reinforcing purposes and they have low densities, high specific properties and renewable sourcing. However without good compatibilization, the interfacial adhesion between the matrix and the fibers is poor due to differences in polarity between the two materials. Maleic anhydride-grafted compatibilizers may be introduced into the system to improve the matrix-fiber interactions. The overall mechanical, thermal and water absorption properties of PP and PBS composites prepared with 30 vol.% short kenaf fibers (KFs) using a twin-screw extruder were being investigated in this study. The flexural properties for both types of composites were enhanced by the addition of compatibilizer, with improvements of 56 and 16 % in flexural strength for the PP/KF and PBS/KF composites, respectively. Good matrix-fiber adhesion was also observed by scanning electron microscopy. However, the thermal stability of the PBS/KF composites was lower than that of the PP/KF composites. This result was confirmed by both DSC and TGA thermal analysis tests. The water absorption at equilibrium of a PBS composite filled with KFs is inherently lower than of a PP/KF composite because the water molecules more readily penetrate the PP composites through existing voids between the fibers and the matrix. Based on this research, it can be concluded that PBS/KF composites are good candidates for replacing PP/KF composites in applications whereby biodegradability is essential and no extreme thermal and moisture exposures are required.     

Biodegradation of Coir and Sisal Applied in the Automotive Industry

This paper discusses the results of biodegradability tests of natural fibers used by the automotive industry, namely: coir, coir with latex, and sisal. The biodegradation of coir, coir with latex, and of sisal fibers was determined by monitoring the production of carbon dioxide (CO₂) (IBAMA—E.1.1.2, 1988) and fungal growth (DIN 53739, 1984). The contents of total extractives, lignin, holocellulose, ashes, carbon, nitrogen and hydrogen of the fibers under study were determined in order to ascertain their actual content and to understand the results of the biodegradation tests. The production of CO₂ indicated low biodegradation, i.e., about 10% in mass, for all the materials after 45 days of testing; in other words, no material inhibited glucose degradation. However, the percentage of sisal fiber degradation was fourfold higher than that of coir with latex in the same period of aging. The fungal growth test showed a higher growth rate on sisal fibers, followed by coir without latex. In the case of coir with latex, we believe the fungal growth was not intense, because natural latex produces a bactericide or fungicide for its preservation during bleeding [1]. An evaluation of the materials after 90 days of aging tests revealed breaking of the fibers, particularly sisal and coir without latex, indicating fungal attack and biodegradation processes.     

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

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

The Relationship Between the Chemical Structure of Poly(alkylene glycol)s and Their Aerobic Biodegradability in an Aqueous Environment

The relationship between the chemical structure of poly(alkylene glycol)s (PAGs) and their biodegradability was studied using a set of polymeric fluids that included poly(ethylene glycol), poly(propylene glycol) (PPG), random copolymers of ethylene oxide (EO) and propylene oxide (PO) differing in the EO/PO ratio as well as PAGs capped with ether or acyl moieties. The PAGs that were tested had an average molecular weight (MW) in the range of 350–3,600 Da and differed in their polymer backbones by either linear (diol type) or branched (triol type) molecules. The ultimate biodegradability of the PAGs was determined according to ISO 14593 (CO₂ headspace test) with a non-pre-exposed (as in OECD 310 test) and pre-exposed (adapted) inoculum. PAGs with the structure of PPG and copolymers of EO/PO of diol or triol structures with average molecular weights lower than 1,000 Da can be considered as readily biodegradable. Their ultimate biodegradation exceeds the limit of 60 % (according to the criteria of the OECD 310 test). PAGs with a copolymer structure and MW values ranging between 1,000 and 3,600 Da are not readily biodegradable, but they can be considered as those of inherent ultimate biodegradability. The increased EO content in PAG structures and the acylation of the terminal hydroxyl groups with carboxylic acids favourably influenced their biodegradability. Capped PAGs containing terminal ether groups appeared to be resistant to biodegradation.     

Influence of aeration rate and biodegradability fractionation on composting kinetics

The influences of aeration rate and biodegradability fractionation on biodegradation kinetics during composting were studied. The first step was the design of a suitable lab-reactor that enabled the simulation of composting. The second step comprised of composting trials of six blends of sludge (originating from a food processing effluent) with wood chips using aeration rates of 1.69, 3.62, 3.25, 8.48, 11.98 and 16.63 L/h/kg DM of mixture. Biodegradation was evaluated by respiration measurements and from the analysis of the substrate (dry matter, organic matter, total carbon and chemical oxygen demand removal). Continuous measurement of oxygen consumption was coupled with the analysis of initial substrate and composted product for chemical oxygen demand (in the soluble and non-soluble fractions), which enabled an evaluation of the organic matter biodegradability. Oxygen requirements to remove both the easily and slowly biodegradable fractions were determined. Dividing the substrate into different parts according to biodegradability allowed explanation of the influence of aeration rate on stabilization kinetics. Considering that the biodegradation kinetics were of the first-order, the kinetic constants of the easily and slowly biodegradable fractions were calculated as a function of temperature. The methodology presented here allows the comparison of organic wastes in terms of their content of easily and slowly biodegradable fractions and the respective biodegradation kinetics.     

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.     

Enhanced Mineralization of PLA Meltblown Materials Due to Plasticization

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

Cradle-to-Grave Life Cycle Assessment and Techno-Economic Analysis of Polylactic Acid Composites with Traditional and Bio-Based Fillers

This research focused on life cycle assessment (LCA) and techno-economic analysis (TEA) comparisons of polylactic acid (PLA) composites, in order to compare organic to inorganic fillers. Organic fillers included DDGS, flax, hemp, rice husks, and wood, and were compared against inorganic fillers (glass and talc) for PLA-based composites. This study utilized LCAI and TEA methodology to estimate and quantify costs, emissions, and energy intensity (EI) associated with material acquisition, processing, transport, and end-of-life treatment used during plastic composite production. Emission categories analyzed include global warming potential (GWP), air acidification (AA), air eutrophication (AE), water eutrophication (WE), ozone layer depletion (OLD), air smog (AS), high carcinogens (HC), and high non-carcinogens (HNC). To achieve a “Cradle-to-Grave” perspective, two models were meshed, the plastic comparator (PC) and EIO-LCA (EIO), to simulate the EI and emissions associated over the entire life cycle. Based assumptions used, this research has shown that utilizing land fill end-of-life treatment and glass filler composite was the most environmentally harmful option, and maintained the highest economic impact, for all impact categories during PLA composite production. Alternatively, both DDGS and wood filler composites paired with recycling end-of-life treatment were shown to be the least environmentally damaging method and incurred the lowest cost of all PLA composites considered. This study also suggests that utilization of organic bio-based fillers produces a lower economic/environmental impact, and EI, compared to utilization of inorganic fillers in PLA composites. Accordingly, this research has demonstrated the impact of LCA/TEA paired analysis when assessing the bioplastic and biocomposite processing, which may be utilized as a precursor for parallel research undertakings.     

An overview of methods for biodegradability testing of biopolymers and packaging materials

This paper gives an overview of the methods used at the Technical Research Centre of Finland (VTT) for the biodegradability testing of solid polymers and packaging materials. Biodegradability of each polymer included in the packaging material should be separately tested. Aquatic aerobic and anaerobic tests and, in specific cases, enzymatic tests are used for screening purposes. The application of aquatic aerobic tests—an automated Sturm test (OECD 301B; ASTM D5209) and a VTT headspace test as well as an anaerobic test (ASTM D5210)—is discussed. Three composting tests and their applications are summarized. These tests are regarded as important because they can be used to simulate the biodegradability under real-life conditions. Several tests are needed to determine the fate of the polymer under real conditions and to study its biodegradability in different environments. The time needed for complete biodegradation of polymers in nature is impossible to predict with laboratory tests and should be studiedin vivo.According to the lecture given in Sweden at the Royal Institute of Technology, at a workshop on polymers from renewable resources and their degradation, November 10–11, 1994.     

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.     

Fiber from DDGS and Corn Grain as Alternative Fillers in Polymer Composites with High Density Polyethylene from Bio-based and Petroleum Sources

The steady increase in production of corn based ethanol fuel has dramatically increased the supply of its major co-product known as distiller’s dried grain with solubles (DDGS). Large amount of DDGS and corn flour are used as an animal feed. The elusieve process can separate DDGS or corn flour into two fractions: DDGS fraction with enhanced protein and oil content or corn flour fraction with high starch content, and hull fiber. This study investigated the feasibility of using fiber from DDGS and corn grain as alternative fillers to wood fiber in high density polyethylene (HDPE) composites made with two different sources of polymers. Two fiber loading rates of 30 and 50% were evaluated for fiber from DDGS, corn, and oak wood (control) to assess changes in various physical and mechanical properties of the composite materials. Two HDPE polymers, a bio-based HDPE made from sugarcane (Braskem), and a petroleum based HDPE (Marlex) were also compared as substrates. The biobased polymer composites with DDGS and corn fibers showed significantly lower water absorption than the Marlex composite samples. The Braskem composite with 30% DDGS fiber loading showed the highest impact resistance (80 J/m) among all the samples. The flexural properties showed no significant difference between the two HDPE composites.     

Evaluation of the Effect of Chemical or Enzymatic Synthesis Methods on Biodegradability of Polyesters

This work compares the biodegradability of polyesters produced by an esterification reaction between glycerol and oleic di-acid (D 18:1) issued from green chemical pathways, via either classical thermo-chemical methods, or an enzymatic method using the immobilized lipase of Candida antartica B (Novozym 435). An elastomeric polymer synthesized by enzymatic catalysis is more biodegradable than an elastomeric thermo-chemical polyester synthesized by a standard chemical procedure. This difference lies in percentage of the dendritic motifs, in values of the degree of substitution, and certainly in cross-links inducing an hyper-branched structure less accessible to the lipolytic enzymes in a waste treatment plant. However, when the elastomeric polymer synthesized by enzymatic catalysis is processed at high temperature as required for certain industrial applications, it presents an identical rate of biodegradation than the chemical polyester. The advantages of the thermo-chemical methods are greater speed and lower cost. Enzymatic synthesis appears be suited to producing polyesters, devoid of metallic catalysts, which must be used without processing at high temperature to keep a high biodegradability.