The influence of biotic and abiotic factors on the rate of degradation of poly(lactic) acid (PLA) coupons buried in compost and soil

Poly(lactic) acid (PLA) is a compostable biopolymer and has been commercialised for the for the manufacture of short-shelf life products. As a result, increasing amounts of PLA are entering waste management systems and the environment; however, the degradation mechanism is unclear. While hydrolysis of the polymer occurs abiotically at elevated temperature in the presence of water, potential catalytic role for microbes in this process is yet to be established. In this study, we examined the degradation of PLA coupons from commercial packaging at a range of temperatures (25°, 37°, 45°, 50° and 55 °C) in soil and compost and compared with the degradation rates in sterile aqueous conditions by measuring loss of tensile strength and molecular weight (Mw). In addition, in order to assess the possible influence of abiotic soluble factors in compost and soil on degradation of PLA, degradation rates in microorganism-rich compost and soil were compared with sterile compost and soil extract at 50 °C. Temperature was determined to be the key parameter in PLA degradation and degradation rates in microorganism-rich compost and soil were faster than in sterile water at temperatures 45° and 50 °C determined by tensile strength and Mw loss. Furthermore, all tensile strength was lost faster after 30 and 36 days in microorganism-rich compost and soil, respectively, than in sterile compost and soil extract, 57 and 54 days, respectively at 50 °C. Significantly more Mw, 68% and 64%, was lost in compost and soil, respectively than in compost extract, Mw, 53%; and in soil extract, 57%. Therefore, degradation rates were faster in microorganism-rich compost and soil than in sterile compost and soil extract, which contained the abiotic soluble factors of compost and soil at 50 °C. These comparative studies support a direct role for microorganisms in PLA degradation at elevated temperatures in humid environments. No change in tensile strength or Mw was observed either 25° or 37 °C after 1 year suggesting that accumulation of PLA in the environment may cause future pollution issues.     

Effect of multiple extrusion on molecular structure of polypropylene impact copolymer

Neat and multiple processed polypropylene impact-copolymer (ICPP) were fractionated using series of hydrocarbon solvents with increasing solvent power. The analyses of the fractions obtained in successive extractions showed significant decrease in weight-average molecular weight (Mw) and narrowing the molecular weight distribution (MWD) of investigated samples after extrusions. Although the changes due to thermooxidation were observed in all phases of the system, the most intensive degradation was found in the prevailing PP homopolymer phase.     

Preparation, characterization and biodegradation of biopolymer nanocomposites based on fumed silica

PLA and PCL based nanocomposites prepared by adding three different types of fumed silica were obtained by melt blending. Materials were characterized by means of Scanning Electron Microscopy (SEM), Differential Scanning Calorimetry (DSC), Thermogravimetric Analysis (TGA) and Dynamic–Mechanical Thermal Analysis (DMTA).A good distribution of the fumed silica into both polymer matrices was observed. The highest thermo-mechanical improvements were reached by addition of the fumed silica with higher surface area. PLA and its nanocomposites were degraded in compost at 58 °C; at this temperature all samples presented a significant level of polymer degradation, but a certain protection action of silica towards PLA degradation was observed, whereas the addition of fumed silica did not show considerable influence on the degradation trend of PCL. These dissimilarities were attributed to the different degradation mechanism of the two polymers.     

Degradation behaviour of PCL/PEO/PCL and PCL/PEO block copolymers under controlled hydrolytic,enzymatic and composting conditions

Short-term hydrolytic and enzymatic degradation of poly(ε-caprolactone) (PCL), one series of triblock (PCL/PEO/PCL) and the other of diblock (PCL/PEO) copolymers, with a low content of hydrophilic PEO segments is presented. The effect of the introduction of PEO as the central or lateral segment in the PCL chain on copolymer hydrolysis and biodegradation properties was investigated. FTIR results revealed higher hydrolytic degradation susceptibility of diblock copolymers due to a higher hydrophilicity compared to PCL and triblock copolymers. Enzymatic degradation was tested using cell-free extracts of Pseudomonas aeruginosa PAO1, for two weeks by following the weight loss, changes in surface roughness, and changes in carbonyl and crystallinity index. The results confirmed that all samples underwent enzymatic degradation through surface erosion which was accompanied with a decrease in molecular weights. Diblock copolymers showed significantly higher weight loss and decrease in molecular weight in comparison to PCL itself and triblock copolymers. AFM analysis confirmed significant surface erosion and increase in RMS values. In addition, biodegradation of polymer films was tested in compost model system at 37 °C, where an effective degradation of block copolymers was observed.     

Chemical degradation of crosslinked ethylene-propylene-diene rubber in an acidic environment. Part I. Effect on accelerated sulphur crosslinks

The time-dependent chemical degradation of accelerated sulphur cured ethylene propylene diene rubber containing 5-ethylidene-2-norbornene as diene in an acidic environment (20% Cr/H₂SO₄) was investigated. Two different rubbers with a similar ethylene to propylene ratio and diene content but with a significant difference in molar mass and level of long chain branching were used in the study. The molecular mechanisms of the chemical degradation occurring at the surface were determined using surface analysis (X-ray photoelectron spectroscopy and attenuated total reflectance Fourier transform infrared spectroscopy). The results reveal formation of several oxygenated species on the surface as a consequence of the acid attack. Furthermore, the crosslink sites of the exposed rubber samples are also found vulnerable to hydrolytic attack as evidenced by the decrease in crosslink density. The extent of surface degradation was strong enough to affect the bulk mechanical properties. Changes in mechanical properties were also monitored through determining retention in tensile strength, (%) elongation at break, modulus at 50% elongation, and change in micro-hardness. A negative correlation is also established between retention in modulus at 50% elongation and decrease in crosslink density. Scanning electron microscopy reveals the topographical damage at the surface due to the aqueous acid induced chemical degradation. The results indicate that the chemical degradation proceeds mainly via hydrolysis of crosslinks but upon prolonged exposure, the oxygenated species tend to combine with each other. The effect of molar mass and level of long chain branching also influences the chemical degradation.     

Changes in the mechanical properties of compression moulded samples of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) degraded by Streptomyces omiyaensis SSM 5670

Streptomyces omiyaensis SSM 5670 was characterized by its ability to use compression moulded samples of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) as its sole carbon source. Biodegradation of PHBV in liquid mineral salts medium was investigated using scanning electron microscopy, gravimetric measurements, capillary viscometry, tensile testing and wide angle X-ray spectroscopy. The biodegradation of PHBV proceeds via surface erosion mechanism, resulting in the formation of pits by microbial attack. PHBV specimens lost about 45% of their original weight after 45 days of exposure. During the degradation process the elastic modulus reduces less than 10%. The formation of pores and microcracks initiated at the degraded pits determines the reduction of the elongation and stress at break. However, the true stress at break is practically independent of the degradation time. No significant changes of PHBV molecular weight or crystallinity were observed during biodegradation. The polymer chain cleavage occurred only at the specimen surface and does not discriminate between crystalline and amorphous states.     

In Vitro Degradation of Poly(lactic-co2-glycolic) Acid Random Copolymers

We have investigated the in vitro degradation of poly(lactic-co-glycolic) acid copolymer with a lactic to glycolic ratio of 65/35. The degradation studies were performed on solvent-cast films of controlled thickness and shape. The samples were then incubated at 37 °C in phosphate buffered saline solution. The degradation was followed using potentiometry, light microscopy, gravimetry, gel permeation chromatography and differential scanning calorimetry. Water was found to diffuse inside the film as soon as the sample was placed in the degradation media. Wrinkles formed on the upper layer while degradation took place via chain scission in the bulk of the film. After 10 days, this led to the creation of a vesicle where liquid low molecular weight oligomers were trapped inside a thin film of high molecular weight polymer. This thin film acted as a membrane allowing only low molecular weight compounds to diffuse out of the film.     

Evaluation of the rate of abiotic and biotic degradation of oxo-degradable polyethylene

The recent introduction of oxo-degradable additive in the Argentinean market has motivated the study of the effect of abiotic (temperature and ultraviolet (UV) radiation) and biotic (aerobic in compost) degradation on the structure and mechanical behavior of films of polyethylene (PE) and oxo-degradable polyethylene (PE+AD).Physico-chemical tests show that the failure strain and the carbonyl index of degraded PE and PE+AD samples depend on the UV irradiation dose. Furthermore, the additive plays a crucial role in the degradation and subsequent decay of the molecular weight.It was observed that, for the same dose, the most deteriorated material was the one exposed to the lowest irradiance, emphasizing the importance of the time of exposure to UV radiation. The ratio between the irradiance and the critical dose, is a characteristic time associated to the sharp decay on the failure strain. The critical dose decreases significantly when increasing the temperature of the photo-degradation assay.PE is more susceptible to thermal degradation than PE+AD; the latter only degrades under thermal aging at the highest temperature.Initially biotic degradation in compost showed an increasing production of carbon dioxide for both previously UV-degraded and untreated PE+AD. It is also remarkable that UV-degraded samples of PE and PE+AD with differences in their abiotic degradation level, reached the same final biotic degradation level. It was observed that although the additive increased the abiotic photodegradation, the molecular weight reduction in compost was not enough to reach the maximum biotic degradation level established by international standards for biodegradable materials.     

Effect of environment on the degradation of starch and pro-oxidant blended polyolefins

The aim of this study was to understand the rate of degradation of commercial pro-oxidant blended and starch blended High Density Polyethylene (HDPE), pro-oxidant blended Low Density Polyethylene (LDPE), and starch blended polypropylene in three different environments, namely under direct sunlight, buried in soil and immersed in marine waters for a period of 150 days. The bio-fouling parameters were also monitored in the case of polymers deployed in sea water. Exposure to sunlight showed highest weight loss (>10%) and samples buried in soil showed the lowest (∼1%). Pro-oxidant blended HDPE showed higher weight loss when compared to starch blended (22.7 as against 11%). Scanning electron microscopy revealed surface deterioration and decrease in contact angle indicated reduction in surface hydrophobicity. Increase in the carbonyl and hydroxyl groups in the infra-red spectrum of the exposed samples suggested abiotic degradation. Starch blended PP exposed to sunlight showed the highest thermo gravimetric weight loss (63.8%) followed by the same polymer buried in soil (46.1%).     

Chemical degradation of crosslinked ethylene-propylene-diene rubber in an acidic environment. Part II. Effect of peroxide crosslinking in the presence of a coagent

An investigation on the time-dependent chemical degradation of ethylene-propylene diene rubber containing 5-ethylidene-2-norbornene as diene cured by peroxide crosslinking in the presence of a coagent in an acidic environment (20% Cr/H₂SO₄) has been made. Two types of rubber, with comparable monomer composition, but having significant differences in molar mass and levels of long chain branching were tested. Dicumyl peroxide and triallylcyanurate under similar conditions were used for curing the rubbers. The molecular mechanisms of chemical degradation at the surface were studied using X-ray photoelectron spectroscopy and attenuated total reflectance Fourier transform infrared spectroscopy, which demonstrate that several oxygenated species evolve during exposure. The primary process of degradation is hydrolytic attack on the crosslink sites, which is manifested by a decrease in crosslink density. The surface degradation is found to be strong enough to alter the bulk mechanical properties as observed by the change in retention in tensile strength, elongation at break, modulus at 50% elongation and, the change in micro-hardness. Retention in modulus at 50% elongation is found to follow a negative linear correlation with decrease in crosslink density. With higher molar mass and level of long chain branching more crosslinking occurs and thus comparatively more hydrolytic attack ensues. Scanning electron microscopy shows that the surface topography is significantly altered upon exposure and supports the notion of the dependence of degradation on the crosslinking density of the samples. Importantly, the coagent used in this study is shown to enhance the chemical degradation through formation of weaker sites for hydrolysis. The results also show that upon prolonged exposure the resulting oxygenated species tend to combine with each other.     

Gel permeation chromatography with interference refractometry for the rapid assay of polydisperse dextrans in biological fluids

A semi-automatic system incorporating an ultra-sensitive interference refractometer coupled to a dual-column gel permeation apparatus has been devised for measurement of the molecular size distribution of dextrans in small samples of serum and urine. The system was calibrated with seventeen defined dextran fractions with a range of 1200-250,000 weight average molecular weight (Mw). Urine samples were prepared for analysis by passage through small ion-exchange columns; serum was pretreated by precipitation with trichloroacetic acid and centrifuged before the ion-exchange treatment. Internal standard (dextran, 2 X 10(6) Mw) was added to each sample before pretreatment. Data were obtained in a form suitable for computerised analysis.     

Studies of the hydrolytic stability of poly(urethane-urea) elastomers synthesized from oligocarbonate diols

Polyurethane and poly(urethane-urea) elastomers synthesized from oligocarbonate diols are characterized by very good mechanical properties, biocompatibility and excellent resistance to both oxidation and hydrolysis and therefore are widely used in medical applications. In this paper the results of studies on hydrolytic stability of poly(urethane-urea) elastomers (PURC) obtained by moisture-curing of corresponding urethane prepolymers synthesized from isophorone diisocyanate (IPDI) and four different oligocarbonate diols (OCD) are presented. OCD were synthesized from dimethyl carbonate and 1,6-hexanediol, from cyclic ethylene carbonate and 1,6-hexanediol as well as from trimethylene carbonate. The changes of the sample weight, mechanical properties and surface properties after immersion in a standard phosphate buffer solution (pH = 7.4) for up to 3 months at 70 °C were monitored. It was shown that neither sample weight nor mechanical properties changed significantly for PURC obtained from OCDs synthesized from 1,6-hexanediol and dimethyl carbonate or ethylene carbonate what confirms good resistance to hydrolysis of those PURC. Also SEM studies of those samples before and after immersion did not reveal any surface degradation effects. However, PURC sample obtained from OCD synthesized from trimethylene carbonate showed significant changes in mechanical properties and distinct change of appearance and surface erosion after 3 months immersion. The initial decrease and later increase of stress at break observed for PURC samples during immersion, was explained by the reaction of residual NCO groups present in PURC with water leading to molecular weight increase which proceeded during immersion period in parallel to hydrolysis of carbonate bond.     

Microcellular antibacterial polylactide‐based systems prepared by additive extrusion with ALUM

This work investigates preparation by extrusion of microcellular antimicrobial polylactide (PLA) with an additive, the latter comprising 1% potassium aluminum sulfate dodecahydrate (ALUM), and 3% or 5% of a mixture of sodium hydrogen carbonate and sodium dihydrogen phosphate (1:1). Study was made as to the properties of the materials, their hydrolysis, release profiles, and antimicrobial properties in comparison with the pure polymer. Measuring the molecular weight of samples by gel permeation chromatography revealed that, during thermal processing, the molecular weight of the PLA prepared with additives mentiond above had reduced by approximately 43%. A mechanical test confirmed a decline in mechanical properties after processing as compared with the pure PLA. Release of the antimicrobial compound and the subsequent antimicrobial activity against Staphylococcus aureus and Escherichia coli was evaluated according to ISO 22196:2007. The release of ALUM from the microcellular specimens took place in two steps. During the first 10 days, the rate of release was extremely high in contrast with the remaining period. However, the release rate of the nonporous sample was seen to equal less than 1% in the first 10 days, a phenomenon probably arising through its less active surface.     

Anisotropic effects in thermogravimetry of polymeric composites

The weight loss of carbon fiber-reinforced polymeric composites in air has been found to depend on the sample surface characteristics such as fiber orientation with respect to the exposed surfaces. This phenomenon can be attributed to the diffusion of oxygen through the sample and the dependence of diffusion rate on fiber orientation. Recently, an anisotropic degradation methodolgy was proposed, based on the unreactedcore principle, commonly used in catalysis, as extended to account for the anisotropic effects. In this work, these anisotropic diffusion effects were also identified for small thermogravimetric (TGA) samples. Isothermal TGA experiments were performed in air at 310°C using samples weighing 10–163mg. Weight loss was found to be a strong function of fiber orientation. The anisotropic degradation methodology successfully predicted the weight loss of all samples, although some deviation attributed to the sample edge effects was observed. When samples were examined by optical microscopy, a degraded zone was observed on the sample surfaces. The thickness of this layer depended on the type of exposed surface, validating the anisotropic degradation methodology. © 1993 John Wiley & Sons, Inc.     

Biodegradation and hydrolysis rate of aliphatic aromatic polyester

The biodegradation and hydrolysis rates of an aliphatic aromatic copolyester were measured in manure, food, and yard compost environments and in phosphate buffer solution (pH = 8.0) and vermiculite at 58 °C. Mineralization, molecular weight reduction, and structural changes determined by DSC, FTIR, and ¹H NMR were used as indicators of the biodegradation and hydrolysis rates. Poly(butylene adipate-co-terephthalate), PBAT, film biodegraded at distinctive rates in manure, food, and yard compost environments having different microbial activities. The highest biodegradation rate was found in manure compost, which had the highest CO₂ emissions and lowest C/N ratio. The possible presence of extracellular enzymes in manure and food composts may facilitate the hydrolytic reaction since greater molecular weight reduction rates were observed in these composts. ¹H NMR and thermal analysis revealed that, while PBAT is a semi-crystalline copolyester with cocrystallization of BT and BA dimers, the soft aliphatic domain (BA) and the amorphous region are more susceptible to hydrolysis and biodegradation than the rigid aromatic domain (BT) and the crystalline region.     

Degradation of the blends of natural and synthetic copolyesters in different natural environments

The paper presents results of the biodegradation of the blends of natural and synthetic copolyesters in two different natural environments. Environmental degradation took place in compost with activated sludge at sewage farm and - for comparison - in the Baltic Sea in Gdynia Harbour. Degradation of these blends was monitored for 16 weeks in compost and for 6 weeks in sea water. The changes in macroscopic features of surface and the weight loss of the samples were measured during the performed experiment. The characteristic parameters of compost and sea water were also controlled during all incubation time and their influence on the rate of biodegradation is discussed. The results of this study revealed that the natural aliphatic copolyester i.e. 3-hydroxybutyrate-co-3-hydroxyvalerate (PHBV) and its blends with the synthetic aliphatic-aromatic copolyester of 1,4-butandiol with adipic and terephthalic acids degrade faster in compost than in sea water. The rate of the biodegradation process depends on the composition of blends and different abiotic parameters of compost and sea water.     

Degradation of medium-chain-length polyhydroxyalkanoates in tropical forest and mangrove soils

Bacterial polyhydroxyalkanoates (PHAs) are perceived to be a suitable alternative to petrochemical plastics because they have similar material properties, are environmentally degradable, and are produced from renewable resources. In this study, the in situ degradation of medium-chain-length PHA (PHA_MCL) films in tropical forest and mangrove soils was assessed. The PHA_MCL was produced by Pseudomonas putida PGA1 using saponified palm kernel oil (SPKO) as the carbon source. After 112 d of burial, there was 16.7% reduction in gross weight of the films buried in acidic forest soil (FS), 3.0% in the ones buried in alkaline forest soil by the side of a stream (FSst) and 4.5% in those buried in mangrove soil (MS). There was a slight decrease in molecular weight for the films buried in FS but not for the films buried in FSst and in MS. However, no changes were observed for the melting temperature, glass transition temperature, monomer compositions, structure, and functional group analyses of the films from any of the burial sites during the test period. This means that the integral properties of the films were maintained during that period and degradation was by surface erosion. Scanning electron microscopy of the films from the three sites revealed holes on the film surfaces which could be attributed to attack by microorganisms and bigger organisms such as detritivores. For comparison purposes, films of polyhydroxybutyrate (PHB), a short-chain-length PHA, and polyethylene (PE) were buried together with the PHA_MCL films in all three sites. The PHB films disintegrated completely in MS and lost 73.5% of their initial weight in FSst, but only 4.6% in FS suggesting that water movement played a major role in breaking up the brittle PHB films. The PE films did not register any weight loss in any of the test sites.     

Effects of hydrolysis-induced molecular weight changes on the phase separation of a polyester polyurethane

A polyester polyurethane, was subjected to humid and dry aging conditions at 70 °C with 75% and 0% relative humidity, respectively. Differences in molecular weight and quasi-static tensile strength between humid- and dry-aged samples are attributed to hydrolysis of the humid-aged polymers. A phase-separation study was performed on selected samples from the aging matrix. Polymer samples were subjected to 110 °C for 10 min, by mixing the polyester (soft) and the polyurethane (hard) domains, then rapidly cooled to room temperature, initiating the phase-separation process. Uniaxial tension, dynamic shear and infrared spectra of these samples were measured as a function of time providing insight into the effects of hydrolytic degradation and the relationship of mechanical and molecular-level properties. An Avrami-type analysis shows two distinct processes whose characteristics vary as a function of increased hydrolysis. LA-UR 04-6447.     

Long term degradation of poly(?-caprolactone) films in biologically related fluids

The aim of this work was to study the long term degradation behaviour of poly(?-caprolactone) (PCL) films, potentially useful as substrates for tissue engineering, obtained by two different methods (compression moulding or casting in chloroform) in two biologically related media: phosphate buffered solution (PBS) and Dulbecco's modified Eagle's medium (DMEM). The films were characterized at different degradation times by differential scanning calorimetry (DSC), Scanning Electron Microscopy (SEM) and Fourier Transform Infrared Spectroscopy (FTIR). The molecular weight was determined by Gel Permeation Chromatography (GPC). Chemiluminescence (CL) was used to assess physical or chemical changes from the early stage of the degradation. A different behaviour is observed in samples immersed in PBS when compared with those treated in DMEM. In this medium, the degradation after one year and a half (18 months) shows that although the chemical structure has been modified, the layers become more fragile but maintain their consistency. A higher degradation rate is obtained for membranes obtained by casting with respect to those obtained by compression moulding.     

Composting and biodegradation of thermally processed feather keratin polymer

Proteins obtained from agricultural sources represent a unique feedstock from which to prepare thermally processable polymers. In this study, thermally processed feather keratin films were composted with three-month-old compost inoculum in self-heating laboratory composters for 30 days and temperature and carbon dioxide development monitored. About 24% of the available carbon in the feather keratin polymer (FKP) was metabolized in this time and this may not be high enough for some applications. Degradation of the feather keratin polymers was observed within 10 days with concurrent molecular weight reduction measured using FT-IR. Visual inspection of the polymers also showed destruction of the films. A change in crystallinity was observed in DSC analysis and some degradation processes could be inferred from this as well.