Tesi sul tema "Plastic Materials - Degradation"

Plastics glazing materials have properties which allow their widespread use in construction, for example as rootlights. However, they are more susceptible than is glass to degradation by weathering, notably the combined effects of ultraviolet light, heat and moisture. Examples of unacceptable durability have been seen in practice, particularly when high operating temperatures occur in sunlight. Artificial weathering tests are used to assess plastics glazing materials in a reasonably short time, two main types being utilised in this study. The applicability of ultra-fast methods of accelerated degradation has been shown to depend on the extent to which the mechanisms of degradation simulate practical weathering, since different procedures were found to promote different mechanisms in the materials tested. Misleading information was obtained when the full spectrum of solar UV and much of the visible was not adequately reproduced in the accelerated tests. In particular an established grade of PVC-U performed unexpectedly poorly under fluorescent lamps. Procedures based on xenon arc sources were found to be the most generally applicable because they better reproduce the full solar spectrum range and, hence, the typical effects observed in plastics materials in practice. Several analytical techniques were used to characterise the virgin polymers and to assess the weathered materials. Two commercial grades of each polymer type (poly[vinylchloride], polycarbonate and poly[methylmethacrylate]) were studied, and measured changes explained in terms of initial polymer properties. Profiling of chemical (e.g. carbonyl index measured by photo-acoustic fourier transform infrared), physical (e.g. molecular weight, surface gloss/roughness), optical (e.g. colour, light transmission) and mechanical properties (e.g. impact resistance) as a function of exposure period and environmental conditions enabled degradation rates and mechanisms to be established for each material. In conducting these tests particular attention was given to the control and effects of sample temperature during weathering, and to the wavelength range of the light source used. Poly(vinylchloride) was affected much more by weathering at higher temperatures, and by exposure to short wavelength radiation, than was polycarbonate, with acrylic being the most durable overall. Practical applications of this work are through Standards committees primarily. in particular with plastics rootlights (B/542/8 and CEN/TCI28/SC9).

Les déchets plastiques s’accumulent dans tous les compartiments environnementaux, et cette présence suscite un vif intérêt de la part de la communauté scientifique. Pourtant, leur étude dans les sols n’est que très récente par rapport aux rivières et océans. Ce travail de doctorat s’est donc concentré sur le comportement des micro- et nanoplastiques et des contaminants associés issus de l’amendement en compost de déchets ménagers, enrichi en débris plastiques dans un sol agricole. Les microplastiques collectés dans le sol ont un degré d’altération avancé qui favorise la libération de petites particules plastiques telles que les nanoplastiques. Afin de les identifier, une méthode d’extraction /identification a été développée et a prouvé pour la première fois la présence de nanoplastiques composés des trois polymères les plus courants dans la couche de surface du sol. Il a ensuite été démontré que ces nanoplastiques étaient présents dans les couches minérales en profondeur alors que les microplastiques n’étaient présents que dans la profondeur de labour. Les nanoplastiques sont donc mobiles dans les sols et ont la capacité d’atteindre les nappes d’eau souterraines sous-jacentes. Enfin, le rôle de déchets plastiques dans la contamination concomitante en métaux relevée dans le sol a été étudié. Les plus fortes concentrations correspondent aux métaux utilisés comme additifs dans la formulation des plastiques mais les plastiques n’ont pu être mis en cause avec certitude dans la contamination du sol. Les métaux et leur signature isotopique représentent cependant de bons candidats pour le traçage des nanoplastiques dans les matrices naturelles complexes
Plastic waste is accumulating in all environmental compartments, and its presence is of great interest to the scientific community. However, plastic waste study in soils is only very recent compared to rivers and oceans. This PhD work therefore focused on the behaviour of micro- and nanoplastics and associated contaminants from the composting of household waste enriched with plastic debris in agricultural soil. The microplastics collected in soil have an advanced degree of weathering that favours the release of small plastic particles such as nanoplastics. In order to identify them, an extraction/identification method was developed and highlighted for the first time, the presence of nanoplastics containing the three most common polymers in the uppermost soil surface layer. It was then demonstrated that these nanoplastics were present in the mineral layers at depth, whereas the microplastics were only present at ploughing depth. Nanoplastics are therefore mobile in soils and can reach the underlying groundwaters. Finally, the role of plastic waste in the concomitant metal contamination found in soil was investigated. The highest concentrations correspond to metals used as additives in the formulation of plastics, but the plastic role could not be implicated with certainty in soil contamination. However, metals and their isotopic signatures are good candidates for tracing nanoplastics in complex natural matrices

Poly ((R)-$ beta$-hydroxybutyrate), PHB, is a naturally-occurring thermoplastic polyester of widespread interest due to its inherent biodegradability. A synthetic racemic analogue, poly ((R,S)-$ beta$-hydroxybutyrate), was prepared via the methylaluminoxane-catalyzed polymerization of (R,S)-$ beta$-butyrolactone, and fractionated to yield a range of tacticities, including new material primarily syndiotactic in nature. Each fraction was characterized, and the syndiotactic crystal structure was examined. An x-ray fibre diagram was recorded, the measured reflections were indexed, and a tetragonal unit cell was assigned.
To supplement the initial characterization and probe the polymerization mechanism, high resolution $ sp{13}$C nmr spectra were obtained for the full tacticity range of the racemic PHB and interpreted with regard to several statistical models. A two-site model involving enantiomorphic and first-order Markovian sites was proposed, and the parameters describing each sample were derived. Average isotactic and syndiotactic block lengths were also calculated.
The connection between stereoregularity and crystalline morphology was probed through the precipitation of single crystals. Lamellar single crystals similar to those of bacterial PHB were obtained from isotactic racemic PHB even of low stereoregularity; syndiotactic PHB gave a non-diffracting precipitate of two morphologies apparently differing in tacticity. Cocrystallization of R and S repeat units was implied.
In recognition of the important of biodegradation to the interest in this material, the enzymatic degradability of the synthetic PHB was investigated, using extracellular PHB depolymerases of both bacterial and fungal origin. For solvent-cast films of PHB, the rates of weight loss decreased in the order bacterial PHB $>>$ synthetic atactic $>$ synthetic isotactic $>$ synthetic syndiotactic in both enzyme systems. The relative degradation rates of the synthetic samples changed significantly when the single crystals of natural and synthetic PHB were degraded. These observations were interpreted in terms of the opposing effects of crystallinity and stereochemistry, and the assumed normalization of crystallinity differenced in the single crystals of different tacticity. Differenced between the two enzyme systems, preferential enzymatic attack on the edge or fold surfaces of the single crystals, and the implications in terms of chain cleavage mechanism were also examined.

E-glass has been widely used as a reinforcing material for years, especially as a plastic reinforcer in the production of GRP (Glass Reinforced Plastic). Failure of GRP materials under stress came in to the picture quite recently. Since then studies have been conducted in an attempt to understand the causes and the underlying behaviour.Except for the last section of the research (analysis using a kinetic approach) where glass fibre was cut out to weigh approximately 1.0g, standard sized specimens were soaked in the required acid solutions of desired concentrations for varying temperatures and time frames. Wherever tensile strength retention was measured, LLOYD instrument was employed. Leaching of the cations were analysed using Inductively Coupled Plasma – Optical Emission Spectroscopy (ICP-OES and also know and ICP-AES).The scope of this project can be divided in to four sections; first section involved investigating the effects of malonic acid. The study of malonic acid was narrowed to investigating the trend in strength retention. A rapid strength loss was observed initially followed by a much steady decline in the strength. However the continuation of the loss of strength was unmistakable throughout the time period of exposure. Furthermore, temperature can be observed as a facilitating factor in this degradation reaction.Secondly the corrosive effect of glyoxylic acid on E-glass fibre was studied. This was explored at two different temperatures for two specific time frames using various concentrations of the acid of interest. The influence of this acid on the glass fibre was found out in terms of strength retention and loss of cations from the glass matrix. The mildness of this acid was accentuated by the fact that 70% or more of the strength was retained at all the conditions employed. A minima in strength retention was observed at 2M acid concentration similar to the trends observed in the past (Betz and Jones 2003 and Jones and Chandler 1986). Leaching of cations reflected this trend. The large strength retention could be related to the fewer amounts of Ca and K leached from the glass matrix (Kumosa and Qui, 1997). Similar to malonic acid, an unusually large amount of B was leached out that could be due to the favourable orientation of the anion with the trivalent ions during the complex formation. Yet again temperature was found to enhance the degradation process.Next the extent of passivation (if any) showed by malonic acid was investigated using E-glass fibre pre-treated in 5M malonic acid and post treated in known corrosive acids hydrochloric acid and oxalic acid. Passivation of malonic acid was put to test through examination of strength retention of the fibres under these conditions. This segment was carried out as an extension of a finding (a behaviour synonymous to passivation) shown by malonic that surfaced the previous year by the present researcher. Increasing the pre-treatment time showed a great improvement in the retained strength for all the post-treatment acid mediums. Furthermore, while Jones and Betz (2004) featured 20-40% strength retention within a short time frame in 3M HCl, the immense amount of strength retention (60-70%) preceding pre-treatment should definitely be noted. Similarly strength retention of about 80% was observed when post-treated with the severely corrosive oxalic acid. Hence its is clear that passivation can be induced through prolonged pre-treatment in 5M malonic acid that could inhibit the attack of corrosive acid at least for a period of time.The last fragment of the study focussed on understanding and working out the mechanism behind the reactions between the E-glass fibre and acid medium in terms of kinetics. The acids utilized were 1.5M malonic acid and 3M glyoxylic acid and the assessments were made through the analysis of the weight changes brought about by the acid medium at various temperatures and time frames. In addition leaching patterns of cations were evaluated as this could contribute in achieving the objective. Maximum weight loss reached 4% in glyoxylic acid while that for malonic acid exceeded 20%. The general trend was that the glass fibres lost weight in both acids for a period of time followed by an evident weight gain. Furthermore the weight loss results fit the first order rate law. While the leaching of cations reflects the weight loss for the shorter time frames, steady loss of ions was visible even for the longer time frames where the weight has increased. The weight gain could be explained in terms of binding of anions to certain cations on the glass surface, accounting for the hindrance in the loss of cations at the longer time frames as well. About 50% of weight loss was associated to Ca while 20% was to Al, leaving 6% to B where as the rest of the ions had shown almost insignificant contribution to the weight loss.

E-glass has been widely used as a reinforcing material for years, especially as a plastic reinforcer in the production of GRP (Glass Reinforced Plastic). Failure of GRP materials under stress came in to the picture quite recently. Since then studies have been conducted in an attempt to understand the causes and the underlying behaviour.
Except for the last section of the research (analysis using a kinetic approach) where glass fibre was cut out to weigh approximately 1.0g, standard sized specimens were soaked in the required acid solutions of desired concentrations for varying temperatures and time frames. Wherever tensile strength retention was measured, LLOYD instrument was employed. Leaching of the cations were analysed using Inductively Coupled Plasma – Optical Emission Spectroscopy (ICP-OES and also know and ICP-AES).
The scope of this project can be divided in to four sections; first section involved investigating the effects of malonic acid. The study of malonic acid was narrowed to investigating the trend in strength retention. A rapid strength loss was observed initially followed by a much steady decline in the strength. However the continuation of the loss of strength was unmistakable throughout the time period of exposure. Furthermore, temperature can be observed as a facilitating factor in this degradation reaction.
Secondly the corrosive effect of glyoxylic acid on E-glass fibre was studied. This was explored at two different temperatures for two specific time frames using various concentrations of the acid of interest. The influence of this acid on the glass fibre was found out in terms of strength retention and loss of cations from the glass matrix. The mildness of this acid was accentuated by the fact that 70% or more of the strength was retained at all the conditions employed. A minima in strength retention was observed at 2M acid concentration similar to the trends observed in the past (Betz and Jones 2003 and Jones and Chandler 1986). Leaching of cations reflected this trend. The large strength retention could be related to the fewer amounts of Ca and K leached from the glass matrix (Kumosa and Qui, 1997). Similar to malonic acid, an unusually large amount of B was leached out that could be due to the favourable orientation of the anion with the trivalent ions during the complex formation. Yet again temperature was found to enhance the degradation process.
Next the extent of passivation (if any) showed by malonic acid was investigated using E-glass fibre pre-treated in 5M malonic acid and post treated in known corrosive acids hydrochloric acid and oxalic acid. Passivation of malonic acid was put to test through examination of strength retention of the fibres under these conditions. This segment was carried out as an extension of a finding (a behaviour synonymous to passivation) shown by malonic that surfaced the previous year by the present researcher. Increasing the pre-treatment time showed a great improvement in the retained strength for all the post-treatment acid mediums. Furthermore, while Jones and Betz (2004) featured 20-40% strength retention within a short time frame in 3M HCl, the immense amount of strength retention (60-70%) preceding pre-treatment should definitely be noted. Similarly strength retention of about 80% was observed when post-treated with the severely corrosive oxalic acid. Hence its is clear that passivation can be induced through prolonged pre-treatment in 5M malonic acid that could inhibit the attack of corrosive acid at least for a period of time.
The last fragment of the study focussed on understanding and working out the mechanism behind the reactions between the E-glass fibre and acid medium in terms of kinetics. The acids utilized were 1.5M malonic acid and 3M glyoxylic acid and the assessments were made through the analysis of the weight changes brought about by the acid medium at various temperatures and time frames. In addition leaching patterns of cations were evaluated as this could contribute in achieving the objective. Maximum weight loss reached 4% in glyoxylic acid while that for malonic acid exceeded 20%. The general trend was that the glass fibres lost weight in both acids for a period of time followed by an evident weight gain. Furthermore the weight loss results fit the first order rate law. While the leaching of cations reflects the weight loss for the shorter time frames, steady loss of ions was visible even for the longer time frames where the weight has increased. The weight gain could be explained in terms of binding of anions to certain cations on the glass surface, accounting for the hindrance in the loss of cations at the longer time frames as well. About 50% of weight loss was associated to Ca while 20% was to Al, leaving 6% to B where as the rest of the ions had shown almost insignificant contribution to the weight loss.

Conventional plastics have been used for decades in a diverse range of applications, however, many are resistant to degradation, leading to environmental pollution and their manufacture is dependent on non-renewable fossil fuels. Therefore, there has been an increasing need for eco-friendly biodegradable materials from renewable resources. Poly(lactic acid) (PLA) is a compostable polyester with a hydrolysable backbone that is susceptible to biodegradation and produced from renewable feedstocks. PLA has mechanical qualities comparable to non-biodegradable plastics, and currently is commercialized as food-packaging polymer for short shelf-life products. However, while PLA hydrolysis at elevated temperatures proceeds abiotically, ultimately releasing lactic acid and short chain oligomers, the role of microorganisms is unclear. Since PLA short-shelf life products are disposed after use, understanding the role of microorganisms and the effect of degradation on microbial populations in the environment is important. Therefore, the aims of this research was to (a) determine the relative importance of biotic and abiotic factors on PLA degradation; (b) to isolate putative fungal PLA degraders from the surface of PLA when buried in compost or soil and to test their ability to degrade PLA; (c) to assess the impact of PLA degradation on fungal communities when entering compost systems. The roles of abiotic and biotic factors in the degradation of high molecular weight PLA were investigated by comparing degradation rates in compost, soil and sterile water at temperatures of 25°, 37°, 45°, 50° and 55°C. Tensile strength loss and molecular weight decline of PLA in microorganism-rich compost and soil were greater than chemical hydrolysis in sterile water at elevated temperatures (above 45°C) indicating microorganisms can directly enhance PLA degradation. Since extensive fungal growth was observed on the surface of PLA when buried in compost and soil, putative fungal PLA degraders were isolated from PLA surface and their community profile on PLA surface was compared with the compost and soil community with a molecular method, terminal restriction fragment polymorphism (TRFLP). Among the identified fungi, Thermomyces lanuginosus was the dominant isolate recovered and shown to enhance PLA degradation in compost at 50°C. The fungal community profile on PLA surface was different than the fungal profile in compost and soil suggesting enrichment for PLA degraders on the surface of PLA. In order to determine the impact of PLA degradation on the fungal compost community, two different high molecular weight PLA sources, films and granules were buried in compost at 10%, 25% and 50% (w/w) concentration for 4 months at 25°C and 50°C and the community profile analysed by TRFLP and pyrosequencing. TRFLP revealed that when PLA did not degrade, the fungal community shifted back toward the initial compost community profile, however, when PLA degraded to its monomers releasing lactic acid at 50°C at a concentration of 50% (w/w) it changed the fungal community profile and decreased the fungal diversity. Pyrosequencing revealed that the presence of PLA enriched for Thermomyces in the compost population over time.

This thesis is focused in three areas: An investigation of a thermodynamic criterion for failure by environmental stress cracking using observations of the wetting behavior of stress-cracking liquids on glassy polymer substrates; Determination of the dominant chemical and physical degradation mechanisms associated with exposure of poly-p-phenylenebisbenzoxazole fiber to moisture moisture and UV-Vis spectrum light; And finally, the effect of constraint on fracture at a bi-material interface is investigated using a model epoxy-metallic adherend specimen. The wetting behavior of an ESC liquid on polycarbonate substrates has been evaluated as a function of substrate stress using a variation of Contact Adhesion Testing, a novel method of measuring small contact angles by refraction and conventional goniometry. The inelastic and elastic strain condition and time to the onset of crazing were also observed. A normalization of the time to onset of crazing using stress state, solubility difference and diffusion coefficients was shown to collapse the kinetic observations. A comprehensive study of the degradation mechanisms of PBO AS fiber exposed in a controlled manner to challenging chemical environments, moisture and UV-Visible spectrum light was undertaken. Fibers were characterized using a broad range of mechanical and physical tests including tensile testing, Elemental Analysis, scanning electron microscopy, small angle X-ray diffraction, wide angle X-ray diffraction and attenuated total reflectance infrared spectroscopy. Degradation by moisture is found to be primarily due to a loosening of the fiber's fibrillar structure. Degradation by UV-Visible spectrum light is found to be chemical in nature involving hydrolytic disruption of the oxazole ring and possible subsequent conversion to an amide bond. Approaches to alleviation of PBO AS fiber degradation were studied including super-critical carbon dioxide extraction of residual acid, the use of UV-Vis blocking coatings, compaction of the fiber microstructure and PBO AS/Siloxane composites prepared in super-critical carbon dioxide. Finally, the effect of constraint on fracture at the interface between a polymer and adherend having orders of magnitude larger stiffness was studied using a model epoxy/metallic adherend system. Fracture energy was measured using an Elastic Wedge Opened Double Cantilevered Beam test and the process zone imaged using photoelastic methods.

High-performance fibers used for ballistic protection are characterized by having outstanding mechanical properties such high modulus and strength. These mechanical properties are granted by the fiber’s chemical and physical structure as well as their high degree of orientation. Twaron fibers are one of the most commonly used fibers on soft body armors such as bulletproof vests. They are made from poly (p-phenylene terephthalamide) (PPTA), a rigid-rod and highly crystalline polymer. Although these fibers are crystalline and have great mechanical properties, their performance can decrease when they are exposed to different degradation factors. Free volume is the unoccupied space between the polymer molecules. It is responsible for characteristics such as diffusion and viscosity. Hence, the free volume changes as the polymer degrades. This thesis focuses on the effects of sonication, pH changes, and sweat on the free volume of PPTA fibers.

A non-destructive technique known as positron annihilation lifetime spectroscopy (PALS) was used to measure the free volume in PPTA. Changes in the free volume of fibers degraded under different conditions were compared to their mechanical performance. Degradation in DI water, pH 4 and pH 10 aqueous solutions was conducted for 10 weeks at 80^oC. Sweat degradation of PPTA fibers was also conducted for 10 weeks at 25^oC, 50^oC, and 100^oC. Fibers degraded in pH4 and sweat solutions had greater loss of mechanical performance and changes in the free volume. PALS was able to detect changes in the nanostructure of PPTA fibers at early stages of degradation. This data was supported by mechanical tests and is complementary to other characterization techniques such as small angle X-ray scattering (SAXS). Results of this research are a steppingstone for future studies on lifetime predictions of bulletproof vests and the development of the next generation of soft body armors.