As the plastics sector moves towards sustainable growth and development, natural fibres start to play an important role as constituents in composite materials in several industries including automotives. However, drawbacks such as fibre-matrix incompatibility and poor fibre dispersion still exist. In this thesis, Kraft pulp fibre (KF)-Polylactic Acid (PLA) composites were prepared using thermal compounding and aqueous blending to study fibre-matrix interactions. Fibre surfaces were also modified to improve fibre dispersion and water absorption properties. A biorefinery lignin was added to PLA and high density polyethylene (HDPE) as a biofiller and potential interface modifier. Aqueous blended composites showed better mechanical and dynamic mechanical performance than the thermally compounded materials. The fibre surface modification improved dispersion and material properties at higher fibre content. Furthermore, the addition of lignin to polymers resulted in improved mechanical properties in both PLA and HDPE; however, lignin failed to improve interface bonding between KF and PLA.

As the plastics sector moves towards sustainable growth and development, natural fibres start to play an important role as constituents in composite materials in several industries including automotives. However, drawbacks such as fibre-matrix incompatibility and poor fibre dispersion still exist. In this thesis, Kraft pulp fibre (KF)-Polylactic Acid (PLA) composites were prepared using thermal compounding and aqueous blending to study fibre-matrix interactions. Fibre surfaces were also modified to improve fibre dispersion and water absorption properties. A biorefinery lignin was added to PLA and high density polyethylene (HDPE) as a biofiller and potential interface modifier. Aqueous blended composites showed better mechanical and dynamic mechanical performance than the thermally compounded materials. The fibre surface modification improved dispersion and material properties at higher fibre content. Furthermore, the addition of lignin to polymers resulted in improved mechanical properties in both PLA and HDPE; however, lignin failed to improve interface bonding between KF and PLA.

Thesis (M.S.)--Michigan State University. Packaging, 2008. / Title from PDF t.p. (Proquest, viewed on Aug. 11, 2009) Includes bibliographical references.

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.

Nowadays, plastic waste poses one of the greatest risks to the environment. Plastics affect the environment at all stages of their life cycle. Bioplastics have become widely used as a substitute for conventional plastics, without detailed examination of their behavior in real environmental conditions. As a result, it is assumed that they can accumulate in the environment and the question arose as to how to identify them. The main goal of this thesis is to develop a method based on sample pyrolysis that is suitable for the identification and determination of the amount of PLA microplastics in soil and other solid matrices. Three types of soils and sludge were used for analysis. These matrices were spiked to obtain concentration ranges 0,2% - 5,0%. The pyrolysis resulted in evolution of gases with the signals m/z 29, 43 and 44, witch originated from PLA and are suitable for qualitative and quantitative analysis. Analysis of PLA in sludge was more complicated due to similarity of gases evolved from pure matrices. We tested three approaches based on analysis of signal´s peak areas, intensities and temperatures of gas evolution. While the first approach failed, the last two approaches appeared to be promising for qualitative and quantitative analysis of PLA in the sludge. Several methods suitable for qualitative and quantitative analysis of even very small amounts of PLA in soils and sludge have also been designed/developed. These methods were based on analysis of the composition and dynamics of the released gases and the characterisctic degradation temperatures.

Alginate is a widely used biomaterial for a variety of biomedical applications ranging from drug delivery to cell transplantation. The unique polysaccharide backbone endows the material with a number of useful properties such as hydrophilicity, biocompatibility, and gelation ability. Despite these advantages, one limitation for alginate is the lack of a tunable degradation rate, and its gels may only partially degrade and implants are not fully cleared from the body long after their purpose is fulfilled. To further extend the utility of this biomaterial, we hypothesized that by creating a polymer chimera between polylactic acid (PLA) and alginate we can integrate tunable degradation properties into alginate hydrogels. The alginate-b-PLA diblock copolymers were synthesized by utilizing an inverse electron demand Diels-Alder reaction, and were then fabricated into hydrogels using two approaches: doping with low viscosity alginate (LWA) and direct gelation. These hydrogel chimeras exhibited degradation rates that could be tuned from days to weeks. Morphologically, the combination of different domain sizes of alginate and PLA contributed to different microstructures within the hydrogel matrix that contributes to its degradability. Drug release was not impacted by matrix degradation rate, as four different encapsulated payloads of variable hydrophobicity and molecular weight were encapsulated with the chimeric hydrogels showed comparable release rates to non-degradable alginates. These new degradable alginates could have future utility as degradable drug-eluting implants. / 2022-09-24T00:00:00Z

No description available.

Biodegradable polyesters, such as poly(DL-lactic-co-glycolic acid) (PLGA), have been used to fabricate porous bone scaffolds to support bone tissue development. These scaffolds allow for cell seeding, attachment, growth and extracellular matrix production in vitro and are replaced by new bone tissue when implanted into bone sites in vivo. Hydroxyapatite (HAP) and μ-tricalcium phosphate (μ-TCP) ceramics have been incorporated into PLGA bone scaffolds and have been shown to increase their osteoconductivity (support cell attachment). Although HAP, μ-TCP, and biodegradable polyesters are osteoconductive, there is no evidence that these scaffold materials are osteoinductive (support cell differentiation). Calcium and phosphate ions, in contrast, have been postulated to be osteogenic factors that enhance osteoblast differentiation and mineralization. Recently, a zirconia-hybridized pyrophosphate stabilized amorphous calcium phosphate (Zr-ACP) has been synthesized which permits controlled release of calcium and phosphate ions and thus is hypothesized to be osteoinductive. Incorporation of Zr-ACP into a highly porous poly(DL lactic-co-glycolic acid) (PLGA) scaffold could potentially increase the osteoinductivity of the scaffold and therefore promote osteogenesis when implanted in vivo. To determine the osteoinductivity of Zr-ACP, a MC3T3-E1 mouse calvarial-derived osteoprogenitor cell line was used to measure cell response to Zr-ACP. To accomplish this objective, Zr-ACP was added to cell culture at different stages in cell maturation (days 0, 4 and 11). DNA synthesis, alkaline phosphatase (ALP) activity, osteopontin synthesis and collagen synthesis were determined. Results indicate that culture in the presence of Zr-ACP significantly increased cell proliferation, ALP activity and osteopontin synthesis but not collagen synthesis. To determine the feasibility of incorporating Zr-ACP into a PLGA scaffold, PLGA/Zr-ACP composite foams (5% or 10% (w/v) polymer:solvent with 25 wt% or 50 wt% Zr-ACP) were fabricated using a thermal phase inversion technique. Scanning electron microscopy revealed a highly porous structure with pores ranging in size from a few microns to about 100 μm. The amorphous structure of the Zr-ACP was maintained during composite fabrication as confirmed by X-ray diffraction measurements. Composite scaffolds also showed significantly greater compressive yield strengths and moduli as compared to pure polymer scaffolds. The results of this study indicate that Zr-ACP enhances the osteoblastic phenotype of MC3T3-E1 cells in vitro and can be incorporated into a porous PLGA scaffold. Porous PLGA/Zr-ACP composites are promising for use as bone scaffolds to heal bone defects. / Master of Science

Dans le contexte actuel, où la préservation des ressources et le développement durable sont devenus des enjeux importants de ce siècle, la production de matériaux tant performants que respectueux de l’environnement est devenue indispensable. Ainsi, ce travail de thèse porte sur l’élaboration de matrices poreuses de biopolymères en utilisant la technologie CO2 supercritique (CO2-SC). L’utilisation du PLA permet de produire des matrices 100% biosourcées et biodégradables, alors que l’utilisation de CO2-SC permet de diminuer l’impact écologique des procédés de mise en forme. Dans un premier temps une étude paramétrique de la mise en forme de matrice de PLA par une méthode de séparation de phase thermique (TIPS) couplée à un séchage par CO2 a été réalisée. Elle a permis de produire des matrices microcellulaires de faible densité (entre 60 et 320 kg/m3) et aux propriétés structurales mécaniques modulables. L’ensemble du procédé a fait l’objet d’une analyse de cycle de vie et il a été démontré que l’utilisation du CO2-SC en remplacement de la lyophilisation a réduit d’entre 50 et 90% l’impact environnemental. Dans un second temps une étude in-situ de la séparation de phase par tomographie-X en rayonnement synchrotron a permis de mieux comprendre la mécanistique de notre procédé. Enfin, la dernière partie de ce travail a été consacré à la mise en forme de matrice de PLA sans solvant, en utilisant le CO2-SC comme agent gonflant. Les résultats obtenus ont servi à réaliser une étude comparative des deux procédés développés. / In the present context, where the preservation of resources and sustainable development became the main issues of this century, the production of more efficient and environmentally friendly materials is essential. Thus, this work deals with thedevelopment of biobased polymeric porous matrix using SC-CO2. The use of PLA makes it possible to produce 100% biosourced and biodegradable matrices, while the use of CO2-SC reduces the ecological impact of the shaping processes. In a first step, a parametric study of PLA matrix shaping by a thermal induced phase separation (TIPS) method coupled to CO2 drying was performed. Low density microcellular matrices were obtained with tunable structural and mechanical properties. The whole process was analyze by life cycle assessment and the results showed that SC-CO2 replacing freeze drying has reduced the environmental impact between 50 and 90%. Secondly, a phase separation in situ study by tomography-X synchrotron radiation tomography allowed us to better understand the mechanics of our process. Finally, the last part of this work was devoted to the implementation of a solvent free process, using SC-CO2 as a blowing agent. The results obtained were used to carry out a comparative study of the two processes developed.

3D printers that precisely fuse plastic filament are enabling medical manufacturers to produce high-quality plastic medical devices and implants. However, the low-temperature fusing process implies that post-production sterilization must also occur at a low temperature or destroy the precision of the product. This study characterizes the effects of hydrogen peroxide (H2O2) vapour sterilization on ASTM-compliant tensile samples of polylactic acid, polycaprolactone, and polycarbonate. The sterilization process caused physical deformations in polycaprolactone. Additionally, increases were observed in polycaprolactone and polycarbonate sample thickness, and in polycarbonate sample width. Decreases in E were found in all three materials, while UTS decreased in polycarbonate, and strain at UTS increased in polycaprolactone. The findings demonstrate that the materials can be compatible with H2O2 vapour sterilization, but products must be designed to accommodate for changes that occur due to sterilization. / February 2017