Ce travail de thèse repose principalement sur l’étude de l’impact des facteurs environnementaux (température, humidité, pH) sur le vieillissement des fils de HT-PVAl destinés à la conception des bandes géosynthétiques. Les objectifs étaient d’identifier les produits, les mécanismes et les cinétiques de dégradation, et de déterminer l’impact du vieillissement sur la structure chimique, les propriétés physiques et mécaniques des fils. Il s’agissait aussi de proposer une méthodologie générale d’étude de la durabilité des produits géosynthétiques à base de fils de HT-PVAl. Ces derniers sont sujets à deux types de vieillissement : un vieillissement physique par absorption de l’humidité existante dans les sols, et un vieillissement chimique par exposition aux conditions physico-chimiques des sols. Pour mieux comprendre l’impact de chaque facteur (température, humidité, pH), des essais de vieillissement accélérés ont été réalisés dans trois distincts environnements : le vieillissement thermique dans l’air entre 70 et 120°C, le vieillissement humide entre 0 et 100 % d’humidité relative et entre 22 et 70°C, et le vieillissement chimique dans des solutions aqueuses acide (acide sulfurique, pH = 2,4) et alcaline (hydroxyde de sodium, pH = 12) entre 50 et 70°C. Les échantillons ont été caractérisés à différentes échelles structurales : moléculaire, macromoléculaire, morphologique et macroscopique. Cette approche multi-technique et multi-échelle a permis de déterminer les principaux paramètres régissant la cinétique de dégradation des fils de HT-PVAl dans des conditions de vieillissement proches de celles de l’application. De plus, elle a permis de mettre en évidence des traceurs de dégradation qui pourront être ensuite utilisés pour évaluer l’état de dégradation des produits de renforcement dans le temps. / This PhD thesis is mainly based on the study of the impact of environmental factors (temperature, humidity, pH) on the aging of HT-PVAl yarns for the design of geosynthetic strips. The objectives were to identify the degradation products, mechanisms and kinetics, and to determine the impact of aging on the chemical structure, the physical and mechanical properties of the yarns. This study was also aimed at proposing a general methodology for studying the durability of geosynthetic products based on HT-PVAl yarns. These latter are subject to two types of aging: physical aging by absorbing moisture existing in soils, and chemical aging by exposure to the physicochemical conditions of soil. In order to better understand the impact of each factor (temperature, humidity, pH), accelerated aging tests were done in three different environments: thermal aging in air between 70 and 120°C, humid aging between 0 and 100% relative humidity and between 22 and 70°C, and chemical aging in acidic (sulfuric acid, pH = 2.4) and alkaline (sodium hydroxide, pH = 12) aqueous solutions between 50 and 70°C. The samples were characterized at different structural scales: molecular, macromolecular, morphological and macroscopic scales. This multi-technical and multi-scale approach allowed determining the main parameters governing the degradation kinetics of HT-PVAl yarns in aging conditions close to application conditions. In addition, it allowed evidencing degradation tracers that will be then help us to evaluate the degradation state of reinforcement products against time of exposure.

This diploma thesis deals with the preparation of solid hydrophilic sponges made of acetalized PVAl. The sponges were produced by foaming by gaseous reaction by-product. The experimental work also includes the study of active compound immobilization into the sponge (finely ground lignite as a heavy metal sorbent).

This diploma thesis deals with a detailed study of photoinitiated radical polymerization of macromers base on PVAl containing lateral GMA moieties. The main goal is the evaluation of the influence of photoinitiator concentration, polymerisable group content and/or other aditives on the polymerisation rate. Other goals include the study of possible influencing the photochemical speed by lowering the glass transition temperature, compatibility with various photoinitiators etc. Attention is also paid to the study of prepared 3D polymeric networks properties

The diploma thesis deals with a detailed study of he esterification reaction between PVAl and acrylic and methacrylic acids. Tha goal is to prepared PVAl-based macromers bearing (meth)acrylic moieties bound to PVAl macromolecular backbone. Attention will be paid especially to equlibrium establishing times and to the influence of reaction mixture composition on the properties of resulting products.

It is necessary to understand the erodibility and hydrological response of mine-site slope forming materials (SFMs), because of increasing awareness of the environmental impacts of mining. Steep engineered slopes in high intensity rainfall environments present a serious erosion risk. Temporary surface stabilisers, such as polyacrylamides (PAMs) and polyvinylacrylic latex (PVALs) are potentially cost effective erosion control solutions. In this study PAM and PVAL efficacy to reduce runoff, leachate and erosion was assessed at two application rates, with and without gypsum on SFMs from an iron ore mine in Guinea (West Africa). NSPASS (near-surface photogrammetry assessment of slope forming materials’ surface roughness) is a novel method that integrates digital image capture and GIS. It is shown to detect and quantify surface micro-relief changes of 2-3 mm, not visible to the naked eye. As expected, soil and non-soil SFMs were significantly different in terms of their physical and chemical properties. Phase I of the study investigated the erodibility of ten SFMs, including soil, ore and waste-rock. The results indicate that the hydrological response to rainfall of most SFMs is to generate leachate. Weathered phyllite (PHY-WEA) is the most erodible SFM by both runoff and leachate. Multiple regression analysis demonstrated that magnetic susceptibility, mineralogy and dry aggregate distribution; parameters not commonly assessed in erosion studies, are important in explaining SFM erodibility and hydrological response. Phase II evaluated critically the effectiveness of three commercially available polymer solutions (two PAMs and one PVAL) at reducing runoff, leachate and erosion from four of the most erodible SFMs identified in Phase I. The results indicate that some PAM and PVAL treatments significantly reduce runoff, leachate and erosion. Polymer efficacy is highly dependent on the physical and chemical properties of the SFM, as well as the mechanism of polymer to SFM adsorption. Increasing the application rate of select treatments lowered leachate volumes, runoff and leachate total sediment loads. Contrary to previous studies, gypsum amendments did not significantly improve polymer efficiency. This research has added to our understanding of the erodibility and hydrological response of soil and non-soil SFMs. This is the first study to evaluate critically the efficacy of PVALs in controlling erosion from mine-site SFMs. Future studies should continue to optimise NSPASS performance in monitoring changes in surface micro-relief.

Orientador: Danielle Goveia / Resumo: Estudos epidemiológicos mostram que uma parcela significativa da população mundial, independente de idade, etnia e localização geográfica, apresenta baixos níveis séricos de vitamina D3. Neste contexto, a incorporação da vitamina D3 em novos sistemas de liberação de fármacos, como os sistemas transdérmicos, têm sido apontados como alternativa para a administração deste medicamento. A extração da nanocelulose de fibras vegetais e sua utilização na fabricação de insumos da área da saúde tem se destacado na medicina, pois apresenta propriedades como biocompatibilidade, biodegradabilidade e baixa toxicidade. A celulose tem um longo histórico de aplicações na área da saúde, agindo como mediador na liberação controlada de fármacos, mas sua utilização nanoestruturada em membranas, como sistema de liberação local de fármacos ainda é um desafio. Neste estudo foi desenvolvida uma membrana, pela técnica de “casting”, de nanocelulose extraída do linter de algodão e vitamina D3 acrescidos dos componentes, álcool polivinílico, glicerina e tween 80. A nanocelulose e as membranas foram caracterizadas por microscopia eletrônica de varredura de alta resolução (MEV-FEG), espectroscopia no infravermelho com transformada de Fourier (FT-IR), teste de tração no dinamômetro e a cinética de liberação do fármaco por espectroscopia molecular no ultravioleta visível (UV-Vis). A membrana apresentou reprodutibilidade na síntese, ótimas propriedades físicas como flexibilidade, transparência e elasticidade,... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Epidemiological studies show that a significant portion of the population has low serum vitamin D3 levels, regardless of age, ethnicity and geographical location. In this context, the incorporation of vitamin D3 in new drug delivery systems, such as transdermal systems, has been suggested as an alternative for the administration of this drug. The extraction of nanocellulose from plant fibers and its use in the manufacture of health inputs has been highlighted in medicine, as it has properties such as biocompatibility, biodegradability and low toxicity. Cellulose has a long history of healthcare applications, acting as a mediator in controlled drug release, but its nanostructured use in membranes as a local drug delivery system is still a challenge. In this study a membrane was developed by casting technique of nanocellulose extracted from cotton linter and vitamin D3 plus the components, polyvinyl alcohol, glycerin and tween 80. Nanocellulose and membranes were characterized by high scanning electron microscopy. resolution (SEM-FEG), Fourier transform infrared spectroscopy (FT-IR), dynamometer tensile test and drug release kinetics by visible ultraviolet molecular spectroscopy (UV-Vis). The membrane showed reproducibility in synthesis, excellent physical properties such as flexibility, transparency and elasticity, as well as adequate resistance for biomedical applications. Through the FT-IR it was observed the presence of all active components in the sample, without structura... (Complete abstract click electronic access below) / Mestre