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.

The rheological behavior analysis of Engineered Cementitious Composites (ECC) is key to understand how the different preparation techniques affect the composite mechanical performance. However, the rheological assessment of reinforced materials becomes more complex since fibers usually cause flow disturbances not found in nonreinforced cementitious materials. Besides that, simple workability measurement techniques are not able to fully understand the composite behavior in the fresh state creating the need for more precise techniques to be employed. The main objectives of this study were to evaluate the ECC rheological behavior using different rheometer devices (Vane system and Ball measuring system) and investigate the influence of mixing processes on the fiber homogenization and rheological behavior. Additionally to this, a link between rheological behavior and mechanical performance was investigated. In the end, the ball measuring system revealed to be more efficient than the vane system when evaluating the composite rheological behavior. In addition, the mixing process influenced the rheological behavior of PVA-ECC especially regarding the moment which fibers are added. Fiber addition after mortar mixture improved fibers homogenization and reduced mixing energy by around 8%. Moreover, a correlation between rheological and mechanical properties showed that a 2-times variation in either yield stress or viscosity can lead to a variation of more than 50% in flexural strength without significantly affecting the composite compressive strength. It was also found that the lower the composite yield stress and viscosity the higher was its ultimate strain. To conclude, all those parameters contributed to understand the composite rheological behavior and globally optimize its performance. / Sem resumo

<p>Inkjet is a digital printing process where the ink is ejected directly onto a substrate from a jet device driven by an electronic signal. Most inkjet inks have a low viscosity and a low surface tension, which put high demands on the coating layer’s porosity and absorbency characteristics.</p><p>The aim of this study has been to gain an increased knowledge of the mechanisms that control the sorption and fixation of inkjet inks on coated papers. The focus has been on printability aspects of high print quality (although not photographic quality) laboratory-coated inkjet papers for printers using aqueous-based inks.</p><p>Papers coated solely with polyvinyl alcohol (PVOH) and starch presented excellent gamut values and good print sharpness over the uncoated substrate, due to good film-forming characteristics observed by light microscopy and ESCA. ESEM analyses showed the complexity and variation of PVOH surface structures, which has probably explained the wide scatter in the colour-to-colour bleed results. Pure PVOH coatings also gave a surface with high gloss variations (2-8 times greater than that of commercial inkjet papers), prolonged ink drying time, and cracked prints when using pigmented inks. When an amorphous silica gel pigment (with broad pore size distribution) was used in combination with binder, a new structure was formed with large pores in and between the pigments and a macro-roughness generated by the large particles. The inkjet ink droplets could quickly penetrate into the large pores and the time for surface wicking was reduced, which was beneficial for the blurriness. However, the macro-roughness promoted bulk spreading in the coarse surface structure, and this tended to increase the line width. Finally, when the ink ends up within the coating, the colorant is partly shielded by the particles, and this reduced the gamut area to some extent. The binder demand of the silica pigments was strongly related to their pore size distributions. Silica gel required two to three times the amount of binder compared to novel surfactant-templated mesoporous silica pigments (with small pores and narrow pore size distribution). This finding was attributed to the significant penetration of PVOH binder into the pores in the silica gel, thereby, increasing its binder demand. Furthermore, this binder penetration reduced the effective internal pore volume available for rapid drainage of the ink vehicle. Consequently, the surfactant-templated pigments required significantly lower amounts of binder, and gave improvements in print quality relative to the commercial pigment.</p>

Inkjet is a digital printing process where the ink is ejected directly onto a substrate from a jet device driven by an electronic signal. Most inkjet inks have a low viscosity and a low surface tension, which put high demands on the coating layer’s porosity and absorbency characteristics. The aim of this study has been to gain an increased knowledge of the mechanisms that control the sorption and fixation of inkjet inks on coated papers. The focus has been on printability aspects of high print quality (although not photographic quality) laboratory-coated inkjet papers for printers using aqueous-based inks. Papers coated solely with polyvinyl alcohol (PVOH) and starch presented excellent gamut values and good print sharpness over the uncoated substrate, due to good film-forming characteristics observed by light microscopy and ESCA. ESEM analyses showed the complexity and variation of PVOH surface structures, which has probably explained the wide scatter in the colour-to-colour bleed results. Pure PVOH coatings also gave a surface with high gloss variations (2-8 times greater than that of commercial inkjet papers), prolonged ink drying time, and cracked prints when using pigmented inks. When an amorphous silica gel pigment (with broad pore size distribution) was used in combination with binder, a new structure was formed with large pores in and between the pigments and a macro-roughness generated by the large particles. The inkjet ink droplets could quickly penetrate into the large pores and the time for surface wicking was reduced, which was beneficial for the blurriness. However, the macro-roughness promoted bulk spreading in the coarse surface structure, and this tended to increase the line width. Finally, when the ink ends up within the coating, the colorant is partly shielded by the particles, and this reduced the gamut area to some extent. The binder demand of the silica pigments was strongly related to their pore size distributions. Silica gel required two to three times the amount of binder compared to novel surfactant-templated mesoporous silica pigments (with small pores and narrow pore size distribution). This finding was attributed to the significant penetration of PVOH binder into the pores in the silica gel, thereby, increasing its binder demand. Furthermore, this binder penetration reduced the effective internal pore volume available for rapid drainage of the ink vehicle. Consequently, the surfactant-templated pigments required significantly lower amounts of binder, and gave improvements in print quality relative to the commercial pigment.

Atherosclerosis is the number one cause of death in the United States and one of the most common treatments is the implantation of a stent. In order to eliminate the two most common complications - restenosis and thrombosis - a novel covered stent is investigated. A covered stent membrane should be able to undergo large stretch, prevent restenosis, and be relatively non-thrombogenic. Polyvinyl alcohol (PVA) cryogels are examined as a candidate material for covered stent membranes. Mechanical testing included uniaxial tensile testing, puncture testing, and the fabrication and expansion of PVA cryogel covered stents. Uniaxial testing showed PVA cryogels to have sufficient ultimate stretch which was similar to bare metal stents during deployment. Puncture testing revealed that PVA cryogels are not likely to puncture in vivo. No tears were seen in the PVA cryogel membrane after expansion of the covered stents. Finite element analysis was used to determine a PVA cryogel membrane's effect on artery wall stress. PVA cryogel covered stents reduced both artery wall stress and tissue prolapse when compared to equivalent uncovered stents. Migration assays were used to determine if PVA cryogels are able to block the smooth muscle cell migration seen during restenosis. PVA cryogels significantly reduced cellular migration in modified Boyden chambers - suggesting that they would be able to prevent restenosis in vivo. Thrombogenicity was tested in vitro with a gravity-fed flow loop using porcine blood and in vivo with a sheep model. PVA cryogels were found to be less thrombogenic than polyester controls with the flow loop system. The sheep study demonstrated the feasibility of implanting PVA cryogel covered stents and good early patency. After explantation, the PVA cryogel membranes were intact - providing in vivo evidence for the durability of PVA cryogel covered stents. Overall, this work provides evidence that covered stents made with PVA cryogels are a feasible device in terms of their mechanics, ability to prevent restenosis, and low thrombogenicity. This work represents a major advancement in the development of PVA cryogel covered stents and provides necessary safety and feasibility data for future clinical trials.

Cardiovascular disease is the leading cause of death in the United States with approximately 49% of the cardiovascular related deaths attributed to coronary heart disease (CHD). CHD is the accumulation of plaque resulting in the narrowing of the vessel lumen and a decrease in blood flow to the downstream heart muscle. In order to restore blood flow, arterial by-pass procedures can be undertaken. However, the patient's own arteries/veins may not be suitable for use as a vessel replacement, and synthetic grafts lack the compliancy and durability needed for these small diameter locations (<5 mm). Therefore, the goal of this research is to develop a nanofibrous material that can be used in vascular applications such as this. In this study, we fabricate coaxial electrospun nanofibers with gelatin in the shell and polyvinyl alcohol (PVA) in the core using 1 Gelatin: 1 PVA and 3 Gelatin: 1 PVA mass ratios. Gelatin, derived from collagen, is highly bioactive while PVA, a synthetic polymer, has appealing mechanical properties. Therefore, by combining these materials in a core-shell structure, we hypothesize that the resulting nanofibers will have enhanced mechanical properties, cellular growth and migration, as well as minimal platelet deposition and activation compared to scaffolds composed solely of gelatin or PVA. First, the coaxial scaffolds exhibited an enhanced Young's modulus and ultimate strength compared to scaffolds composed of PVA or gelatin alone. Endothelial cells had high proliferation and migration on the coaxial electrospun scaffolds with higher migration seen on the stiffer, coaxial scaffolds. The smooth muscle cells had less proliferation and lower migration rates on the coaxial scaffolds than the endothelial cells. Using a modified prothrombinase assay, the coaxial scaffolds had minimal platelet activation. Lastly, when pre-seeding the coaxial scaffolds with endothelial cells or smooth muscle cells, the platelet deposition decreased in comparison to platelet deposition with no cell pre-seeding. Overall, the 1 Gel: 1 PVA coaxial scaffolds promoted endothelial cell growth and migration, minimized smooth muscle cell growth and migration, and had minimal platelet activation. Therefore, the 1 Gel: 1 PVA coaxial nanofibers are an intriguing material for use in vascular applications.

No description available.

Polyvinyl alcohol (PVA) desize effluent is a high COD contributor to towel manufacturing plant's Primary Oxygenation Treatment of Water operation, and being non-biodegradable, is a threat to the environment. When all-PVA/wax size is used in weaving, significant incentives exist to recover the synthetic polymer material from the desize wash water stream and reuse it. A new technology that would eliminate the disadvantages of the current Reverse Osmosis Ultrafiltration (UF) PVA recovery process is Vacuum Flash Evaporation (VFE). This research adapts the VFE process to the recovery and reuse of all-PVA size emanating from towel manufacturing, and compares the economics of its implementation in a model plant to current plant systems that use PVA/starch blend sizes with no materials/water recovery. After bench scale research optimized the VFE PVA recovery process from the desize effluent and determined the mass of virgin PVA that was required to be added to the final, recycled PVA size formulations. The physical changes in the recycled size film and yarn composite properties from those of the initial (conventional) slashing were determined using a number of characterization techniques, including DSC, TGA, SEM, tensile testing, viscometry, number of abrasion cycles to first yarn breaks, microscopy and contact angle measurements. Cotton chemical impurities extracted from the yarns during desizing played an important role in the recovered PVA film physical properties. The recovered PVA improved the slashed yarn weave ability. Along with recovered PVA, pure hot water was recovered from the VFE. Virgin wax adds to the final, recycled size formulations were determined to be unnecessary, as the impurities extracted into the desize effluent stream performed the same functions in the size as the wax. Using the bench results, the overall VFE process was optimized and demonstrated to be technically viable through six cycles, proof-of-concept trials conducted on a Webtex Continuous Pilot Slasher. Based on the pilot scale trials, comparative economics were developed. Incorporation of the VFE technology for PVA size recovery and recycling resulted in ~$3.2M/year in savings over the conventional PVA/starch/wax process, yielding a raw ROI of less than one year based on a $3M turnkey capital investment.

No description available.

Orientadores: Vitor Baranauskas, William Dias Belangero / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Elétrica e de Computação / Made available in DSpace on 2018-08-18T04:41:56Z (GMT). No. of bitstreams: 1 Rodrigues_AnaAmelia_D.pdf: 6206304 bytes, checksum: 977d7fa603d9906b66ff83abcb8b5466 (MD5) Previous issue date: 2011 / Resumo: O hidrogel de polivinil álcool puro e reforçado com duas diferentes nanopartículas de carbono, produzidas pelo método de deposição química a partir da fase vapor, foi avaliado por ensaios in vitro e in vivo, para verificar seu potencial de uso para tratamento de defeitos osteocondrais. A caracterização das nanopartículas foi feita por microscópio Raman, microscopia eletrônica por emissão de campo e microscopia eletrônica de alta transmissão. Foi avaliada a citotoxicidade dos materiais com células do Vero do tipo fibroblasto e células-tronco mesenquimais derivadas da medula óssea de ratos Wistar-kyoto por ensaios de viabilidade e análise citoquimica e a diferenciação osteogênica pela atividade da enzima fosfatase alcalina e corante vermelho de alizarina. Os materiais foram implantados por 3 e 12 semanas em defeitos osteocondrais de ratos Wistar e analisados por microscopia eletrônica de varredura, microscopia óptica, ensaio mecânico de indentação e espectrometria de fluorescência de raios X. Os resultados sugerem que os materiais não interferiram na viabilidade e morfologia de nenhum tipo celular. Foi identificada a atividade da enzima fosfatase alcalina e formação de matriz orgânica mineralizada. Após implante os materiais não apresentaram sinais de desgaste ou mudança de cor. A região de interface apresentou tecido conjuntivo denso e ósseo neoformado após 3 e 12 semanas. Foi observado aumento do módulo de fluência e maior concentração de cálcio nos materiais ao longo do tempo. Os resultados indicaram que os hidrogéis com nanopartículas de carbono não interferiram na atividade metabólica de ambas as células e na diferenciação osteogênica das células mesenquimais. O desempenho destes materiais pode ser considerado melhor que o hidrogel sem nanopartículas / Abstract: Poly(vinyl alcohol) hydrogel pure and reinforced with two different carbon nanoparticles, produced by hot-filament chemical vapor deposition method, was evaluated by in vitro and in vivo assays, to assess its potential employment for the treatment of osteochondral defects. Nanoparticles characterization was done by Raman microscope, field emission scanning electron microscopy and high-resolution transmission electron microscopy. It evaluated the cytotoxicity of the materials with Vero fibroblast-type cellular and mesenchymal stem cells derived from bone marrow of Wistar-Kyoto rats by assays of viability and citochemistry analyses and osteogenic differentiation by alkaline phosphatase activity and alizarin red staining. The materials were implanted by 3 and 12 weeks in the osteochondral defects of Wistar rats and analyzed by scanning electron microscopy, optical microscopy, creep indentation and X-ray fluorescence spectroscopy. The results suggest that the materials didn't interfere in the viability and morphology of any cell type. Alkaline phosphatase activity and nodules of mineralized organic matrix formation was identified. After implantation the materials did not showed signs of wear or color change. The interface region showed connective dense tissue and bone tissue neoformed after 3 and 12 weeks. It was observed increased of creep module and more concentration of calcium of samples over time. The results indicate that the hydrogels with carbon nanoparticles not interfere in metabolic activity of both cells and osteogenic mesenchymal differentiation. The performance of these materials can be considered better than the hydrogel without nanoparticles / Doutorado / Eletrônica, Microeletrônica e Optoeletrônica / Doutor em Engenharia Elétrica