Poly(vinyl alcohol) (PVA) is a polymer used in numerous applications, principally those in which its high water solubility is a desirable asset. However there are also areas where PVA is limited by its inherent solubility (for example some specific environments in the biomedical field). This work has sought to overcome such limits by manipulating the surface of PVA in order to propose various means by which the surface solvent resistance might be increased while maintaining the bulk properties of the polymer. Both chemical and physical modifications have been tried and in each case progress has been made towards insolubilizing a single surface of the polymer when in film form. Grafting various species onto the surface of PVA was successfully performed. It is believed that such species bonded to the PVA via attachment to the hydroxyl groups (though this has not been proven conclusively). The data contained herein has led to the conclusion that the primary factor in reducing solubility this way is the removal of the hydroxyl groups, and not the attachment of specifically highly hydrophobic molecules. Introducing permanent cross-links into the surface region has been attempted via various routes. The data recorded shows promise however the system is far from optimised. The biggest challenge remaining is to optimise the depth of material cross-linked. Some steps have been made towards understanding and controlling this parameter though there is much scope for further investigation. The methods used have built on those used for bulk cross-linking and as such are new for the case of surface specific treatment. An interesting phenomenon in some semi-crystalline polymers reported in recent years is that of surface specific crystallization. This effect has been successfully induced and observed in PVA to produce what is believed to be a highly crystalline surface layer, and crystalline regions of PVA are generally accepted to be more water resistant than amorphous ones. In summary, in this work several surface-specific treatments for PVA have been trialled, providing options for post-film forming modification to reduce the surface water sensitivity whilst retaining the bulk properties of the polymer.

Pyrolysis-capillary gas chromatography combined with FID, ECD and MS detection were used to characterize refuse-derived fuel and aquatic fulvic acids. Different pyrolysis methods and programs were evaluated. Pyrolysis temperatures of 700-800°C produced the strongest signal for organics present in RDF and fulvic acid. Cellulose and fatty acids pyrolyzates were identifiable by GC-MS following preparative pyrolysis fractionation. At organic chloride content of 0.023%, only three halogenated compounds were detected in the GC-MS of the fractions. None of the priority pollutants were detected at lower detection limit of 0.72 to 24 mg/ kg RDF. Selective solvent extraction improves the reproduciblities of the technique and allows the detection of polymeric structures. Pyrograms of polyvinyl chloride and regular typing paper showed some common peaks that are present in the RDF pyrogram. About 65% of the peaks in the RDF pyrogram might be of paper origin. The organic chloride content of the RDF was evaluated by ion chromatography of the trapped pyrolyzates in 2% NaOH trap and it was found to be 221 mg Cl/ kg dry RDF. Pyrolysis conditions and temperature programs for FA were systematically evaluated. Samples included purified FA, methylated FA and HPLC separated fractions. Characteristic pyrograms were developed. Profiles of benzene, toluene, phenol, m-cresol and biphenyl from FA were evaluated. The production of phenol was the largest at 800°C, at concentration of 1.61 mg per gram of FA pyrolyzed. The profiles of benzene and toluene followed the same pathways. Both pyrolyzates had at least two precursors. HPLC fractions of FA showed some regular retention patterns characteristic of polymeric material. DL-proline, seriene and vanillic acid pyrograms showed some peaks with the same retention times as those in FA pyrogram under the same conditions. A reproducibility of 6% relative standard deviation was achieved in the pyrolysis of RDF and 0.91% in the case of FA.

Electrospinning is widely used technique to produce nanoscale constructs for tissue engineering. This technique can be used to spin wide range of polymers. One of them is polyvinyl alcohol (PVA), which has very good properties for use in this field. PVA is nontoxic, has good mechanical strength and it's degradable and biocompatible. Electrospun PVA nanofibers have limitations because of their -OH side groups. These groups cause solubility of PVA in water. The solubility can be adjusted with crosslinking techniques, but PVA still remains very hydrophilic, which is causing low adhesion of cells. In recent research we decided to reduce the hydrophilicity of PVA using plasma modification. Polymer modification with cold plasma is an economic and quite simple process to change the surface chemistry without side effects that come with conventional chemical treatment. With radical, formed by discharge, we have deposited hydrocarbons on the PVA surface and we rapidly increased hydrophobicity of the polymer surface. The change of surface chemistry has only a little effect on the fiber morphology. The increase of hydrophobicity allowed better adhesion of mesenchymal stem cells on plasma modified PVA as compared to non-modified PVA and a huge change in cell morphology was observed. These changes suggest that we...

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.

Neste trabalho foram formados, sobre uma superfície de liga de alumínio AA7075-T6, revestimentos de polianilina (PANI) e da blenda polianilina/policloreto de vinila na proporção massa-massa de 1/1 (PANI/PVC 1/1), com diferentes espessuras. Os revestimentos foram avaliados quanto as suas habilidades na proteção da corrosão da liga de alumínio. Utilizou-se uma solução de NaCl 3,5%, como solução corrosiva em todos os ensaios de corrosão. A espessura dos revestimentos de PANI foi variada de 5 a 35 µm e estudou-se a relação entre espessura, rugosidade e hidrofobicidade e a proteção por estes revestimentos. Os revestimentos com espessuras de 12 a 23 µm apresentaram menor rugosidade, maior ângulo de contato e melhor proteção da corrosão verificada por medidas eletroquímicas, tais como espectroscopia de impedância eletroquímica e polarização linear. As imagens obtidas por microscopia eletrônica de varredura mostraram que os revestimentos de PANI são homogêneos e que não exibiam defeitos decorrentes da exposição no ambiente corrosivo. Já a blenda, apresentou um desempenho maior na proteção da corrosão quando comparado com a PANI pura. Medidas de espectroscopia de impedância eletroquímica e de polarização linear mostraram que a blenda possui alta resistência de polarização, com potenciais de corrosão estáveis e deslocados à região anódica para os eletrodos com revestimentos de maior espessura (26,3 ± 0,9 µm). Imagens obtidas por microscopia eletrônica de varredura e de força atômica, juntamente com a análise de composição por espectroscopia de energia dispersiva de raios-X (EDX) contribuíram para entender a maior eficiência de proteção promovida pela blenda. / In this study, an aluminum alloy (AA7075-T6) was coated with polyaniline (PANI) and polyaniline/polyvinyl chloride (PANI/PVC in 1:1 ratio by mass) blend coatings of different thickness. These coatings were evaluated for their ability to protect the aluminum alloy against corrosion. For studying the corrosion of aluminum alloy in saline environment, a 3.5% NaCl solution was used in all the corrosion tests. The thickness of PANI-based films was varied between 5 to 35 µm and the effect of film thickness, roughness and hydrophobicity on the corrosion protection properties of the coatings was evaluated. The coatings with thickness between 12 and 23 µm exhibited lower roughness, higher contact angles and better corrosion protection as confirmed by electrochemical measurements such as electrochemical impedance spectroscopy and linear polarization. Morphological analysis by scanning electron microscopy confirmed that the PANI coatings are homogeneous and present almost no defects upon exposure to the corrosive environment. Compared to pure PANI coatings, the coatings consisting of PANI/PVC blend presented better performance against corrosion. Electrochemical impedance spectroscopy and linear polarization measurements showed that the blends have high polarization resistance with stable corrosion potentials that are shifted to the anodic region for the electrodes with thicker coatings (26.3 ± 0.9 µm). Surface analysis by scanning electron microscopy, atomic force microscopy and elemental analysis by energy-dispersive X-ray spectroscopy were used to gather information that helped understanding the better corrosion resistance of PANI/PVC coatings.

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

Neste trabalho foram formados, sobre uma superfície de liga de alumínio AA7075-T6, revestimentos de polianilina (PANI) e da blenda polianilina/policloreto de vinila na proporção massa-massa de 1/1 (PANI/PVC 1/1), com diferentes espessuras. Os revestimentos foram avaliados quanto as suas habilidades na proteção da corrosão da liga de alumínio. Utilizou-se uma solução de NaCl 3,5%, como solução corrosiva em todos os ensaios de corrosão. A espessura dos revestimentos de PANI foi variada de 5 a 35 µm e estudou-se a relação entre espessura, rugosidade e hidrofobicidade e a proteção por estes revestimentos. Os revestimentos com espessuras de 12 a 23 µm apresentaram menor rugosidade, maior ângulo de contato e melhor proteção da corrosão verificada por medidas eletroquímicas, tais como espectroscopia de impedância eletroquímica e polarização linear. As imagens obtidas por microscopia eletrônica de varredura mostraram que os revestimentos de PANI são homogêneos e que não exibiam defeitos decorrentes da exposição no ambiente corrosivo. Já a blenda, apresentou um desempenho maior na proteção da corrosão quando comparado com a PANI pura. Medidas de espectroscopia de impedância eletroquímica e de polarização linear mostraram que a blenda possui alta resistência de polarização, com potenciais de corrosão estáveis e deslocados à região anódica para os eletrodos com revestimentos de maior espessura (26,3 ± 0,9 µm). Imagens obtidas por microscopia eletrônica de varredura e de força atômica, juntamente com a análise de composição por espectroscopia de energia dispersiva de raios-X (EDX) contribuíram para entender a maior eficiência de proteção promovida pela blenda. / In this study, an aluminum alloy (AA7075-T6) was coated with polyaniline (PANI) and polyaniline/polyvinyl chloride (PANI/PVC in 1:1 ratio by mass) blend coatings of different thickness. These coatings were evaluated for their ability to protect the aluminum alloy against corrosion. For studying the corrosion of aluminum alloy in saline environment, a 3.5% NaCl solution was used in all the corrosion tests. The thickness of PANI-based films was varied between 5 to 35 µm and the effect of film thickness, roughness and hydrophobicity on the corrosion protection properties of the coatings was evaluated. The coatings with thickness between 12 and 23 µm exhibited lower roughness, higher contact angles and better corrosion protection as confirmed by electrochemical measurements such as electrochemical impedance spectroscopy and linear polarization. Morphological analysis by scanning electron microscopy confirmed that the PANI coatings are homogeneous and present almost no defects upon exposure to the corrosive environment. Compared to pure PANI coatings, the coatings consisting of PANI/PVC blend presented better performance against corrosion. Electrochemical impedance spectroscopy and linear polarization measurements showed that the blends have high polarization resistance with stable corrosion potentials that are shifted to the anodic region for the electrodes with thicker coatings (26.3 ± 0.9 µm). Surface analysis by scanning electron microscopy, atomic force microscopy and elemental analysis by energy-dispersive X-ray spectroscopy were used to gather information that helped understanding the better corrosion resistance of PANI/PVC coatings.

Orientador: Marcos David Ferreira / Resumo: Objetivo. Analisar a eficácia antimicrobiana in vitro de compósito em pó a base de prata e sua aplicação em diferentes concentrações em filmes de policloreto de vinila (PVC) produzidos em escala industrial e em laboratório. Métodos. Um material compósito constituído por dióxido de sílicio (SiO2) e nanopartículas de prata (NpAg), produzido e cedido por uma empresa de soluções tecnológicas, foi caracterizado por Microscopia Eletrônica de Varredura (MEV), Espectroscopia no Infravermelho com Transformada de Fourier (FTIR) e Difração de Raio X (DRX). Filmes de PVC industrial aditivados com 6,25, 12,5, 25 e 100 ppm de NpAg e filmes produzidos laboratorialmente pelo método de casting aditivados com 12,5, 25 e 100 ppm de NpAg foram caracterizados por Microscopia Eletrônica de Varredura (MEV), Espectroscopia no Infravermelho com Transformada de Fourier (FTIR) e Difração de Raio X (DRX). Testes microbiológicos in vitro foram realizados com o compósito de prata e com os filmes de PVC. Com o compósito realizou-se o Teste de Difusão em Ágar por poço e a Contagem de Microrganismos Viáveis. Com os filmes industrial e laboratorial realizou-se o teste da Norma JIS Z 2801:2000, e com os filmes industriais realizou-se os testes de Agitação em Frasco e Contagem de Microrganismos Viáveis. Resultados. O compósito apresentou inibição para Escherichia coli em todas as concentrações estudadas e para Staphylococcus aureus nas concentrações de 12,5, 25 e 100 ppm de NpAg. A adição de compósito na matriz... (Resumo completo, clicar acesso eletrônico abaixo) / Mestre

<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.