Made available in DSpace on 2014-06-11T19:25:30Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-02-08Bitstream added on 2014-06-13T20:14:00Z : No. of bitstreams: 1 santos_alr_me_guara.pdf: 967831 bytes, checksum: 8cbbf37b87afd6e4a7c7ecc3380f9ebf (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Materiais poliméricos têm sido amplamente utilizados em várias áreas tecnológicas e biomédicas, devido às suas excelentes propriedades mecânicas, térmicas e elétricas. No entanto, estes materiais têm baixa energia de superfície e, portanto, não aderem facilmente a outros materiais. Por isso, para muitas aplicações é necessário modificar a superfície do polímero, a fim de aumentar a sua energia de superfície. Tratamentos a plasma à pressão atmosférica têm sido muito utilizados para modificar as propriedades superficiais de polímeros comerciais, devido aos baixos custos do processo. Este trabalho apresenta os resultados do tratamento de tereftalato de polietileno (PET), poliuretano (PU) e de politetrafluoretileno (PTFE) em plasma de descargas com barreira dielétrica (DBD) em ar, nitrogênio e argônio, à pressão atmosférica. As superfícies tratadas foram caracterizadas por medidas de ângulo de contato, espectroscopia de fotoelétrons de raios-X (XPS) e microscopia de força atômica (AFM). A superfície polimérica, modificada nas DBD a pressão atmosférica, mostraram uma redução significativa no ângulo de contato da água, embora uma recuperação parcial da molhabilidade ocorresse nos primeiros dias após o tratamento. Todavia, a recuperação foi insuficiente para que as amostras tratadas recuperassem a sua molhabilidade original. Análises de XPS mostraram um aumento na concentração de oxigênio na superfície, devido à formação de grupos polares, tais como C-O e OC= O. Um pequeno aumento na concentração de nitrogênio também foi observada. Imagens de AFM mostraram um aumento da rugosidade de polímeros tratados, decorrentes da interação física entre as espécies geradas na descarga e a superfície do polímero. A superfície ativada e a elevada tensão superficial dos polímeros tratados devem levar a um aumento da aderência do polímero. / Polymeric materials have been widely used in various biomedical and technological applications, due to their excellent mechanical, thermal and electric properties. However, these materials have low surface energy, and thus not easily adhere to other materials. Therefore, for many applications it is necessary to modify the polymer surface in order to increase its surface energy. Plasma treatments at atmospheric pressure have been frequently used to modify the surface properties of commercial polymers, due to their low process costs. This work reports the results of polyethylene terephthalate (PET), polyurethane (PU) and polytetrafluoroethylene (PTFE) treatments in plasma by dielectric barrier discharges (DBDs) in air, nitrogen and argon at atmospheric pressure. The plasma-modified surfaces were characterized by contact angle measurements, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The polymer surface, modified by DBD at atmospheric pressure, showed a significant decrease in water contact angle although a partial recovery of the surface wettability occurred during the first few days after the treatment. However, the process of hydrophobic recovery was insufficient for complete recovering of the samples original wettability. XPS analysis showed an increase of the oxygen concentration on the surface, due to the formation of polar groups, such as C-O and OC= O. A small increase in the concentration of nitrogen was also observed. AFM images exhibit an increased roughness of the treated polymers because of the physical interaction between the species generated in the discharge and the polymer surface. The activated surface and high surface tension of treated polymers should promote an enhancement of the polymer adhesion to paints and coatings.

Resumo: Materiais poliméricos têm sido amplamente utilizados em várias áreas tecnológicas e biomédicas, devido às suas excelentes propriedades mecânicas, térmicas e elétricas. No entanto, estes materiais têm baixa energia de superfície e, portanto, não aderem facilmente a outros materiais. Por isso, para muitas aplicações é necessário modificar a superfície do polímero, a fim de aumentar a sua energia de superfície. Tratamentos a plasma à pressão atmosférica têm sido muito utilizados para modificar as propriedades superficiais de polímeros comerciais, devido aos baixos custos do processo. Este trabalho apresenta os resultados do tratamento de tereftalato de polietileno (PET), poliuretano (PU) e de politetrafluoretileno (PTFE) em plasma de descargas com barreira dielétrica (DBD) em ar, nitrogênio e argônio, à pressão atmosférica. As superfícies tratadas foram caracterizadas por medidas de ângulo de contato, espectroscopia de fotoelétrons de raios-X (XPS) e microscopia de força atômica (AFM). A superfície polimérica, modificada nas DBD a pressão atmosférica, mostraram uma redução significativa no ângulo de contato da água, embora uma recuperação parcial da molhabilidade ocorresse nos primeiros dias após o tratamento. Todavia, a recuperação foi insuficiente para que as amostras tratadas recuperassem a sua molhabilidade original. Análises de XPS mostraram um aumento na concentração de oxigênio na superfície, devido à formação de grupos polares, tais como C-O e OC= O. Um pequeno aumento na concentração de nitrogênio também foi observada. Imagens de AFM mostraram um aumento da rugosidade de polímeros tratados, decorrentes da interação física entre as espécies geradas na descarga e a superfície do polímero. A superfície ativada e a elevada tensão superficial dos polímeros tratados devem levar a um aumento da aderência do polímero. / Abstract: Polymeric materials have been widely used in various biomedical and technological applications, due to their excellent mechanical, thermal and electric properties. However, these materials have low surface energy, and thus not easily adhere to other materials. Therefore, for many applications it is necessary to modify the polymer surface in order to increase its surface energy. Plasma treatments at atmospheric pressure have been frequently used to modify the surface properties of commercial polymers, due to their low process costs. This work reports the results of polyethylene terephthalate (PET), polyurethane (PU) and polytetrafluoroethylene (PTFE) treatments in plasma by dielectric barrier discharges (DBDs) in air, nitrogen and argon at atmospheric pressure. The plasma-modified surfaces were characterized by contact angle measurements, X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The polymer surface, modified by DBD at atmospheric pressure, showed a significant decrease in water contact angle although a partial recovery of the surface wettability occurred during the first few days after the treatment. However, the process of hydrophobic recovery was insufficient for complete recovering of the samples original wettability. XPS analysis showed an increase of the oxygen concentration on the surface, due to the formation of polar groups, such as C-O and OC= O. A small increase in the concentration of nitrogen was also observed. AFM images exhibit an increased roughness of the treated polymers because of the physical interaction between the species generated in the discharge and the polymer surface. The activated surface and high surface tension of treated polymers should promote an enhancement of the polymer adhesion to paints and coatings. / Orientador: Konstantin Georgiev Kostov / Coorientador: Roberto Yzumi Honda / Banca: Konstantin Georgiev Kostov / Banca: Rogério Pinto Mota / Banca: Gilberto Petraconi Filho / Mestre

Atomization conditions for tin hydride in the planar dielectric barrier discharge (DBD) plasma atomizer were optimized with detection by atomic absorption spectrometry (AAS). The effects of apparatus arrangement such as the shape of a waveform function of the high voltage power supply source, DBD atomizer design as well as presence of a dryer tube filled with NaOH pellets to prevent residual aerosol and moisture transport into the DBD were investigated in detail. The optimal experimental setup consisted of a square wave high voltage power supply source coupled to a DBD with vapor-deposited electrodes in the presence of NaOH dryer upstream the DBD atomizer. Argon was found as the best discharge gas under a flow rate of 120 mL min-1 while the DBD optimum high voltage supply rate was 7 kV. A sensitivity of 0.05 s ng-1 Sn and a limit of detection of 1.1 ng mL-1 Sn were reached under optimized conditions. Optimization of the whole experimental setup resulted in 7-fold improvement of sensitivity compared to the original arrangement consisting of a sinusoidal source coupled to a DBD atomizer with glued electrodes in absence of the dryer. Keywords atomic absorption spectrometry, hydride generation, hydride atomization, quart tube atomizer, dielectric barrier discharge (DBD)

Textiles ultrahochmolekulares Polyethylen (UHMWPE) besitzt, aufgrund seiner außerordentlich hohen Molmasse und einem kristallinen Anteil von mehr als 80 %, exzellente spezifische Reißfestigkeiten sowie sehr gute Beständigkeiten gegenüber biologischen, chemischen und physikalischen Einflüssen, wodurch es sich für den Einsatz in Schutztextilien, als textiler Träger für funktionelle Partikel, zur Faserverstärkung in Kunststoffen für hochbelastbare Bauteile und auch zur Herstellung hochwertiger, technischer Textilmembranen anbietet. Voraussetzung für diese Applikationen ist ein hohes Wechselwirkungsvermögen der Fasergrenzflächen. Im Rahmen dieser Dissertationsschrift wurden systematisch die Möglichkeiten zur Oberflächenaktivierung von textilem UHMWPE mittels Atmosphärendruckplasma (ADP) untersucht und Eigenschafts-Wirkungsbeziehungen verschiedener Einflussparameter, u. a. Plasmaleistung, Elektrodenabstand, Behandlungsintensität, aufgeklärt. Dabei lag ein besonderes Augenmerk auf den textilen Eigenheiten des Materials und der dadurch stark beeinflussten Durchdringung des Plasmas. Entsprechend wurden umfangreiche Messreihen zu chemischen und physikalischen Veränderungen der Faseroberfläche erstellt, um schließlich eine industrielle Nutzbarkeit der ADP-Behandlung ableiten zu können. Hierzu wurden auch zwei weitere Verfahren vergleichend begutachtet und in Kooperation mit dem Leibniz-Institut für Polymerforschung Dresden e.V. eine mögliche Anwendung aktivierter UMHWPE-Garne als Träger für magnetisierbare Nanopartikel betrachtet.

L'objectif de cette thèse est de développer un procédé plasma qui puisse se substituer au procédé de dépôt électrolytique de laiton, actuellement appliqué sur les fils d'acier utilisés comme matériaux de renforcement dans un pneu, pour les faire adhérer au caoutchouc. La stratégie employée consiste à déposer une couche mince organochlorée en continu sur un fil d'acier zingué, qui traverse une décharge à barrière diélectrique tubulaire, fonctionnant à la pression atmosphérique, dans une configuration fil-cylindre. Dans un premier temps, les travaux se concentrent sur la caractérisation de la décharge et de la couche mince déposée à la fois en mode statique (substrat immobile dans le réacteur) et dynamique (substrat en défilement). Des relations sont établies entre les paramètres plasma (puissance dissipée dans la décharge, fréquence de la source haute tension, flux de précurseur), les propriétés de la décharge et les caractéristiques du revêtement plasma. Des études morphologique, cinétique et chimique de la couche mince sont réalisées. Dans un second temps, la préparation de la surface du substrat et le dépôt plasma sont optimisés pour permettre d'obtenir les meilleurs niveaux d'adhésion entre l'acier zingué et le caoutchouc. À l'issue de ce travail d'optimisation, des analyses sont réalisées pour identifier la nature de la nouvelle interphase d'adhésion. Cette étude se conclut alors par une discussion sur l'origine possible des liens qui s'opèrent dans ce nouveau système / The primary objective of this thesis project is to develop a plasma process able to replace the electrolytic brass plating process, which is currently performed on steel wires used as reinforcing materials in tires to make them bond with rubber. The chosen strategy consists in depositing organo-chlorinated thin films in a continuous way on zinc-plated steel wires going across a tubular atmospheric pressure dielectric barrier discharge in a wire-cylinder configuration. In a first time, works focus on characterization of both the discharge and the plasma layer, deposited in the static (substrate stationary in the reactor) and dynamic (moving substrate) modes. Relationships are established between the plasma parameters (power dissipated in the discharge, high voltage source frequency, precursor flow rate), the discharge properties and the thin film characteristics. Morphological, kinetic and chemical studies of the plasma layer are carried out. In a second time, the substrate surface preparation and the coating are optimized to enhance the adhesion between zinc-plated steel wires and rubber. Analyses are performed to identify the new adhesion interface nature. At the end of this study, hypotheses concerning the adhesion origin in this system are formulated