Efeito protetivo produzido pela aplicação de um filme de carbono amorfo na superfície de um ferramental para conformação

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Síntese de filmes finos a-C:H pela técnica de implantação e deposição por imersão em plasma

Pós-graduação em Ciência e Tecnologia de Materiais - FC

Ligas Ti-Al-Nb como biomaterial: elaboração, caracterização, modificação eletroquímica da superfície e estudo da biocompatibilidade utilizando culturas primárias de células da medula óssea humana

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Comportamento eletroquímico do crômio em soluções contendo íons cloreto

Pós-graduação em Química - IQ

Diodo planar orgânico Schottky: construção e caracterização

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Development of Cutaneous Bioadhesive Ureasil-Polyether Hybrid Films

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Electrochemical behaviour of copper electrode in concentrated sulfuric acid solutions

The electrochemical behaviour of copper in 6.0 mol 1-1 sulfuric acid at 30°C, was studied by means of the potentiodynamic method. At low potential sweep rates, v < 200 m V s-1, the data reveal that the anodic process is basically constituted of copper dissolution and a film formation which inhibits further metal oxidation and which may undergo further dissolution. For higher potential sweep rates, a modification in the passivation region of the voltammogram is observed. It can be ascribed to a change in the passivation mechanism which possibly involves different surface species. The kineticrelationships derived from the potentiodynamic I/E curves obtained at low v suggest a film formation via a dissolution/precipitation mechanism. © 1993.

Untersuchung der Ordnung und Diffusion von Polymerdispersionen bei ihrer Verfilmung

Im Rahmen dieser Arbeit wurde die, für industrielle Applikationen sehr wichtige, Trocknung und Verfilmung von Latexdispersionen untersucht. Unter der Verfilmung wird in diesem Zusammenhang allgemein der Übergang einer Polymerdispersion in einen transparenten, mechanisch stabilen Polymerfilm während ihrer Trocknung verstanden. Für die Untersuchungen wurden schwerpunktmäßig Streumethoden verwendet. Die Untersuchungen haben gezeigt, daß die Streuung eine besonders geeignete Methode zur Untersuchung der Verfilmung ist, die in Abhängigkeit des beobachteten Streuvektorbereichs, der verwendeten Strahlung, der Probenpräparation und des resultierenden Kontrasts eine Vielzahl unterschiedlicher Informationen über die Verfilmung in ihren verschiedenen Phasen liefert. Von besonderem Interesse war es, den prinzipiellen Verlauf der Verfilmung bei den heterogen trocknenden Reinacrylatlatices zu untersuchen. Dazu wurde mit Hilfe der Röntgenultrakleinwinkelstreuung gezielt der Zustand der Partikel in den einzelnen Phasen der heterogen trocknenden Proben beobachtet. Mit Hilfe der Neutronenkleinwinkelstreuung konnte das Verhalten des Emulgators während der Verfilmung und dessen Verteilung im resultierenden Film genauer untersucht werden. Die Röntgenkleinwinkelstreuung erlaubte eine eingehende Untersuchung der Kristallisation des Emulgators im trockenen Film. Geeignete Kontrastierung durch gezielte Deuterierung ermöglichte die Untersuchung des Comonomereinflusses auf die Interdiffusion von Latexpartikeln mit Neutronenkleinwinkelstreuung. Aus den Meßergebnissen wurde ein Modell zur heterogenen Trocknung von Latexdispersionen entwickelt, das den Ablauf der Verfilmung in einem konsistenten Bild zusammenfaßt.

Untersuchung der Filmbildung aus Polymerdispersionen mit Hilfe der forcierten Rayleighstreuung

Der Filmbildungsprozess wässriger Polymerdispersionen wurde mit forcierter Rayleighstreuung untersucht.Diffusionskoeffizienten D von Farbstoffsonden sind damit zwischen 10^-21 und 10^-9 m^2s^-1 zugänglich. Das Diffusionsverhalten der hydrophoben FarbstoffsondeAberchrome in feuchten und trockenen Filmen aus Poly(n-butylmethacrylat-co-acrylsäure)-Dispersionen sowie bei der Wiederbefeuchtung trockener Filme wurde untersucht.Die Dynamik von Aberchrome weicht in feuchten Filmen von Fickscher Diffusion ab. Dies äußert sich in Abweichungen vomcharakteristischen q^2-Verhalten der Relaxationsrate tau^-1 (tau^-1 = Dq^2; q:Streuvektor) und im Auftreten gestrecktexponentieller Intensitätsrelaxationskurven. Diese Anomalie wurde mit einem apparenten, längenskalenabhängigen Diffusionskoeffizienten Dapp(Lambda) (Lambda= 2Pi/q) beschrieben, der für Lambda -> 0 Werte annimmt, die einem homogen hydroplastifizierten Polymermaterial entsprechen, während Dapp(Lambda) für Lambda -> Unendlich stark anwächst. Diese Anomalien verschwinden bei Wassergehalten entsprechend der Polymerwasserlöslichkeit. Weiteres Trocknen führt zum Absinken des Fickschen-Diffusionskoeffizienten auf einen Grenzwert für trockene Filme. Die Ergebnisse konnten mit einem Zwei-Zustands-Modell beschrieben werden: Die Sonde diffundiert Ficksch in einer hydrophilen Grenzflächenphase und einer langsamen Polymerphase. Austausch zwischendiesen Phasen ist ohne Einschränkung möglich. Das Modell erlaubt die Quantifizierung des Einflusses des Trocknungsprozesses auf Polymer- und Grenzflächenphaseneigenschaften.Dies wurde durch systematische Veränderungen der Grenzflächeneigenschaften demonstriert. Dies geschah durch Acrylsäuregehaltvariationen in den Poly(n-butylmethacrylat-co-acrylsäure)-Dispersionen und Emulgatorbedeckungsgradvariationen. In beiden Fällen reflektieren sich Dispersionsveränderungen in einer Veränderung der Modellparameter in der Grenzflächenphase.

Abscheidung und Charakterisierung von Plasmapolymerschichten auf Fluorkohlenstoff- und Siloxan-Basis

In dieser Arbeit wurden Fluorkohlenstoff-basierte und siliziumorganische Plasmapolymerfilme hergestellt und hinsichtlich ihrer strukturellen und funktionalen Eigenschaften untersucht. Beide untersuchten Materialsysteme sind in der Beschichtungstechnologie von großem wissenschaftlichen und anwendungstechnischen Interesse. Die Schichtabscheidung erfolgte mittels plasmachemischer Gasphasenabscheidung (PECVD) an Parallelplattenreaktoren. Bei den Untersuchungen zur Fluorkohlenstoff-Plasmapolymerisation stand die Herstellung ultra-dünner, d. h. weniger als 5 nm dicker Schichten im Vordergrund. Dies wurde durch gepulste Plasmaanregung und Verwendung eines Gasgemisches aus Trifluormethan (CHF3) und Argon realisiert. Die Bindungsstruktur der Schichten wurden in Abhängigkeit der eingespeisten Leistung, die den Fragmentationsgrad der Monomere im Plasma bestimmt, analysiert. Hierzu wurden die Röntgen-Photoelektronenspektroskopie (XPS), Rasterkraftmikroskopie (AFM), Flugzeit-Sekundärionenmassenspektrometrie (ToF-SIMS) und Röntgenreflektometrie (XRR) eingesetzt. Es zeigte sich, dass die abgeschiedenen Schichten ein homogenes Wachstumsverhalten und keine ausgeprägten Interfacebereiche zum Substrat und zur Oberfläche hin aufweisen. Die XPS-Analysen deuten darauf hin, dass Verkettungsreaktionen von CF2-Radikalen im Plasma eine wichtige Rolle für den Schichtbildungsprozess spielen. Weiterhin konnte gezeigt werden, dass der gewählte Beschichtungsprozess eine gezielte Reduzierung der Benetzbarkeit verschiedener Substrate ermöglicht. Dabei genügen Schichtdicken von weniger als 3 nm zur Erreichung eines teflonartigen Oberflächencharakters mit Oberflächenenergien um 20 mN/m. Damit erschließen sich neue Applikationsmöglichkeiten ultra-dünner Fluorkohlenstoffschichten, was anhand eines Beispiels aus dem Bereich der Nanooptik demonstriert wird. Für die siliziumorganischen Schichten unter Verwendung des Monomers Hexamethyldisiloxan (HMDSO) galt es zunächst, diejenigen Prozessparameter zu identifizieren, die ihren organischen bzw. glasartigen Charakter bestimmen. Hierzu wurde der Einfluss von Leistungseintrag und Zugabe von Sauerstoff als Reaktivgas auf die Elementzusammensetzung der Schichten untersucht. Bei niedrigen Plasmaleistungen und Sauerstoffflüssen werden vor allem kohlenstoffreiche Schichten abgeschieden, was auf eine geringere Fragmentierung der Kohlenwasserstoffgruppen zurückgeführt wurde. Es zeigte sich, dass die Variation des Sauerstoffanteils im Prozessgas eine sehr genaue Steuerbarkeit der Schichteigenschaften ermöglicht. Mittels Sekundär-Neutralteilchen-Massenspektrometrie (SNMS) konnte die prozesstechnische Realisierbarkeit und analytische Quantifizierbarkeit von Wechselschichtsystemen aus polymerartigen und glasartigen Lagen demonstriert werden. Aus dem Intensitätsverhältnis von Si:H-Molekülen zu Si-Atomen im SNMS-Spektrum ließ sich der Wasserstoffgehalt bestimmen. Weiterhin konnte gezeigt werden, dass durch Abscheidung von HMDSO-basierten Gradientenschichten eine deutliche Reduzierung von Reibung und Verschleiß bei Elastomerbauteilen erzielt werden kann.

Strukturbildung in Polyurethandispersionen und -filmen

Mechanische Eigenschaften nach Verfilmen sind häufig die wichtigsten Anforderungen für Polyurethandispersionen, so werden beispielsweise in den Hauptanwendungen im Beschichtungs- und Klebstoffsektor oftmals hohe Festigkeiten benötigt. Diese Anforderungen werden in der Dissertation durch eine gezielte Strukurbildung in den Polymeren adressiert. Mit einer hohen Kontrolle über den Polymeraufbau, durch die Ausbildung von kristallinen Bereichen, sowie mit phasenseparierten Morphologien werden drei Konzepte für die Modifikation der mechanischen Eigenschaften vorgestellt: Eine chemische bzw. kovalente Vernetzung wird mit funktionalisierten Polyurethanen erreicht, die physikalische Vernetzung kann reversibel die mechanische Festigkeit von Filmen erhöhen und Hybride mit kontrollierter Morphologie zeigen eine Kombination von Vorteilen ihrer Einzelbestandteile. Ferner zeichnen sich die synthetisierten Polyurethane gegenüber anderen Polymerklassen durch ihre relativ einfache Synthese und die Möglichkeit zur Herstellung multifunktionaler Materialien aus.

Influence of polymers on microstructure and adhesive strength of cementitious tile adhesive mortars

The impact of polymer modification on the physical properties of cementitious mortars is investigated using a multimethod approach. Special emphasis is put on the identification and quantification of different polymer components within the cementitious matrix. With respect to thin-bed applications, particularly tile adhesives, the spatial distributions of latex, cellulose ether (CE), polyvinyl alcohol (PVA), and cement hydration products can be quantified. It is shown that capillary forces and evaporation induce water fluxes in the interconnected part of the pore system, which transport CE, PVA, and cement ions to the mortar interfaces. In contrast, the distribution of latex remains homogeneous. In combination with results from qualitative experiments, the quantitative findings allow reconstruction of the evolution from fresh to hardened mortar, including polymer film formation, cement hydration, and water migration. The resulting microstructure and the failure modes can be correlated with the final adhesive strength of the tile adhesive. The results demonstrate that skinning prior to tile inlaying can strongly reduce wetting properties of the fresh mortar and lower final adhesive strength.

Desenvolvimento de matrizes poliméricas como veículo de ácido ascórbico: caracterização e avaliação da estabilidade

A administração de princípios ativos pela mucosa oral é uma forma eficiente para a distribuição de fármacos e nutrientes, oferecendo diversas vantagens como uma fácil aplicação, evitando o metabolismo de primeira passagem hepática e potencialmente melhorando a biodisponibilidade dessas substâncias. A acerola e o camu-camu apresentam uma alta concentração de vitamina C e são consideradas fontes de diferentes compostos ativos, porém a vitamina C presente nas frutas é facilmente oxidada pelos fatores ambientais, e essas frutas são pouco acessíveis ao consumo populacional. Filmes de desintegração oral (FDO) podem apresentar rápido tempo de desintegração e fácil administração, o que os torna um material interessante para a veiculação de compostos com atividades farmacêuticas ou nutricionais. Assim, este trabalho teve como objetivo o desenvolvimento e caracterização de filmes de desintegração oral à base de amido e gelatina com adição de extrato seco de acerola e camu-camu produzidos por \"spray dryer\" como uma alternativa para a administração de vitamina C. Os FDOs foram produzidos pela técnica de casting, variando-se a proporção de amido e gelatina. Como plastificante foi utilizado o sorbitol (20 g / 100 g de polímero), mantendo-se constante a concentração de polímeros (2 g /100 g de solução filmogênica) e de extrato seco de acerola (4 g /100 g de solução filmogênica) e camu-camu (4 g / 100 g de solução filmogênica). Os extratos secos de acerola e camu-camu foram caracterizados com relação à concentração da vitamina C e da estabilidade desses extratos nessas condições (30 °C, UR 75 % e 40 °C, UR 75%). Os FDOs foram caracterizados em relação a espessura, propriedades mecânicas, ângulo de contato, FT-IR, microscopia electrônica de varredura, concentração de vitamina C, atividade antioxidante, atividade antimicrobiana, estabilidade da vitamina C, tempo de desintegração, estabilidade da atividade de eliminação de radicais de DPPH•, avaliação sensorial. Os extratos secos apresentaram uma boa estabilidade em relação à vitamina C e aos compostos antioxidantes (sequestro do radical DPPH•). Os FDOs sem adição de extrato, independente da formulação, mostraram-se homogêneos, com ausência de partículas insolúveis e alta capacidade de formação de filme. Para os FDOs com maior concentração de amido foi observado reduzido tempo de desintegração e pH próximo ao bucal. Após a adição dos extratos, os FDOs apresentaram redução do tempo de desintegração, boa aceitação sensorial, propriedades antioxidantes e estabilidade pelo sequestro do radical DPPH•. O pH de superfície dos filmes com adição de extrato seco de acerola foi mais próximo ao bucal quando comparado com os filmes com camu-camu. No entanto, os FDOs com acerola apresentaram reduzida estabilidade da vitamina C em relação ao tempo de armazenamento, enquanto que os filmes com camu-camu apresentaram melhor estabilidade. De modo geral, na formulação produzida apenas com amido (100 g de amido / 100 g de polímeros) observou-se uma maior concentração da vitamina C no final da estabilidade realizada à 30 °C e umidade relativa de 75 %, elevada estabilidade dos compostos ativos (DPPH) e alta taxa de uniformidade na distribuição da vitamina C no filme de desintegração oral. Dessa forma, os FDOs podem ser considerados uma boa alternativa para a suplementação de vitamina C.

Development and evaluation of a non-destructive adhesion test

The object of this work was to further develop the idea introduced by Muaddi et al (1981) which enables some of the disadvantages of earlier destructive adhesion test methods to be overcome. The test is non-destructive in nature but it does need to be calibrated against a destructive method. Adhesion is determined by measuring the effect of plating on internal friction. This is achieved by determining the damping of vibrations of a resonating specimen before and after plating. The level of adhesion was considered by the above authors to influence the degree of damping. In the major portion of the research work the electrodeposited metal was Watt's nickel, which is ductile in nature and is therefore suitable for peel adhesion testing. The base metals chosen were aluminium alloys S1C and HE9 as it is relatively easy to produce varying levels of adhesion between the substrate and electrodeposited coating by choosing the appropriate process sequence. S1C alloy is the commercially pure aluminium and was used to produce good adhesion. HE9 aluminium alloy is a more difficult to plate alloy and was chosen to produce poorer adhesion. The "Modal Testing" method used for studying vibrations was investigated as a possible means of evaluating adhesion but was not successful and so research was concentrated on the "Q" meter. The method based on the use of a "Q" meter involves the principle of exciting vibrations in a sample, interrupting the driving signal and counting the number of oscillations of the freely decaying vibrations between two known preselected amplitudes of oscillations. It was not possible to reconstruct a working instrument using Muaddi's thesis (1982) as it had either a serious error or the information was incomplete. Hence a modified "Q" meter had to be designed and constructed but it was then difficult to resonate non-magnetic materials, such as aluminium, therefore, a comparison before and after plating could not be made. A new "Q" meter was then developed based on an Impulse Technique. A regulated miniature hammer was used to excite the test piece at the fundamental mode instead of an electronic hammer and test pieces were supported at the two predetermined nodal points using nylon threads. This instrument developed was not very successful at detecting changes due to good and poor pretreatments given before plating, however, it was more sensitive to changes at the surface such as room temperature oxidation. Statistical analysis of test results from untreated aluminium alloys show that the instrument is not always consistent, the variation was even bigger when readings were taken on different days. Although aluminium is said to form protective oxides at room temperature there was evidence that the aluminium surface changes continuously due to film formation, growth and breakdown. Nickel plated and zinc alloy immersion coated samples also showed variation in Q with time. In order to prove that the variations in Q were mainly due to surface oxidation, aluminium samples were lacquered and anodised Such treatments enveloped the active surfaces reacting with the environment and the Q variation with time was almost eliminated especially after hard anodising. This instrument detected major differences between different untreated aluminium substrates.Also Q values decreased progressively as coating thicknesses were increased. This instrument was also able to detect changes in Q due to heat-treatment of aluminium alloys.

The study of ultra-low energy deposition of hydrogenated amorphous carbon thin films

This thesis is dedicated to the production and analysis of thin hydrogenated amorphous carbon films. A cascaded arc plasma source was used to produce a high density plasma of hydrocarbon radicals that deposited on a substrate at ultra low energies. The work was intended to create a better understanding of the mechanisms responsible for the film formation, by an extensive analysis on the properties of the films in correlation with the conditions used in the plasma cell. Two different precursors were used: methane and acetylene. They revealed a very different picture for the mechanism of film formation and properties. Methane was less successful, and the films formed were soft, with poor adhesion to the substrate and decomposing with time. Acetylene was the better option, and the films formed in this case were harder, with better adhesion to the substrate and stable over time. The plasma parameters could be varied to change the character of films, from polymer-like to diamond-like carbon. Films deposited from methane were grown at low deposition rates, which increased with the increase in process pressure and source power and decreased with the increase in substrate temperature and in hydrogen fraction in the carrier gas. The films had similar hydrogen content, sp3 fractions, average roughness (Ra) and low hardness. Above a deposition temperature of 350°C graphitization occurred - an increase in the sp2 fraction. A deposition mechanism was proposed, based upon the reaction product of the dissociative recombination of CH4+. There were small differences between the chemistries in the plasma at low and high precursor flow rates and low and high substrate temperatures; all experimental conditions led to formation of films that were either polymer-like, soft amorphous hydrogenated carbon or graphitic-like in structure. Films deposited from acetylene were grown at much higher deposition rates on different substrates (silicon, glass and plastics). The film quality increased noticeably with the increase of relative acetylene to argon flow rate, up to a certain value, where saturation occurred. With the increase in substrate temperature and the lowering of the acetylene injection ring position further improvements in film quality were achieved. The deposition process was scaled up to large area (5 x 5 cm) substrates in the later stages of the project. A deposition mechanism was proposed, based upon the reaction products of the dissociative recombination of C2H2 +. There were large differences between the chemistry in the plasma at low and medium/high precursor flow rates. This corresponded to large differences in film properties from low to medium flow rates, when films changed their character from polymer-like to diamond-like, whereas the differences between films deposited at medium and high precursor flow rates were small. Modelling of the film growth on silicon substrates was initiated and it explained the formation of sp2 and sp3 bonds at these very low energies. However, further improvements to the model are needed.