Measurement and mapping of the pressure distribution across the surface of a suitably scaled model is an integral step in the design of any aircraft or automobile. For this purpose, the traditional workhorses of the aeronautic and automotive industries have been pressure taps--small orifices that contain electronic pressure transducers. Unfortunately, in addition to the limited spatial resolution achievable with such devices, their technical complexity and cost constitute serious disadvantages. For more than 35 years, researchers have pursued a fundamentally different alternative: indirect measurement of pressure via oxygen-induced quenching of the luminescence emitted by certain chemical species. Porphyrin complexes of dipositive palladium and especially platinum have emerged as one of the principal classes of oxygen-sensitive luminophores; ruthenium(II) polypyridyl complexes comprise another. Various other metals also form luminescent coordination complexes that are susceptible to quenching by O2, however, and these too have contributed to the diversity of luminophores that are now available for incorporation into pressure-sensitive paints and related films and coatings. After treating the photophysics of luminescence quenching by molecular oxygen and quantitative descriptions of this phenomenon in the ideal case and in heterogeneous media, the thesis presents a comprehensive survey of the chemical literature on oxygen-sensitive luminophores. Efforts to prepare and characterize a novel porphyrin-pillared mixed zirconium phosphonate are then detailed. Following complexation of Pt(II) ions by the porphyrin moieties, this material is expected to display oxygen-sensitive luminescence and should ameliorate such difficulties as luminophore aggregation and matrix photodegradation that are associated with many existing pressure-responsive coatings. Its preparation necessitated preliminary formation of a porphyrin functionalized with two phenylphosphonic acid groups, which was obtained by synthesizing dipyrromethane and diethyl 4-formylphenylphosphonate and condensing these two precursors. The mixed phosphonate, a layered material assembled from ZrOCl2 · 8H2O, methylphosphonic acid, and the aforementioned porphyrin, was then prepared in refluxing HF. Solid-state 31P NMR spectra and powder X-ray diffraction patterns were acquired for the final product, its estimated interlayer spacing of 22.8 Å figuring prominently in analysis and discussion of the X-ray data.

Orientador: Prof. Dr. José Fernando Queiruga Rey / Dissertação (mestrado) - Universidade Federal do ABC, Programa de Pós-Graduação em Nanociências e Materiais Avançados, 2015. / Neste trabalho foram construídos filmes finos automontados a base da imida aromática N,N¿-(2-fosfonoetil)-3,4,9,10-perilenodiimida (PPDI) utilizando a técnica de fosfonato de zircônio (ZP). Os filmes foram crescidos em substratos de silício e de ITO (óxido de índio dopado com estanho). O crescimento dos filmes foi acompanhado por espectroscopia de absorção no UV-visível no caso dos filmes em ITO e refletância especular no caso dos filmes em silício. No caso de filmes em ITO foram crescidas duas séries de filmes para avaliar os efeitos do tratamento térmico. A caracterização dos filmes foi feita por microscopia de força atômica (AFM) e refletividade de raios-X (XRR). As imagens de topografia obtidas por AFM mostram que o tratamento térmico proporcionou uma cobertura mais completa no substrato de ITO. Os valores de rugosidade quadrática média (RMS) obtidos mostram que a rugosidade dos filmes aumenta inicialmente mas passa a diminuir com a deposição de mais camadas. Isto sugere que o substrato pode influenciar na rugosidade do filme até um determinado número de camadas, e após isto, as camadas de filme previamente depositadas passam a ser o efeito predominante. As curvas de refletividade de raios-X sugerem que os filmes em silício estão mais organizados do que os filmes em ITO, demonstrando a influência do substrato na organização dos filmes automontados crescidos sobre ele. / In this work were constructed self-assembled thin films based on the aromatic imide N, N '- (2-phosphonoethyl) -3,4,9,10-perylendiimide (PPDI) using zirconium phosphonate method (ZP). The films were grown on silicon and ITO (indium-tin oxide) substrates. The growth of the films was monitored by absorption spectroscopy in the UV-visible in the case of films on ITO and specular reflectance in the case of films on silicon. Two series of films were grown on ITO substrates to evaluate the effects of heat treatment. The characterization of the films was made by atomic force microscopy (AFM) and X-ray reflectivity (XRR). The AFM topography images obtained show that the heat treatment provided a more complete coverage of the ITO substrate. The mean square roughness values (RMS) obtained show that the roughness of films initially increases but decrease with deposition of further layers. This suggests that the substrate can influence the roughness of the film up to a certain number of layers, and after that, the previously deposited film layers become the predominant effect. The reflectivity curves of X-rays suggest that the silicon films are more organized than the ITO films, demonstrating the influence of substrate on the organization of self-assembled films grown on it.