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The visualisation and rendering of digital elevation dataHobbs, Kenneth Frank January 2000 (has links)
The thesis addresses a longstanding cartographic problem, of how to visualise the Earth's surface relief in an effective and meaningful way. The problem is narrowed to relief defined by digital elevation data and visualised as a static, orthographic representation. It is approached in three steps: firstly research focuses on determining the most useful form of graphical representation to be pursued; secondly the theoretical basis of computer visualisation is investigated through a three-model framework, prompting a number of directions where solutions might be developed; and thirdly the development and engineering of a system is reported which models and renders widely available elevation data, and which provides flexibility in its input variables. The developed system is then applied to specific cases of relief visualisation, and new graphical forms are developed. The investigation of past and current approaches to relief representation, and a review of computer-graphic rendering of simpler geometrically defined objects, have revealed some limitations in commonly used relief visualisation systems, but have established the simulation of light and shade as still the most promising line of development. Analysis of the component variables of surface visualisation and rendering has led to the visualisation paradigm of three parametric models - of elevation, illumination and reflectance. Some attractive qualities, including widespread availability, of the contour elevation model have been identified, and a system has been developed which reconstructs surfaces from this data structure in a more effective way than typical current approaches. The system is also designed to support more complex illumination and surface reflectance models than the somewhat simplistic scenarios commonly available. The thesis reports the application of the system to generate surfaces from contour data, and experimentation with multiple coloured light sources and varying degrees of surface specularity. Evaluation of system implementation, and of the qualities of a representative set of graphical products, is addressed through six design criteria within a context defined by a typical mapping application. This has led to conclusions that the system and the new graphical forms have a number of virtues, including close fidelity with the source data, and significant improvements in visualisation.
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The effect of variation in illuminant direction on texture classificationChantler, Michael J. January 1994 (has links)
No description available.
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Feasibility study of using optical moir?? interferometry technique for fine-grain surface relief in heritage recording.Al-Ratrout, Samer Abdulmunim 01 November 2005 (has links)
In order to prepare for the prospective need for heritage 3D recording, the main
objective of this research was to investigate a new depth measuring method that
can reduce identified limitations of current point-to-point measuring approaches.
The limitations were time-money consumption, intrusiveness, accuracy
assumption and efficiency.
In many disciplines other than heritage recording, optical moir??
interferometry techniques (OMIT) are well developed as a measuring method
and are considered fast, non-intrusive, accurate, and efficient. Based on these
considerations, this research hypothesized that OMIT, as a measuring method,
is feasible with respect to time-consumption and accuracy in acquiring depth
measurement for fine-grain surface relief for historic recording.
To test this hypothesis, a feasibility investigation was carried in which
OMIT was used for surface relief topographic recording. This goal was
approached by performing a comparison study between the OMIT measuring
method as the investigated method and the hand measuring method as the
control method. For each method, the comparison required performing eight
experimental samplings of relief recording for a pre-designed physical model
surface.
The data collected from the hand measuring samples were the depth
measurements of predefined points on the model surface and the timeconsumption
for both measuring and data preparing processes. The data
collected from the OMIT measuring samples were moir?? dark fringes generated
on the model surface and the time-consumption for both moir?? generating and
data preparing processes. For measurement accuracy evaluation, the collected
depth data were prepared in the form of topographic contour drawings.
For the OMIT feasibility evaluation, a comparison was carried out to
examine the resulting topographic contour drawings for depth measurement
accuracy level and measuring process time-consumption.
In conclusion, the OMIT method showed higher depth measurement
accuracy levels and lower process time-consumption than the hand method. The
OMIT method also demonstrated less intrusiveness and more efficiency. This
superiority validates the feasibility of using fine-grain surface relief for heritage
recording purposes.
Finally, the observed advantages of the OMIT method were presented to
establish potentials for future developments and investigations. The observed
limitations of the method were also pointed out to establish trends for
recommendations and further studies.
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Oberflächengitter in azobenzenhaltigen Schichten für organische DFB-Laser / Surface relief gratings in azobenzene containing layers for organic DFB lasersDöring, Sebastian January 2011 (has links)
Ein neuentwickeltes azobenzenhaltiges Material, das auf einem supramolekularen Konzept basiert, wird bezüglich seiner Strukturbildung während einer holografischen Belichtung bei 488 nm untersucht. Im Mittelpunkt stehen dabei eindimensionale, sinusförmige Reliefs mit Periodizitäten kleiner 500 nm. Es wird gezeigt, wie der Grad der Vernetzung der photosensitiven Schicht die Strukturbildung in diesem Größenbereich beeinflusst. Zur Maximierung der Strukturtiefe werden gezielt Prozessparameter der Belichtung sowie Materialparameter variiert. Unter Standardbedingungen und moderaten Belichtungsintensitäten von ca. 200 mW/cm² bilden sich innerhalb weniger Minuten bei einer Periode von 400 nm Strukturtiefen von bis zu 80nm aus. Durch die Beeinflussung von Materialparametern, wie Oberflächenspannung und Viskosität, wird die maximale Strukturtiefe auf 160nm verdoppelt. Durch Mehrfachbelichtungen wird auch die Bildung von zweidimensionalen Gittern untersucht. Die Originalstrukturen werden in einem Abformverfahren kopiert und in Schichten von unter UV-Licht aushärtenden Polymeren übertragen. Durch das Abformen kommt es zu einer geringfügigen Verschlechterung der Oberflächenqualität sowie Abnahme der Strukturtiefe. Dieser Verlust wird durch eine Verringerung der Prozesstemperatur verringert.
Mithilfe kopierter Oberflächengitter werden organische Distributed Feedback-(DFB)-Laser zweiter Ordnung hergestellt, um den Einfluss von Gitterparametern auf die Emissionseigenschaften dieser Laser zu untersuchen. Dazu erfolgt zunächst die Charakterisierung der optischen Verstärkungseigenschaften ausgewählter organischer Emittermaterialien mittels der Variablen Strichlängenmethode. Das mit dem Laserfarbstoff Pyrromthen567 (PM567) dotierte Polystyrol (PS) zeigt dabei trotz konzentrationsbedingter geringer Absorption eine vergleichsweise geringe Gewinnschwelle von 50µJ/cm² bei ca. 575 nm. Das aktive Gast-Wirt-System der konjugierten Polymere MEH-PPV und F8BT* weist eine hohe Absorption und eine kleine Gewinnschwelle von 2,5 µJ/cm² bei 630 nm auf. Dieses Verhalten spiegelt sich auch in den Emissionseigenschaften der damit hergestellten DFB-Laser wieder. Die Dicke der aktiven Schichten liegen im Bereich hunderter Nanometer und wird so eingestellt, dass sich nur die transversalen Grundmoden im Wellenleiter ausbreiten können. Die Gitterperiode sind so gewählt, dass ein Lichtmode im Verstärkungsbereich des Emittermaterials liegt. Die Emissionslinien der Laser sind mit FWHM-Werten von bis zu 0,3 nm spektral sehr schmalbandig und weisen auf eine sehr gute Gitterqualität hin. Die Untersuchungen liefern minimale Laserschwellen und maximale differentielle Effizienzen von 4,0µJ/cm² und 8,4% für MEH-PPV in F8BT* (bei ca. 640nm) sowie 80 µJ/cm² und 0,9% für PM567 in PS (bei ca. 575 nm). Die Vergrößerung der Strukturtiefe von 40nm auf 80nm in mit MEH-PPV dotierten F8BT*-Lasern zu einem deutlichen Anstieg der ausgekoppelten Energie sowie der differentiellen Effizienz und einem geringen Absinken der Laserschwelle. Dies ist ein Resultat der erhöhten Kopplung von Lasermode und Gitter. Die Emission von DFB-Lasern mit zweidimensionalen Oberflächengittern zeigen eine Verringerung der Divergenz aber kein Einfluss auf die Laserschwelle. Abschließend erfolgt eine Vermessung der Photostabilität von DFB-Lasern unter verschiedenen Bedingungen. Das Einbringen eines konjugierten Polymers in eine aktive Matrix sowie der Betrieb in einer Stickstoffatmosphäre führen dabei zu einer Erhöhung der Lebensdauer auf über eine Million Pulse.
Durch die Kombination von Oberflächengittern in PDMS-Filmen mit elektroaktiven Substraten wird eine elektrisch steuerbare Deformation des Beugungsgitters erreicht und auf einen DFB-Laser übertragen. Die spannungsinduzierte Verformung wird zunächst in Beugungsexperimenten charakterisiert und ein optimaler Arbeitspunkt bestimmt. Mit den beiden Elastomeren SEBS12 und VHB4910 werden in den Gittern maximale Periodenänderungen von 1,3% bzw. 3,4% bei einer Steuerspannung von 2 kV erreicht. Der Unterschied resultiert aus den verschiedenen Elastizitätsmoduln der Materialien. Übertragen auf DFB-Laser resultiert eine Variation der Gitterperiode senkrecht zu den Gitterlinien in einer kontinuierlichen Verschiebung der Emissionswellenlänge. Mit einem Spannungssignal von 3,25 kV wird die schmalbandige Emission eines elastischen DFB-Lasers kontinuierlich um fast 50nm von 604 nm zu 557 nm hin verschoben. Aus dem Deformationsverhalten sowohl der reinen Beugungsgitter als auch der Laser werden Rückschlüsse auf die Elastizität der verwendeten Materialien gezogen und erlauben Verbesserungen der Bauteile. / The photoinduced surface relief formation in a newly developed azobenzene containing material is investigated. A photosensitive film based on a supramolecular material concept is illuminated in a holographic setup with light at 488 nm leading to sinusoidal surface structures. It can be shown how the degree of network formation within the material influences structure formation at periods below 500nm. Different material and process parameters are varied to determine maximum possible structure amplitude. At moderate recording conditions and illumination intensities of 200 mW/cm² maximum structure amplitudes of 80 nm are formed within several minutes at periods of approximately 400 nm. Changing material parameters like surface tension and viscosity leads to an increase of maximum amplitude to 160 nm. Additionally, twodimensional structures are fabricated by multiple recording steps. Original surface structures are copied by soft lithography methods into films of UV cured polymers. This replication leads to a decrease of structure contrast and increase of surface roughness. It is shown that structure contrast is preserved by reduction of process temperature.
Organic second order distributed feedback (DFB) lasers are prepared with the help of replicated surface gratings covered with organic active layers with thicknesses of several hundred nanometers. The lasers are investigated regarding the influence of grating amplitude on laser threshold and slope efficiency. For this, the optical gain of two green/red emitter materials, polystyrene (PS) doped with laser dye pyrromethene567 (PM567) and active guest host system of conjugated polymers MEH-PPV and F8BT*, is measured. PS doped with PM567 shows relatively low gain threshold of 50 µJ/cm² at 575 nm caused by the low dye concentration while F8BT* doped with MEH-PPV shows threshold gain of 2.5 µJ/cm² at 630 nm. Similar behavior is observed during laser action. Following Bragg-condition grating periods at approximately 400nm lead to laser emission within the gain spectra of the materials. DFB lasers show single mode narrow line emission with FWHMs of down to 0.3nm. This is a result of high grating quality. Lasers based on MEH-PPV-F8BT* exhibit laser thresholds and slope efficiencies of 4.0µJ/cm² and 8.4%, respectively. PM567-PS lasers exhibit 80 µJ/cm² and 0.9%. An increase of grating amplitude of a MEH-PPV-F8BT*-DFB laser from 40nm to 80nm leads to a considerable increase of energy output and a slight decrease of laser threshold. This is a result of an increase of coupling between light mode and grating which relates to an increase of reflectivity. The use of a two dimensional grating leads to a decrease of divergence angle of laser emission but shows no influence on laser threshold. Finally, laser lifetime is observed under different conditions. Doping the conjugated polymer MEH-PPV in an active matrix in combination with the allocation of nitrogen atmosphere leads to an prolongation of half life time to several million pulses.
The combination of elastic surface relief gratings with electro active substrates enables electrical controlled deformation of the surface structure. This deformation is characterized by diffraction measurements. At optimal working conditions electro active substrates based on elastomers SEBS12 and VHB4910 show maximum grating deformation of 1.3% und 3.4% at actuation voltages of 2kV, respectively. The different results are caused by the different elastic modulus of the elastomer materials. The transfer of deformation principle to elastic DFB lasers leads to a continuously shift of emission wavelength. At an actuation voltage of 3.25kV an elastic DFB laser based on polyvinylacetate doped with PM567 shows a shift of nearly 50 nm, from 604 nm to 557 nm. Deformation behavior of grating and laser allow to draw conclusions on elasticity of the material and with this is tool for the improvement of the device.
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Photoinduced material transport in amorphous azobenzene polymer filmsGrenzer, Marina January 2007 (has links)
The role played by azobenzene polymers in the modern photonic, electronic and opto-mechanical applications cannot be underestimated. These polymers are successfully used to produce alignment layers for liquid crystalline fluorescent polymers in the display and semiconductor technology, to build waveguides and waveguide couplers, as data storage media and as labels in quality product protection. A very hot topic in modern research are light-driven artificial muscles based on azobenzene elastomers.
The incorporation of azobenzene chromophores into polymer systems via covalent bonding or even by blending gives rise to a number of unusual effects under visible (VIS) and ultraviolet light irradiation. The most amazing effect is the inscription of surface relief gratings (SRGs) onto thin azobenzene polymer films. At least seven models have been proposed to explain the origin of the inscribing force but none of them describes satisfactorily the light induced material transport on the molecular level.
In most models, to explain the mass transport over micrometer distances during irradiation at room temperature, it is necessary to assume a considerable degree of photoinduced softening, at least comparable with that at the glass transition. Contrary to this assumption, we have gathered a convincing evidence that there is no considerable softening of the azobenzene layers under illumination. Presently we can surely say that light induced softening is a very weak accompanying effect rather than a necessary condition for the formation of SRGs.
This means that the inscribing force should be above the yield point of the azobenzene polymer. Hence, an appropriate approach to describe the formation and relaxation of SRGs is a viscoplastic theory. It was used to reproduce pulse-like inscription of SRGs as measured by VIS light scattering. At longer inscription times the VIS scattering pattern exhibits some peculiarities which can be explained by the appearance of a density grating that will be shown to arise due to the final compressibility of the polymer film.
As a logical consequence of the aforementioned research, a thermodynamic theory explaining the light-induced deformation of free standing films and the formation of SRGs is proposed. The basic idea of this theory is that under homogeneous illumination an initially isotropic sample should stretch itself along the polarization direction to compensate the entropy decrease produced by the photoinduced reorientation of azobenzene chromophores.
Finally, some ideas about further development of this controversial topic will be discussed. / Azobenzenhaltige Polymere sind in modernen photonischen, elektronischen und opto-mechanischen Anwendungen nicht mehr wegzudenken. Diese Polymere werden erfolgreich in der Bildschirm- und Halbleitertechnologie eingesetzt, um Ausrichtungsschichten für flüssig-kristalline fluoreszierende Polymere zu produzieren sowie Wellenleiter und Wellenleiterkoppler herzustellen. Auch dienen sie als Medien für Datenspeicher oder der Sicherung von Qualitätsprodukten. Ein wichtiges Thema in der modernen Forschung sind lichtgetriebene künstliche Muskeln basierend auf azobenzenhaltigen Elastomeren.
Die Inkorporation von Azobenzene in Polymersysteme durch kovalente Bindungen oder durch Vermischung resultiert in einer Anzahl ungewöhnlicher Effekte, welche unter Bestrahlung mit sichtbarem und ultraviolettem Licht auftreten. Der erstaunlichste Effekt ist das Erzeugen von Oberflächengittern (Surface Relief Gratings - SRGs) auf dünnen azobenzenhaltigen Polymerfilmen. Es wurden mindestens sieben Modelle zur Erklärung der Herkunft der dieses Gitter erzeugenden Kraft vorgeschlagen aber keines von diesen kann befriedigend den lichtinduzierten Massetransport auf molekularem Niveau beschreiben.
Um einen Massetransport über Mikrometerabstände zu erklären, ist es in den meisten Modellen notwendig, eine deutliche lichtinduzierte Erweichung, die mit der Erweichung bei dem Glasübergang vergleichbar ist, anzunehmen. Entgegen dieser Annahme wurden in dieser Arbeit überzeugende Beweise gesammelt, dass es keine signifikante Erweichung in azobenzenhaltigen Schichten bei homogener Bestrahlung gibt. Deshalb kann man davon ausgehen, dass die lichtinduzierte Erweichung eher ein schwacher begleitender Effekt als eine notwendige Voraussetzung für die Bildung derartiger Oberflächengitter ist.
Aus dieser Beobachtung muss geschlussfolgert werden, dass die erzeugende Kraft oberhalb der Fließgrenze azobenzenhaltiger Polymer liegt. Deshalb ist die viskoplastische Theorie ein geeigneter Ansatz zur Beschreibung der Formation von Oberflächengittern und deren Relaxation. Dieser Ansatz wurde genutzt, um die beim pulsartigen Erzeugen von Oberflächengittern gemessene Lichtstreuung mit einem Modell zu beschreiben. Bei längeren Bestrahlungszeiten weist das Streumuster einige Besonderheiten auf, die durch die Bildung eines Dichtegitters erklärt werden können. Dieses Gitter entsteht infolge der begrenzten Kompressibilität des Polymerfilms.
Als logische Konsequenz der oben genannten Erkenntnisse wird eine thermodynamische Theorie, die die lichtinduzierte Deformation des freistehenden Filmes und die Oberflächen-gitterbildung wiedergeben kann, vorgeschlagen. Die Hauptidee ist, dass eine ursprünglich isotrope Probe sich unter homogener Bestrahlung entlang der Polarisationsrichtung ausdehnen muss, um die Entropieabnahme, die durch die lichtinduzierte Reorientierung der Azobenzene entstanden ist, zu kompensieren.
In der Folge werden einige Ideen über die weitere Entwicklung dieses interessanten Themas diskutiert.
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The study of two-dimensional structure on dye-doped polymer film fabricated by holographyYao Huang, Bing- 19 July 2010 (has links)
The dual-writing process of holographic technique was applied to fabricate the two-dimensional surface relief gratings on azo-dye doped polymer film in this study. The structure of two-dimensional grooves was investigated under the various polarization state of writing beam, the various angle between two stages of writing, and the adoption of nematic liquid crystals as the interface. The results revealed that the depth of two-dimensional surface relief gratings produced by the writing beams with P-polarization and the interface of nematic liquid crystals in contact with azo-dye polymer film was about 2~3 times of that without nematic liquid crystals as the interface. As the angle between two stages of writing increases, the first order diffraction efficiency and the depth of surface relief structure in the second writing becomes smaller for the writing beam with S polarization; while the first order diffraction efficiency and the depth of surface relief structure becomes larger for the writing beam with P polarization.
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The Study of Laser-Induced Holographic Grating in Azo Dye-Doped PMMA Thin Film With Liquid CrystalsTsai, Shih-Pin 16 July 2003 (has links)
The laser-induced holographic gratings in the Azo dye-doped PMMA thin films with liquid crystal were investigated by changing the temperature of the sample, the angle of two writing beams and the rubbing. The high power Q-switch pulse laser has been used as the writing beams and the He-Ne cw laser has been used as a real-time probe beam to detect the first order diffraction singals. The grating are the results of photo-isomerization of azo dye and diffusions of liquid crystal. The model has been established to analyze the first order diffraction signals in order to understand the mechanism of grating and the effect of temperature and angle.
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From Holographic Video Monitors to Optogenetic Probes: How Advancements to Leaky-Mode Modulator Technology Are Saving the WorldMcLaughlin, Stephen Dalton 05 June 2018 (has links)
The research presented in this dissertation focuses on improvements made to lithium niobate leaky-mode modulators for both holographic video and optogenetic applications. The specific improvements found herein are: (1) characterization of leaky-mode modulators to decrease driver bandwidth to match that of commodity graphics processing units, (2) the implementation of surface relief gratings as input couplers to replace rutile prism coupling, (3) the addition of backside surface relief gratings to create an orthogonal output face for the leaky-mode modulator, and (4) the creation of superimposed surface relief gratings in lithium niobate to enable multiple wavelength coupling at a single input angle. These advancements for leaky-mode modulators open avenues in display technologies and optogenetics. As a display technology, the leaky-mode modulator can not only be used more effectively in holographic monitors, but can stand alone as a transparent near-eye display. In regards to optogenetics, these technologies allow for the creation of a highly advanced light delivery method, with multiple illumination angles through non-mechanical steering, a large output area to probe size ratio, and support for simultaneous multiple wavelength output in both common and disparate locations.
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Compósitos poliméricos nanoestruturados de azocorantes,ftalocianinas e polímeros luminescentes / Polymeric nanocomposites containing azodyes, phthalocyanines and luminescent polymersZucolotto, Valtencir 31 October 2003 (has links)
Esta tese descreve a fabricação, caracterização e possíveis aplicações de compósitos poliméricos nanoestruturados obtidos pela técnica de automontagem. Três sistemas distintos foram analisados: i) nanocompósitos contendo azopolímeros e azocorantes, ii) nanocompósitos contendo compostos de coordenação macrocíclicos (ftalocianinas), e iii) nanocompósitos contendo materiais do tipo doador-receptor, à base de poli(p-fenileno vinileno) (PPV) e azocorantes. Nos compósitos contendo azobenzeno, exploramos as propriedades de birrefringência e a formação de grades de relevo fotoinduzidas. Dois compostos contendo azobenzeno foram utilizados: um copolímero com cromóforos de azobenzeno ligados covalentemente à cadeia principal (Ma-co-DR13) e um azocorante comercial de baixo peso molecular, Brilliant Yellow (BY). Verificou-se através de experimentos de armazenamento óptico que o tempo de escrita até a saturação é muito maior (cerca de 30 min.) que em filmes de azopolímeros produzidos por outras técnicas como casting, em que este tempo é da ordem de dezenas de segundos. O longo tempo foi atribuído às fortes interações eletrostáticas entre as camadas dos filmes automontados, restringindo o processo de reorientação molecular, necessário à indução da birrefringência. Verificamos também que a presença de água entre as camadas do filme exerce influência significativa sobre o tempo de escrita. O tempo característico de escrita diminui de 8 min. para um filme seco para 2 min. após imersão em água. Este efeito é completamente reversível, ou seja, o tempo característico volta a aumentar se o filme for mantido em dessecador durante alguns dias. Grades de relevo foram inscritas nos filmes de BY e analisadas com micro-espectroscopia Raman. Os resultados mostraram um grau variável de fotodegradação no processo de inscrição das grades, dependendo do policátion ou dos parâmetros de fabricação dos filmes, como o pH das soluções. Qualitativamente, a menor ocorrência de fotodegradação foi observada em filmes de poli(alilamina hidroclorada) (P AH) e BY, preparados em soluções de pH = 10. Para os filmes fabricados com ftalocianina tetrasulfonada de ferro (FeTsPc), a combinação das técnicas de espectroscopia no UV-VIS. e no infavermelho (modos transmissão e reflexão) revelou a existência de ligações não-usuais específicas entre o átomo central de ferro da FeTsPc e os grupos não ionizados (NH2) da PAH, usada como policátion. A existência dessas interações ainda não havia sido relatada na literatura e é devida à estrutura de camadas extremamente finas de PAH e FeTsPc. A espessura média de uma bicamada de PAHlFeTsPc foi estimada em cerca de 10 \'Angstron\'. No terceiro tópico abordado, estudamos o processo de transferência de energia entre camadas automontadas de poli(p-fenileno vinileno) (PPV) e do azocorante BY. A transferência de energia pôde ser controlada não só pela variação da distância entre doador e receptor, mas principalmente pelo foto alinhamento das moléculas do BY (receptor) numa direção perpendicular à direção preferencial de emissão do PPV. Esse fotoalinhamento diminui a transferência de energia entre PPV e BY, resultando em um aumento de até 4 vezes na intensidade da fotoluminescência do filme. / This thesis describes the fabrication and possible applications of layer-by-Iayer (LBL) nanostructured films for three distinct systems comprising i) azopolymers and azodyes, ii) organometallic molecules (phthalocyanines) and iii) luminescent polymers and azodyes. Optically induced birefringence and surface relief gratings (SRGs) were studied in the azobenzene-containing composites, using a side-chain azopolymer (Ma-co-DR13) and a commercially available azodye, viz. Brilliant Yellow (BY). Optical storage experiments showed that the writing time required to induce birefringence (up to the saturation) in LBL films of Ma-co-DR13 is ca. 30 min, which is considerably longer than the times required in cast films of azopolymers (tens of seconds). The long writing time was attributed to the electrostatic interactions between the layers in the LBL film, which preclude photoisomerization or the reorientational processes for the azobenzene molecules.ln addition, entrained water in the films was found to affect the writing time. For example, the characteristic writing time decreases from 8 min. for a dry film to ca.2 min. for a film immersed for some minutes in water. This effect was completely reversible. Surface relief gratings were inscribed on LBL films from BY and analyzed with micro-Raman spectroscopy. The Raman spectra revealed that the process for SRG inscription is not entirely light-driven, with the occurrence of photodegradation. Such photodegradation can be minimized upon the appropriate choice of the polycations as well as the experimental conditions used for film fabrication. The lowest level of photodegradation was observed for films of poly(allylamine hydrochloride) (PAH) and BY fabricated from pH 10 solutions. Organometallic supramolecular composites were built using iron tetrasulfonated phthalocyanine (FeTsPc) and P AH as polycation. The combination of electronic and vibrational spectroscopic techniques showed the presence of unusual specific interactions between the central atom of FeTsPc and non-protonated groups from P AH (NH2). These interactions are believed to occur due to the intimate contact between the materials in the very thin PAH/FeTsPc LBL films, whose thickness was 10 ?Angstron? per bilayer. In the poly(p-fenilene vinylene) (PPV) (donor) and BY (acceptor) system, the resonant energy transfer process was exploited to control luminescence. The quenching in luminescence could be controlled by varying the distance between the PPV and BY layers, similarly to what has been reported in the literature. The novelty in this work, however, was the fine-tuning of luminescence achieved with the photoalignment of the acceptor molecules (BY). For example, the intensity of the photoluminescence increased 4 times upon the photoalignment for 10 min. of the BY chromophores.
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Compósitos poliméricos nanoestruturados de azocorantes,ftalocianinas e polímeros luminescentes / Polymeric nanocomposites containing azodyes, phthalocyanines and luminescent polymersValtencir Zucolotto 31 October 2003 (has links)
Esta tese descreve a fabricação, caracterização e possíveis aplicações de compósitos poliméricos nanoestruturados obtidos pela técnica de automontagem. Três sistemas distintos foram analisados: i) nanocompósitos contendo azopolímeros e azocorantes, ii) nanocompósitos contendo compostos de coordenação macrocíclicos (ftalocianinas), e iii) nanocompósitos contendo materiais do tipo doador-receptor, à base de poli(p-fenileno vinileno) (PPV) e azocorantes. Nos compósitos contendo azobenzeno, exploramos as propriedades de birrefringência e a formação de grades de relevo fotoinduzidas. Dois compostos contendo azobenzeno foram utilizados: um copolímero com cromóforos de azobenzeno ligados covalentemente à cadeia principal (Ma-co-DR13) e um azocorante comercial de baixo peso molecular, Brilliant Yellow (BY). Verificou-se através de experimentos de armazenamento óptico que o tempo de escrita até a saturação é muito maior (cerca de 30 min.) que em filmes de azopolímeros produzidos por outras técnicas como casting, em que este tempo é da ordem de dezenas de segundos. O longo tempo foi atribuído às fortes interações eletrostáticas entre as camadas dos filmes automontados, restringindo o processo de reorientação molecular, necessário à indução da birrefringência. Verificamos também que a presença de água entre as camadas do filme exerce influência significativa sobre o tempo de escrita. O tempo característico de escrita diminui de 8 min. para um filme seco para 2 min. após imersão em água. Este efeito é completamente reversível, ou seja, o tempo característico volta a aumentar se o filme for mantido em dessecador durante alguns dias. Grades de relevo foram inscritas nos filmes de BY e analisadas com micro-espectroscopia Raman. Os resultados mostraram um grau variável de fotodegradação no processo de inscrição das grades, dependendo do policátion ou dos parâmetros de fabricação dos filmes, como o pH das soluções. Qualitativamente, a menor ocorrência de fotodegradação foi observada em filmes de poli(alilamina hidroclorada) (P AH) e BY, preparados em soluções de pH = 10. Para os filmes fabricados com ftalocianina tetrasulfonada de ferro (FeTsPc), a combinação das técnicas de espectroscopia no UV-VIS. e no infavermelho (modos transmissão e reflexão) revelou a existência de ligações não-usuais específicas entre o átomo central de ferro da FeTsPc e os grupos não ionizados (NH2) da PAH, usada como policátion. A existência dessas interações ainda não havia sido relatada na literatura e é devida à estrutura de camadas extremamente finas de PAH e FeTsPc. A espessura média de uma bicamada de PAHlFeTsPc foi estimada em cerca de 10 \'Angstron\'. No terceiro tópico abordado, estudamos o processo de transferência de energia entre camadas automontadas de poli(p-fenileno vinileno) (PPV) e do azocorante BY. A transferência de energia pôde ser controlada não só pela variação da distância entre doador e receptor, mas principalmente pelo foto alinhamento das moléculas do BY (receptor) numa direção perpendicular à direção preferencial de emissão do PPV. Esse fotoalinhamento diminui a transferência de energia entre PPV e BY, resultando em um aumento de até 4 vezes na intensidade da fotoluminescência do filme. / This thesis describes the fabrication and possible applications of layer-by-Iayer (LBL) nanostructured films for three distinct systems comprising i) azopolymers and azodyes, ii) organometallic molecules (phthalocyanines) and iii) luminescent polymers and azodyes. Optically induced birefringence and surface relief gratings (SRGs) were studied in the azobenzene-containing composites, using a side-chain azopolymer (Ma-co-DR13) and a commercially available azodye, viz. Brilliant Yellow (BY). Optical storage experiments showed that the writing time required to induce birefringence (up to the saturation) in LBL films of Ma-co-DR13 is ca. 30 min, which is considerably longer than the times required in cast films of azopolymers (tens of seconds). The long writing time was attributed to the electrostatic interactions between the layers in the LBL film, which preclude photoisomerization or the reorientational processes for the azobenzene molecules.ln addition, entrained water in the films was found to affect the writing time. For example, the characteristic writing time decreases from 8 min. for a dry film to ca.2 min. for a film immersed for some minutes in water. This effect was completely reversible. Surface relief gratings were inscribed on LBL films from BY and analyzed with micro-Raman spectroscopy. The Raman spectra revealed that the process for SRG inscription is not entirely light-driven, with the occurrence of photodegradation. Such photodegradation can be minimized upon the appropriate choice of the polycations as well as the experimental conditions used for film fabrication. The lowest level of photodegradation was observed for films of poly(allylamine hydrochloride) (PAH) and BY fabricated from pH 10 solutions. Organometallic supramolecular composites were built using iron tetrasulfonated phthalocyanine (FeTsPc) and P AH as polycation. The combination of electronic and vibrational spectroscopic techniques showed the presence of unusual specific interactions between the central atom of FeTsPc and non-protonated groups from P AH (NH2). These interactions are believed to occur due to the intimate contact between the materials in the very thin PAH/FeTsPc LBL films, whose thickness was 10 ?Angstron? per bilayer. In the poly(p-fenilene vinylene) (PPV) (donor) and BY (acceptor) system, the resonant energy transfer process was exploited to control luminescence. The quenching in luminescence could be controlled by varying the distance between the PPV and BY layers, similarly to what has been reported in the literature. The novelty in this work, however, was the fine-tuning of luminescence achieved with the photoalignment of the acceptor molecules (BY). For example, the intensity of the photoluminescence increased 4 times upon the photoalignment for 10 min. of the BY chromophores.
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