In this research, the polarization converters were manufactured by impinging intensity-gradient-distribution laser on DDLC (dye-doped liquid crystal) samples, which the gradient distributed light intensity was produced by applying linear variable ND filter. The performances of these polarization converters were demonstrated, which can convert a linear polarized incident light into a circular polarized light or an elliptic polarized light. The influence of cell gap and beam size of probe beam on the DDLC polarization converter has been discussed.

Xenobiotic compounds, which are exclusively man made, are produced in large quantities every year and released to the environment. Besides, anaerobic sludge digestion offers advantage in co-treatment of hazardous substances produced by the industry. The performance of the digesters can be monitored by modeling efforts. In this study, Anaerobic Digestion Model No.1 (ADM1) was calibrated, and validated for full-scale digester, lab-scale digester, and lab-scale digester seeded with totally different anaerobic biomass than that of full-scale digester. The model xenobiotic compound, a mono azo dye RO107, was co-treated with sewage sludge in an anaerobic digester. High removal efficiencies as 98% was found for azo dye at standard operating conditions of anaerobic digesters. The digester performance was not effected from azo dye or its reduction products. The dye reduction mechanism was modeled by biochemical mechanism due to unspecific enzymes and by chemical mechanism due to sulfide reduction. Some of the dye metabolites were suggested to be degraded by aerobic biotreatment. The anaerobic reduction metabolites of RO107 were identified as 2-(4-aminophenylsulfonyl) ethanol and 2,5-diamino-4-formamidobenzenesulfonic acid, and sulfanilic acid.

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.

This work discusses the effect of photo-alignment in a liquid-crystal film that is doped with nanoparticles and azo-dye. The vertical alignment that is induced by nanoparticles of polyhedral oligomeric silsesquioxanes can be changed into homogeneous alignment by the absorption of photo-excited azo-dye. Both electro-optical and surface properties are analyzed to confirm this phenomenon. An electrically tunable polarization-dependent LC phase grating is produced using the method. By this method, we also present a transflective liquid crystal display with a single cell-gap in a dual-alignment configuration. This dual structure was fabricated via a single-step laser-light exposure through a photomask. The vertical alignment induced by nanoparticles of polyhedral oligomeric silsesquioxanes can be changed into a homogeneous alignment via absorption of photo-excited azo dye. The LC molecules at the transmissive and reflective pixels are homogeneous and hybrid alignment, respectively, at which optimal phase retardations of half and quarter wavelengths are achieved. Both nanoparticle- and azo-dye-induced vertical and homogeneous alignments are non-contact alignment processes and have potential for practical application.

Η φωτοκαταλυτική διάσπαση υδατικών διαλυμάτων του Acid Orange 7 (ΑΟ7), ενός αζωχρώματος που αποτελεί τυπικό δείγμα των μη-βιοαποδομήσιμων χρωστικών ουσιών που απαντώνται στα υγρά απόβλητα βιομηχανιών υφαντουργίας, μελετήθηκε με χρήση καταλύτη TiO2 και τεχνητής ηλιακής ή ορατής (>400 nm) ακτινοβολίας. Βρέθηκε ότι όταν χρησιμοποιείται ηλιακή ακτινοβολία, η διάσπαση των μορίων του ΑΟ7 λαμβάνει χώρα στην επιφάνεια του φωτοκαταλύτη μέσω μιας σειράς βημάτων οξείδωσης που οδηγούν στον σχηματισμό ενδιαμέσων, κυρίως αρωματικών και αλειφατικών οξέων, τα οποία στη συνέχεια οξειδώνονται περαιτέρω προς ενώσεις με προοδευτικά μικρότερο μοριακό βάρος. Τελικά, επιτυγχάνεται πλήρης αποικοδόμηση του αζωχρώματος, με σχηματισμό CO2 στην αέρια φάση και ανόργανων ιόντων στο διάλυμα. Όταν χρησιμοποιούνται φωτόνια ορατού φωτός, τα ενδιάμεσα της αντίδρασης είναι παρόμοια με αυτά που παρατηρήθηκαν με τη χρήση ηλιακής ακτινοβολίας, αλλά ο αποχρωματισμός λαμβάνει χώρα με μικρότερους ρυθμούς. Επιπλέον, μετά τον αποχρωματισμό του διαλύματος, το COD δεν μειώνεται περαιτέρω και τα ενδιάμεσα της αντίδρασης μένουν σταθερά με το χρόνο ακτινοβόλησης υποδεικνύοντας ότι, στην περίπτωση αυτή, η φωτοκαταλυτική διάσπαση με χρήση ορατής ακτινοβολίας λαμβάνει χώρα μέσω του μηχανισμού “φωτοευαισθητοποίησης”. Σύμφωνα με τα αποτελέσματα της κινητικής μελέτης του συστήματος, ο αρχικός ρυθμός αποχρωματισμού εξαρτάται από την ένταση και το μήκος κύματος της προσπίπτουσας ακτινοβολίας, από την κάλυψη της επιφάνειας, από την αρχική συγκέντρωση του αζωχρώματος, από τη συγκέντρωση του TiO2 και από το αρχικό pH. Από την κινητική μελέτη προκύπτει κινητικό μοντέλο το οποίο περιγράφει ικανοποιητικά τα πειραματικά δεδομένα. Μελετάται η επίδραση των φυσικοχημικών ιδιοτήτων του φωτοκαταλύτη, όπως κρυσταλλογραφική δομή, ειδική επιφάνεια, μέσο μέγεθος κρυσταλλιτών, απορρόφηση στη UV/vis περιοχή και μορφολογία, καθώς και της μεθόδου παρασκευής του TiO2 στον ρυθμό αποχρωματισμού. Τέλος, διερευνάται η δυνατότητα βελτίωσης των φωτοκαταλυτικών ιδιοτήτων του TiO2 με ενίσχυση με διάφορα ετεροσθενή κατιόντα και με διασπορά μετάλλου στην επιφάνειά του. / The photocatalytic degradation of aqueous solutions of Acid Orange 7 (AO7), a model non-biodegradable textile azo-dye, is investigated with the use of TiO2 photocatalyst and artificial solar- or visible (>400 nm)-light irradiation. It is shown that when the full solar spectrum is utilized, the dye molecules adsorbed on TiO2 surface undergo a series of oxidation steps, which lead to rapid decolorization and formation of a number of intermediates, mainly aromatic and aliphatic acids, which are further oxidized toward compounds of progressively lower molecular weight and, eventually, to CO2 and inorganic ions. Under these conditions, complete decolorization and mineralization of the solution is achieved with appreciable reaction rates. When the solution is irradiated with visible light (λ> 400 nm), reaction intermediates are similar to those observed under artificial solar-light irradiation but decolorization takes place with much lower rates. In addition, when the solution is bleached, the COD does not further decrease with time of irradiation and reaction intermediates remain unchanged, indicating that the visible-light induced photocatalytic degradation of AO7 is governed by the “photosensitization mechanism”. Kinetic results show that the initial rate of decolorization depends on the intensity and the wavelength of incident light irradiation, the surface coverage, the initial concentration of the azo-dye, the concentration of the photocatalyst and the initial pH of the solution. From the kinetic investigation, a kinetic model is obtained which fits well the experimental data. The influence of the physicochemical properties of the photocatalyst such as crystal structure, specific surface area, average crystallite size, absorption in the UV/vis region and morphology, as well as the preparation method of TiO2 on the rate of decolorization is investigated. The improvement of the photocatalytic activity of semiconductor photocatalysts by doping with different altervalent cations and by deposition of noble metals onto the TiO2 surface is studied.

Darbo tikslas: dviem metodais gauti azodažiklius iš aromatinių aminų diazonio druskų, nustatyti jų pKa reikšmes, įvertinti spektrines savybes bei pritaikyti kaip indikatorius. Darbo uždaviniai: Gauti azodažiklius iš metilanilinų ir 4-nitroanilino vykdant jų diazonio druskų hidrolizę arba jungiant su 1-naftoliu bei 2-naftoliu, apskaičiuoti gautų junginių išeigas, nustatyti jų pKa reikšmes, spektrines savybes, galimą kaip indikatorių pritaikymą. Metodai: Tyrimui atlikti naudojami du azodažiklių sintezės metodai. Apskaičiuotos abiem metodais gautų azodažiklių procentinės išeigos. ESC įvertintas junginių grynumas. Gautų azodažiklių pKa reikšmės bei pH ribos, kuriose keičiasi jų spalva, vertinamos atliekant potenciometrinį titravimą. Vandeniniai azodažiklių tirpalai vertinti spektrofotometriškai, matuojant tirpalų absorbcijos maksimumus ir optinius tankius. Rezultatai: Azodažikliai, atliekant aromatinių aminų diazonio druskų hidrolizę (hidrolizatas sudarytas iš 44 ml vandens ir 20 ml koncentruotos H2SO4), gaunami veikiant aminus koncentruota HCl, kai hidrolizato temperatūra pakeliama iki 104-110 oC. Atliekant tradicinę azodažiklių sintezę išeigos yra geros-labai geros (vidutinė išeiga yra 76,95 proc.), o vykdant diazonio druskų hidrolizę – vidutinės (junginiai gaunami su vidutine 41,44 proc. išeiga). Tradiciniu metodu gautų naftolinių azodažiklių pKa reikšmės yra 8,8-11,0 ribose, o fenolinių, gautų atliekant eksperimentinę sintezę, - 7,5 8,0. Spektrofotometrinis tyrimas parodė... [toliau žr. visą tekstą] / Aim of the work: synthesis of azo dyes from aromatic amines diazonium salts by two methods, determination of their pKa values, spectral features and applicability as indicators of produced azo dyes. Main objectives: to obtain azo dyes from methylanilines and 4-nitroaniline by hydrolysis of their diazonium salts or by binding with 1-naphtol and 2-naphtol, to calculate yields of obtained compounds, to determine their pKa values, spectral features and their possible application as indicators. Methods: Two methods of azo dyes synthesis are used to perform the assay. Percentage yields of synthesized compounds, obtained by both methods, are calculated. Purity of compounds is evaluated by HPLC. pKa values and range of pH where the colour changes of received compounds are evaluated by potentiometric titration. Aqueous solutions of azo dyes are assessed by measuring absorption peaks and optical densities with a spectrophotometer. Results: it is necessary to synthesise aromatic amines diazonium salts with conc. HCl and to perform hydrolysis in 104-110 oC temperature when hydrolysate consist of 44 ml water and 20 ml conc. H2SO4 in order to obtain azo dyes by experimental method. Yields of traditional method are good-very good (average yield is 76,95 proc.), yields of experimental method are moderate (average yield is 41,44 proc.). pKa values of naphtolic azo dyes which are obtained by traditional method are 8,8-11,0 and phenolic azo dyes – 7,5-8,0. Spectrophotometric studies showed that... [to full text]

Orientador: Carlos Renato Corso / Banca: Cassiana Maria Reganhan Coneglian / Banca: Sandra Mara Martins Franchetti / Resumo: Entre as questões ambientais mais discutidas pela sociedade, está a poluição pelos diversos ramos da indústria. As indústrias têxteis estão entre os responsáveis pela contaminação, pois, muitas vezes, eliminam seus efluentes sem tratamento adequado nos mananciais, portanto, sem a completa remoção dos corantes. Os corantes azóicos são os mais utilizados pela indústria têxtil e são caracterizados pela presença de grupos azo (N=N). Dos vários métodos de tratamento de efluentes existentes, o tratamento biológico tem sido amplamente estudado. Buscando uma maneira de melhorar o tratamento biológico, o presente trabalho teve como objetivo comparar a capacidade de biossorção e biodegradação do corante azóico Direct Blue 71 em solução pelos fungos Phanerochaete chrysosporium e Aspergillus oryzae, na forma paramorfogênica. Para isso utilizou-se uma solução de corante DB71 a 100 μg/mL. Foram realizados testes de biossorção, por um período de 2 horas, com cinco diferentes concentrações de biomassa e três valores de pH, 2.5, 4.5 e 6.5, sendo que o pH 2.5 proporcionou a melhor condição para a biossorção. A adsorção do corante pela parede celular de ambos os fungos foi avaliado com o auxílio das isotermas de Freundlich, modelo seguido por P. chrysosporium, e Langmuir, seguido por A. oryzae. Para os testes de biodegradação, por 240 horas, utilizou-se apenas uma concentração de biomassa. Com espectrofotometria UV-VIS foi possível determinar porcentagem de descoloração e absorbância relativa do corante após realização dos testes de biossorção e biodegradação, respectivamente. Análises de FTIR permitiram a identificação de moléculas presentes na solução antes e após a biodegradação. Com A. oryzae obteve-se os melhores resultados de biossorção e biodegradação. Contudo, P. chrysosporium também se mostrou eficiente para os tratamentos... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Among many environmental issues discussed in society, all sorts of pollution from industrial branches arise as an important matter. Textile industries are responsible by such contamination, since they often eliminate their effluents in the environment without proper treatment, therefore, without complete dye removal. Azo dyes are frequently used in textile industry and characterized by the presence of azo groups (N = N). Of the various methods of wastewater treatment available, biological treatment has been extensively studied. Thus, to improve biological treatment in textile industries, this study aimed to compare the ability of biosorption and biodegradation of Azo dye Direct Blue 71 solution by Phanerochaete chrysosporium and Aspergillus oryzae fungi in paramorfogenic form. In order to achieve this, a 100 μg/mL DB7 dye solution was used. Biosorption tests were performed within two hours with five different biomass concentrations and three pH values, 2.5, 4.5 and 6.5. It was observed that pH 2.5 solutions presented best biosorption conditions. The dye adsorption through studied fungi cell wall was evaluated with the Freundlich isotherm model for P. chrysosporium, and Langmuir for A. oryzae. For the biodegradation tests in 240 hours, it was used only one biomass concentration. Through an UV-VIS spectrophotometry the percentage of relative absorbance and dye discoloration was determined after biosorption and biodegradation tests respectively. FTIR analysis allowed molecular compounds identification in solution before and after biodegradation. The best results were obtained with A. oryzae in both biosorption and biodegradation. Yet even then P. chrysosporium was also efficient in all treatments. Hence, both A. oryzae and P. chrysosporium have great potential of dye removal in wastewaters. These results may contribute to improve effluent treatment systems in textile industries. / Mestre

Transparent conducting oxides (TCOs) have become an integral part of modern life through their essential role in touchscreen technology. The growing demand for cheap and superior transparent conducting layers, primarily driven by the smart phone market, has led to renewed efforts to develop novel TCOs. Currently, the most widely used material for transparent conducting applications is Sn-doped indium oxide (ITO), which has outstanding optical and electrical properties. This material is expensive though, due to the extensive use of In, and efforts to develop new low-cost transparent conducting oxides (TCO) have become increasingly important. Similarly attempts to reduce the cost of the fabrication and post-sintering steps used in making doped metal oxide thin films through innovative technologies have gained a lot of attention. With these points in mind, this research project has focused on the development of a novel low-cost aerosol assisted physical deposition method for TCO thin film fabrication and the development of new highly conducting materials to replace the expensive ITO for TCO applications. In this study, a new and simple aerosol assisted vapour deposition technique (i.e AACT) is developed to fabricate TCO films using TCO nanoparticle suspensions. Firstly, to test the validity of the method, ITO thin films are fabricated on float glass substrates from a nanoparticle suspension. The influence of the deposition parameters on the structural and opto-electronic properties of the thin films are investigated to understand the intricacies of the process. In order to investigate the fabrication of replacement materials for ITO, a range of doped zinc oxide powders are synthesised and processed using microwave radiation. Nominally, Al doped ZnO (AZO), Ga doped ZnO (GZO), Si doped ZnO (SZO), Cu doped ZnO (CZO) and Mn doped ZnO (MZO) singly doped ZnO powders are all investigated to determine the best metal dopants for transparent conducting ZnO. AZO and GZO pellets are found to present the best electrical conductivity for the singly doped microwave fabricated powders with values of 4.4 x 10-3 and 4.3 x 10-3 Ω.cm achieved reproducibly. In an effort to further improve the properties of ZnO, co-doping experiments, utilising the two best dopants from the previous work (i.e. Al and Ga) is investigated. ZnO structures that are co-doped with Al and Ga (AGZO) are found to exhibit significantly enhanced electrical properties than the singly doped powders. Typically, electrical conductivity value of 5.6 x 10-4 Ω.cm is obtained for AGZO pellets, which is an order of magnitude better than the previously fabricated materials. Finally, the best AZO, GZO and AGZO materials are utilised to fabricate thin films using the previously verified AACT technique. Further investigations into the opto-electrical properties of the resulting thin films is presented prior to the utilisation of the best films in a practical application. Transparent heaters are fabricated using the best AGZO thin films, which are capable of reaching a mean temperature of 132.3 °C after applying a voltage of 18 V for 10 min. This work highlights the potential for using highly conducting AGZO, particularly fabricated by the microwave synthesis route, as a potential alternative for ITO in a wide variety of applications. The research also highlights the advantages of using microwaves in the thermal processing of TCO materials which significantly reduces the energy impact of the production process.

Made available in DSpace on 2014-10-09T12:34:29Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:12Z (GMT). No. of bitstreams: 0 / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Neste trabalho estudamos o processo de absorção de dois fótons em compostos azoaromáticos, abordando tanto aspectos fundamentais quanto aplicados. Moléculas azo-aromáticos têm recebido especial atenção nos últimos anos devido as suas potencias aplicações em dispositivos para armazenamento óptico de informação, modulação da luz e geração de relevos em superfície, processes estes associados ao mecanismo de foto isomerização. Os trabalhos apresentados nessa tese tiveram como principal foco explorar o fenômeno de absorção de dois fótons, utilizando a propriedade de foto-isomerização das moléculas azo-aromáticas. Nosso objetivo foi estudar as vantagens que podem ser obtidas pela utilização de pulsos intensos de luz, que interagem de maneira não linear com a matéria, para desenvolver aplicações utilizando compostos azo-aromáticos. Inicialmente, estudamos o processo de absorção de dois fótons em uma nova família de compostos azo-aromáticos, denominados Salen Dyes. Investigamos a influencia da presença de íons metálicos no processo de absorção de dois fótons dessas moléculas. Nossos resultados mostraram que, devido a ausência de conjugação entre as estruturas azo-aromáticas conectadas pelo metal, este tem pouca influência no processo não linear estudado. Pelo uso de um modelo de soma de estado para a seção de choque de absorção de dois fótons, fomos capazes de determinar os momentos de dipolo de transição destas moléculas. Em seguida, implementamos uma técnica para estudar o processo de armazenamento óptico, induzido através da orientação molecular dos compostos azo-aromáticos, via absorção de dois fótons. Observamos que de fato é possível se observar birrefringência induzida por dois fótons nestas moléculas, a qual esta confinada ao volume focal, conforme demonstrado pela obtenção de armazenamento tri-dimensional. Finalmente, exploramos o processo de controle coerente via formatação de pulsos ultra-curtos para manipular o processo de birrefringência induzida por dois fótons em compostos azo-aromáticos. Foi demonstrado que apenas a através da manipulação da fase do pulso ultra-curto, é possível modular a birrefringência induzida em filmes de compostos azo-aromáticos. / Here we investigated fundamental and applied aspects of the two-photon absorption process in azoaromatic compounds. Azoaromatic molecules have been studied in the last few years due to their applications in optical storage devices, light modulators and surface relief gratings, processes related to the photo-isomerization mechanism. The main focus of the results presented in this thesis was to explore the two-photon absorption process, taking advantage of the intrinsic photo-isomerization of the azo-aromatic chromophores. Our main goal was to study the advantages of utilizing intense pulses, which promote nonlinear excitation, to develop application with azo-aromatic compounds. Initially, we studied the two-photon absorption process in a new class of azo-aromatic compounds, named Salen Dyes. We investigated the influence of metal ions, presented in the Salen Dyes structure, on the two-photon absorption spectrum. Our results revealed that the metals have practically no influence in the nonlinear optical properties due to the lack of conjugation between the azo-moieties in the Salen Dyes. Through a theoretical model based on a sum-over-states calculation, we were able to determine the transition dipole moment of these molecules. Subsquently, we implememnted a technique to study the two-photon induced birefringence, resulting from the molecular re-orientation, in azo-aromatic compounds. We observed that the two-photon induced birefringence is confined to the focal volume, s demonstrated in a three dimensional optical storage experiment. Finally, we used coherent control processes to manipulate the two-photon induced birefringence in azo-compounds. It was demonstrated that it is possible to modulate the optically induced birefringence by manipulating the phase of the ultra-short pulses, via pulse shaping techniques.