Orientadores: Elias Basile Tambourgi, Galba Maria de Campos Takaki / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-20T14:07:57Z (GMT). No. of bitstreams: 1 Ohashi_Tadashi_D.pdf: 6399027 bytes, checksum: f5bf8e93a0ded1fdf4cda419e21a6a7a (MD5) Previous issue date: 2012 / Resumo: Neste trabalho foi investigado o tratamento físico-químico para a remoção do corante reativo Preto Remazol B por adsorção utilizando quitina isolada de resíduo industrial (exoesqueleto de camarão). A extração da quitina foi feita a partir do resíduo industrial de exoesqueleto de camarão através do tratamento de descoloração com NaClO, seguido de desproteinização por álcali à temperatura de 100ºC e liofilização. A quitina obtida foi separada por granulometria, sendo selecionada para os estudos com adsorção a fração da malha 16. O processo de remoção do corante reativo Preto Remazol B foi utilizado como um novo método, aplicando a técnica de adsorção, com posterior laqueadura com soluções inorgânica e orgânica como mordentes, no sentido de aumentar e melhorar a fixação do corante hidrolisado. Um planejamento fatorial de dois níveis foi empregado para analisar a influência da velocidade de agitação, pH, tempo de adsorção e temperatura num sistema de banho finito, contendo uma solução do corante Preto Remazol B, operando em sistema de pressão ambiente. Nos experimentos, o volume do banho e as quantidades do adsorvente foram mantidas constantes em sistema aberto, sob agitação constante. A variação das velocidades foi planejada em baixa, média e alta agitação em Banho-Maria. Os resultados obtidos demonstraram que a adsorção realizada em temperatura elevada apresentou melhor rendimento nos tingimentos, como também no pH 3,0 do banho. O produto formado da complexação Preto remazol B e quitina foi separado da solução por decantação, sendo a quantidade do corante não adsorvida determinada por espectrofotometria em UV-Vis, usando uma curva de calibração do corante a 597nm. Os ensaios 11 e 13 respectivamente, indicaram absorbância zero a ? = 597 nm, sugerindo que, no tingimento propriamente dito, a eficiência de adsorção dos corantes ocorreu no meio ácido, e que outros fatores como tempo, temperatura e velocidade não influenciaram diretamente no rendimento. A operação pós-tingimento denominada de polimento, determinou definitivamente o resultado final da adsorção, onde o uso da solução de sulfato de alumínio a 2%, como mordente possibilitou maior adesão do corante reativo hidrolisado à quitina no banho de tintura. O novo tratamento físico-químico proposto removeu totalmente o corante do efluente têxtil, apresentando baixo custo, além de gerar um produto similar a não-tecido / Abstract: In this work was investigate the physical-chemical treatment for the removal Remazol Black B dye reagent by adsorption using chitin isolated from industrial waste (exoskeleton shrimp). The extraction of chitin was made from industrial waste of shrimp (exoskeleton of shrimp) in the decolorization treatment with NaClO, followed by deproteinization of alkali solution at temperature of 1000C, and freeze dried. The chitin were separated by granulometry corresponding to fraction mesh 16. The removal process of Remazol Black B dye was used a new method applying the technique of adsorption with subsequent ligation with inorganic and organic mordants solutions, in order to enhance and improve the fixing of dye hydrolyzate. A two -level of factorial design was employed to analyze the influence of stirring speed, the pH, and temperature in adsorption system containing a finite bath synthetic solution of Remazol Black B dye, operating in pressure system. In the experiments, the volume of the bath and the amount of the adsorbent were kept constant agitation. The ranges of speeds were planned in low medium and higher agitation in water bath. The results showed that the adsorption carried out at elevate temperature has a better efficiency in dyeing, but also the bath pH3.0. The product formed by complexation Remazol Black B and chitin was separated from the solution by decantation, and the amount of the dye do not adsorbed was determined by UV-Vis spectrophometer using a calibration curve in colorant at 597nm. The assays 11 and 13, respectively, indicated absorbance at ? = 597 nm zero, suggesting adsorption efficiency of the dyes takes place in acid médium, and other factors such as time, temperature and speed (rpm) do not directly influenced the process. The operation after dyeing called polishing definitively determine the final result of adsorption, where the use of aluminium sulphate solution at 2%, promoted greater adherence allowed hydrolyzate of the reactive dye in the bath and chitin, suggesting the new proposed physical-chemical treatment to removal dyes pigments from textile effluent, and showed low cost, beyond that generate similar to a non-woven / Doutorado / Sistema de Processos Quimicos e Informatica / Doutor em Engenharia Química

Les composés organiques à base d'hétérocycles pyraniques peuvent être utilisé dans les cellules photovoltaïques ou dans des matériaux du domaine des télécommunications grâce à leurs propriétés en optique non linéaire. Plusieurs de ces composés ont été synthétisés, analysés et testés dans des cellules solaires à colorants. Des rendements photovoltaïques ont pu ainsi être obtenus et des modifications sur ses composés ont été effectuées afin d'obtenir une meilleure conversions de l'énergie solaire en courant électrique. / Organic compounds with pyranic heterocycles could be used in solar cells or in materials for telecommunications due tot their nonlinear optic properties. Several compounds synthesized were tested in dyes solar cells. The efficiencies of these dyes were obtained and the effect of structural modifications were studied with the goal to obtain a better efficiency.

This work presents the syntheses, photophysical and photochemical characterization of arylthio zinc phthalocyanines and their gold nanoparticle conjugates. Spectroscopic and microscopic studies confirmed the formation of the phthalocyanine-gold nanoparticle conjugates which exhibited enhanced photophysicochemical properties in comparison to the phthalocyanines. The studies showed that the presence of gold nanoparticles significantly lowered fluorescence quantum yields and lifetimes. However, this interaction did not restrict the formation of excited singlet and triplet states and hence the formation of singlet oxygen required for photocatalysis. The conjugates showed significantly higher singlet oxygen quantum yields and therefore enhanced photocatalytic activity compared to the phthalocyanines. The zinc phthalocyanines and their gold nanoparticle conjugates were successfully incorporated into electrospun polymer fibers. Spectral characteristics of the functionalized electrospun fibers indicated that the phthalocyanines and phthalocyanine-gold nanoparticle conjugates were bound and their integrity was maintained within the polymeric fiber matrices. The photophysical and photochemical properties of the complexes were equally maintained within the electrospun fibers. The functionalized fibers were applied for the photoconversion of 4-chlorophenol and Orange G as model organic pollutants. / Microsoft� Word 2010 / Adobe Acrobat 9.53 Paper Capture Plug-in

The continuing industrial development has led to a corresponding increase in the amount of waste water generation leading to a consequential decline in levels and quality of the natural water in the ecosystem. Textile industries consume over 7 x 10[superscript 5] tons of dyes annually and use up to 1 litre of water per kg of dye processed and are third largest polluters in the world, the problem being aggravated by the inefficiencies of the dye houses. An abundance of physio-chemical methods are in use world wide, however, there is increasing concern as to their impact in effectively treating textile effluents as they introduce secondary pollutants during the ‘remediation’ process which are quite costly to run, maintain and clean up. Research on biological treatment has offered simple and cost effective ways of bioremediating textile effluents. While aerobic treatment of textile dyes and their effluents has been reported, its major draw back is commercial up-scaling and as such anaerobic systems have been investigated and shown to degrade azo dyes, which form the bulk of the dyes used world wide. However, the mechanisms involved in the bioremediation of these dyes are poorly understood. The aims of this study were to identify and investigate the role of enzymes produced by sulphate reducing bacteria (SRB) in bioremediating textile dye and their effluents. Sulphate reducing bacteria were used in this study because they are tolerant to harsh environmental conditions and inhibit the proliferance of pathogenic micro-organisms. The appearance of clear zones in agar plates containing azo dye concentrations ranging from 10 – 100 mgl[superscript -1] showed the ability of SRB to decolourize dyes under anaerobic conditions. Assays of enzymes previously reported to decolourise azo dyes were not successful, but led to the identification of hydrogenase enzyme being produced by SRB. The enzyme was found to be localised in the membrane and cytoplasm. A surface response method was used to optimize the extraction of the enzyme from the bacterial cells resulting in approximately 3 fold increase in hydrogenase activity. Maximum hydrogenase activity was found to occur after six days in the absence of dyes but was found to occur after one day in the presence of azo dyes. A decline in hydrogenase activity thereafter, suggested inhibition of enzymatic activity by the putative aromatic amines produced after azo cleavage. Purification of the hydrogenase by freeze drying, poly ethylene glycol, and Sephacryl – 200 size exclusion- ion exchange chromatography revealed the enzyme to have a molecular weight of 38.5 kDa when analyzed by a 12 % SDS-PAGE. Characterisation of the enzyme revealed optimal activity at a pH of 7.5 and temperature of 40 °C while it exhibited a poor thermal stability with a half-life of 32 minutes. The kinetic parameters V[subscript max] and K[subscript m] were 21.18 U ml[superscript -1} and 4.57 mM respectively. Application of the cell free extract on commercial dyes was not successful, and only whole SRB cells resulted in decolourisation of the dyes. Consequently trials on the industrial dyes and effluents were carried out with whole cells. Decolourisation rates of up to 96 % were achieved for the commercial dyes and up to 93 % for the industrial dyes over a period of 10 days.

The textile industry in South Africa is a significant contributor to the chemical load that public wastewater treatment plants have to process, and the discharge of toxic substances, especially to the aquatic environment. In order to address this issue at factory level, the processes at a textile plant, JMV Textiles were chosen for investigation into the possibilities of minimization of discharges of harmful substances into the environment. The study followed the principles of cleaner production, and the processes that were investigated and revised were: The conventional peroxide bleaching process employed a peroxide stabilizer that did not biodegrade easily. The bleaching process was changed, so that the prevailing conditions in the fabric and dyebath facilitated bleaching without the addition of peroxide stabilizer, and also reduced the alkali and energy requirements. Polyester‐viscose fabric was pretreated by bleaching with hydrogen peroxide, which seemed to be unnecessarily rigorous, because polyester and viscose, unlike natural fibres, are relatively clean and have good whiteness in comparison with natural fibres. The proposed alternate pretreatment was a scour with detergent and alkali. The pretreatment for all polyester‐cotton fabrics was also a hydrogen peroxide bleach. Due to the ability of medium and dark shades to mask the natural tint of cotton fibres, a simpler alternate pretreatment, consisting of an alkaline scour with sequestering agent, was trialled. An unacceptable proportion of the dyeings on polyester was rejected for dye‐stains and dye‐marks. A possible solution exploited the properties of using the finishing auxiliary chemical to alleviate dye‐stains and dye‐marks during the dyeing stage, instead of using the chemical after dyeing. The highly toxic carrier that was used to facilitate level dyeing of polyester fibres that had unacceptable variation in their dyeing properties, was replaced by a less toxic carrier. The formulation for dyeing polyester was simplified to eliminate the auxiliary chemicals that were not essential to the dyeing process. Pale reactive dyed shades on cellulose and polyester‐cellulose were washed off only with hot water instead of detergent. The revised procedures consequential to the study, offered significant environmental benefits by reducing the concentration and volume of effluent produced, substituting a highly toxic carrier with a less toxic one and saving energy and water. Implementation of the suggested changes also offered financial benefits. The management of the factory, however, accepted and implemented some changes, but wanted further investigations for others and a phased approach to the other suggested changes.

Reactive Black 5 and Procion Red MX 5B, an azo and anthraquinone dye repectively were decoulorized by mean of microorganisms growing on wood chips. The process consisted of three reactors, two anaerobic reactors and one aerobic reactor. The anaerobic process was used in order to make it possible to break the nitrogen bond of the azo group, (-N=N-) and the aerobic one to increase the possibility for the degradation of possible intermediates. After pumping wastewater through the system it was shown that mixtures or Reactive Black 5 and Procion Red MX 5B were efficiently decolourised at 50 mg/l as well as 200 mg/l of each of the dyes.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Environmental problems have become increasingly acute and frequent in recent decades, mainly due to unrestrained population growth and increased industrial activity. The textile industry merits especial attention in this context, since large volumes of water are used in finishing processes, which results in substantial quantities of liquid effluent. The objective of this work was to determine the optimum conditions for adsorption/desorption of reactive dyes, employing humin in batch experiments and with fixed bed columns where the humin was immobilized on silicate. Immobilization was confirmed by Fourier transform infrared analysis. Adsorption isotherms were constructed, and the kinetic data fitted to literature models. Multiple adsorption/desorption cycles were investigated using the fixed bed column. Results of the batch experiments showed that adsorption of Reactive Red 120 (RR 120) and Reactive Orange 16 (RO 16) by humin was most effective at pH 1.0, while optimum adsorption of Reactive Blue 2 (RB 2) was obtained at pH 2.0. Adsorption equilibria were rapidly achieved for all initial dye concentrations tested. Temperature measurements indicated that all of the processes were exothermic and could be described using a pseudo-second order kinetic model. The Freundlich isotherm provided the best fit for RO 16, while the Langmuir isotherm best described the adsorption of RR 120 and RB 2. In column experiments, adsorption efficiencies of 96.2 %, 62.1 % and 44.6 % were obtained for RR 120, RO 16 and RB 2, respectively, while the corresponding desorption efficiencies for these dyes were 81.4 %, 51.3 % and 23.7 %, respectively. Reductions in retention efficiency of 16 % (RO 16), 21 % (RR 120) and 26 % (RB 2) were observed between the first and second cycles. Reductions between the second and third cycles were of 7 %, 1 % and 1 %, respectively, indicating that the column could be used in further cycles. Overall, the biosorbent showed excellent performance in removal of reactive dyes, with the additional advantage that it could be regenerated and reused. : / Nas últimas décadas, os problemas ambientais têm se tornado cada vez mais críticos e frequentes, principalmente devido ao desmedido crescimento populacional e ao aumento da atividade industrial. A indústria têxtil merece atenção redobrada nesse contexto pela elevada quantidade de água utilizada nos processos de acabamento e geração de grandes volumes de efluentes líquidos. Esse trabalho teve como objetivo determinar as condições ótimas de adsorção / dessorção de corantes reativos utilizando experimentos em bateladas e colunas de leito fixo com humina imobilizada em silicato. A imobilização da humina foi verificada utilizando-se a técnica de espectroscopia de infravermelho com transformada de Fourrier. Isotermas de adsorção foram construídas e os dados cinéticos foram ajustados aos modelos encontrados na literatura. Resultados dos experimentos em batelada mostraram que a adsorção de Reactive Red 120 e Reactive Orange 16 por humina foi mais efetiva em pH 1,0 e pH 2 para o RB 2. E múltiplos ciclos de adsorção/dessorção foram testados nos experimentos em coluna de leito fixo com humina imobilizada em silicato. Os equilíbrios de adsorção foram alcançados rapidamente para todas as concentrações iniciais de corante utilizadas. Medições da temperatura indicaram que o processo foi exotérmico e descrito por um modelo cinético de pseudo-segunda ordem para todos os corantes. A isoterma de Freundlich se ajustou melhor para o RO 16, enquanto que a isoterma de Langmuir descreveu melhor a adsorção de RR 120 e do RB 2. Experimentos em coluna mostraram eficiências de adsorção de 96,2; 62,1 e 44,6% para o RR120, RO 16 e RB 2, respectivamente, bem como boa eficiência de dessorção de 81,4; 51,3 e 23,7% para os mesmos corantes, respectivamente. Uma diminuição da eficiência de retenção foi observada entre o primeiro e o segundo ciclo para o RO 16, RR 120 e RB 2 de aproximadamente 16, 21 e 26%, respectivamente. Entre o segundo e o terceiro ciclo de 7, 1 e 1% para os mesmos corantes. O que mostra a possibilidade de utilização da coluna em ciclos adicionais. O biossorvente apresenta um excelente desempenho na remoção de corantes reativos, com a vantagem que pode ser regenerado e reutilizado.

Neste trabalho foi investigado o processo de relaxação em copolímeros metacrilicos funcionalizados com o grupo cromóforo 4-[N-etil-N-(2-hidroxietil)]amino-2\'-cloro-4\'nitro-azobenzeno (MMADRI3). Os copolímeros sintetizados foram caracterizados por espectrofotometria de visível e infravermelho, calorimetria diferencial de varredura, análise termogravimétrica e elipsometria. O triodo de corona foi utilizado para induzir a orientação dos cromóforos dipolares a temperaturas próximas da transição vítrea. Os valores do coeficiente eletroóptico linear r13 de filmes obtidos por derramento de solução podem alcançar 14 pm/V em amostras funcionalizadas com 43%de cromóforo.O efeito piezoelétricoé significativo para amostras contendo 4% de cromóforo sendo a sua origem atribuída à carga espacial. A relaxação orientacional dos cromóforos foi estudada medindo-se o decaimento do coeficiente eletroóptico e a relaxação dielétrica a diferentes temperaturas. O processo de relaxação foi interpretado utilizando a equação de Kohlraush-Williams-Watts (KWW) aplicada aos domínios do tempo e da freqüência. O tempo de relaxação característico &#964 e o parâmetro b da equação de KWW foram obtidos como função da temperatura desde a temperatura ambiente até acima da temperatura de transição vítrea. O parâmetro b à temperatura de transição vítrea aproxima-se de 0,6 valor que é atribuído a forças de curto alcance. As medidas dielétricas revelaram duas bandas de relaxação &#946 e &#945 respectivamente a baixas e a altas temperaturas. A relaxação a está relacionada com a transição vítrea e à desorientação dos cromóforos. A dependência de &#964 foi fundamentada nas equações de Arrhenius e de Vogel-Fulcher-Tarmnann-Hesse (VFTH), respectivamente a baixas e a altas temperaturas. Os parâmetros de VFTH encontram-se próximos dos considerados universais. O comportamento de &#964 em toda a gama de temperaturas, foi explicado pela equação de Adam-Gibbs, usando-se os parâmetros de VFTH. O resfriamento a taxas lentas após o processo de polarização aumenta substancialmente o tempo de relaxação e a sua energia de ativação. Os expoentes m e n do modelo de Dissado-Hill baseado na interação de multicorpos foram obtidos em função da temperatura. Os valores do parâmetro n ficam dentro do esperado pela teoria / The relaxation process of side-chain methacrylate copolymers functionalized with the nonlinear optical azo chromophore 4-[Nethyl-N-(2-hydroxyethyl)]-amino-2\'-chloro-4-nitroazobenzene (MMADR13) was investigated. The copolymers synthesized were characterized by visible and infrared spectrophotometry, differential scanning calorimetry, thermogravimetric analysis and ellipsometry. The corona triode was employed to induce the orientation of the dipolar chromophore at a temperature near the glass transition. The linear eletrooptic coefficient r13 of cast fllms can reach values as high as 14 pm/V in samples with 43% of chromophore contento The piezoeletric effect attributed to space charge was only significant in the lowest chromophore content samples (4%). Electrostriction was shown to affect to some extent the quadratic electrooptic measurements. The chromophore relaxation at different temperatures was investigated by both electrooptic decay and dielectric measurements. The relaxation process was interpreted using the Kohlraush-Williams-Watts (KWW) equation both in the time and frequency domains. From the KWW equation the characteristic relaxation time &#964 and the stretching parameter b were obtained from room temperature to temperatures above the glass transition. Near the glass transition b is ca 0.6 which is characteristic of short range interactions. Dielectric measurements revealed two relaxation bands, &#946 and &#945, at low and high temperatures, respectively. The &#945 relaxation was attributed to the glass transition and to the 10ss of chromophore orientational order. The temperature behavior of &#964 was interpreted by the Arrhenius and Vogel-Fulcher-Tammann-Hesse (VFTH) equations. at low and high temperatures. respectivelly. The VFTH parameters lie close to the so-called universal values. In addition the overall temperature dependence was explained by the Adam-Gibbs equation using the VFTH parameters. Using a small cooling rate after corona poling increases substantially the relaxation time and the activation energy .The power law exponents m and n. from Dissado-Hill manybody interactions model were obtained as a function of temperature. The n values are in the range of expected values for the many-body interactions model

Os corantes são substâncias adicionadas para conferir ou intensificar a cor dos alimentos. Sendo a aparência dos alimentos fundamental para a escolha do consumidor, a indústria justifica o uso de corantes como forma de melhorar a aparência dos mesmos e aumentar o consumo. Os corantes artificiais adquiriram seu espaço no mercado por terem a vantagem de ser mais estáveis ao processamento, possuírem maior poder tintorial e serem mais baratos do que os naturais. Contudo, estudos ao longo dos anos têm apontado que corantes alimentares artificiais podem estar relacionados a problemas de saúde, principalmente em crianças. Nesse contexto, o presente estudo visou verificar qual a percepção da população do Rio Grande do Sul (RS) em relação a esse tipo de aditivo, através de um questionário online de opinião. Além disso, a pesquisa também procurou estudar o consumo de corantes artificiais por crianças residentes no Rio Grande do Sul. No estudo de percepção (n = 531) foi verificada uma baixa percepção de benefício e alta percepção de perigo dos corantes artificiais, principalmente por pessoas do gênero feminino, pessoas com filho e pessoas de maior faixa etária. Contudo, apesar da sua opinião sobre corantes artificiais, o consumidor não parece afetar o seu padrão de consumo, uma vez que os respondentes afirmaram consumir produtos com esse tipo de aditivo Foi verificado também uma alta desconfiança por parte do público quanto a regulamentação da área de alimentos e falta de conhecimento do consumidor em relação aos rótulos dos alimentos. No estudo de consumo de corantes artificiais por crianças (n = 218), os resultados demonstraram que embora a maioria das crianças (~90%) consuma corantes em quantidades inferiores aquelas estipuladas como seguras, algumas extrapolam o consumo em níveis que podem acarretar em risco à saúde. Em média, os corantes mais consumidos com relação à IDA foram: o Bordeaux (~29% da IDA), Amarelo crepúsculo (~6,5% da IDA), Amarelo Tartrazina (~3,1% da IDA) e Azul Brilhante (~2,8% da IDA). O corante Bordeaux foi o que apresentou maior porcentagens de crianças que ultrapassaram a sua IDA (7,3%). O principal alimento responsável pelo consumo é o refresco em pó. O estudo demonstrou que algumas crianças estão colocando em risco sua saúde ao consumir quantidades elevadas de corantes artificiais. / Dyes are added substances to confer or intensify the color of food. As the appearance of food is fundamental to consumer’s choice, the industry justifies its use as a way to improve their appearance and increase consumption. Artificial dyes have acquired their space in the market because they have the advantage of being more stable to the processing, possessing greater color power and being cheaper than the natural ones. However, studies over the years have pointed out that artificial food colorings may be related to health problems, especially in children. In this context, the present study aimed to verify the perception of the population of Rio Grande do Sul (RS) in relation to this type of additive, through an online opinion questionnaire. In the study of perception (n = 531), a low perception of benefit and a high perception of the risk of artificial dyes were observed, mainly by people of the female gender, people with children and people of greater age. However, in spite of his opinion about artificial colors, the consumer does not seem to affect his consumption pattern, since the respondents stated that they consume products with this type of additive There was also a high public distrust regarding the regulation of the food area and lack of consumer knowledge about food labels. In the study of artificial colorants consumption by children (n = 218), the results showed that although most children (~ 90%) consume dyes in amounts lower than those stipulated as safe, some extrapolate consumption to levels that may be at risk the health. On average, the most consumed dyes with respect to IDA were: Bordeaux (~ 29% of IDA), Sunset Yellow (~ 6.5% of IDA), Yellow Tartrazine (~ 3.1% of IDA) and Bright Blue ~ 2.8% of the ADI). The Bordeaux dye showed the highest percentage of children who exceeded their ADI (7.3%). The main food that is responsible for consumption is soft drink powder. The study showed that some children are putting their health at risk by consuming high amounts of artificial colorants.

This study presents various methods of measuring ozone and consolidates current state of knowledge in the field of disposable printed ozone dosimeters. The paper also identifies prospective dyes for preparation of ozone dosimeters available on the market. Information gathered from literature review was used to prepare dosimeters based on two different dyes. These were calibrated for screen printing technology and their sensitivity to ozone was optimized to achieve visual detectability. Prepared samples were observed and studied while being exposed to ozone. Then, long term mechanical and chemical properties of these were tested in order to identify appropriate conditions for storage.