Le risque d'épuisement de ressources naturelles fossiles à partir desquelles nombres d'oléfines sont fabriqués, a permis le développement de nouveaux matériaux polymères, 100% renouvelables dénommés biopolymères. L'acide poly lactique est sans doute le plus prometteur d'entre eux. D'origine naturelle, ce polyester est synthétisé à partir d'aliments riches en amidon tels que le maïs, la betterave ou la pomme de terre. Son caractère biodégradable lui offre un large éventail d'applications dans les domaines aussi variés et divers que la médecine, le bâtiment, l'industrie automobile, le biomédicale ou encore le textile habillement. Ce travail consiste à étudier la structure et la texture de l'isomère mixte (PDLA) et de déterminer l'incidence de sa morphologie sur les propriétés mécaniques et tinctoriales requises pour des applications textiles. Nous avons par des méthodes spectrales, caractérisé le polymère afin d'en déterminer entre autre, la composition massique, et la stéréorégularité, paramètres très importants ayant une forte influence sur les propriétés mécaniques du polymère, notamment la stabilité thermique ou la résistance à l'hydrolyse. Nos expériences menées sur la stabilité thermique du polymère révèlent que le polymère est susceptible de s'hydrolyser sous l'action combinée de l'eau, de la température et du pH, entraînant ainsi une diminution de la masse moléculaire, donc, une perte de propriétés mécaniques de la fibre.Le PLA est également un polymère qui supporte mal la teinture, et seuls les colorants dispersés sont susceptibles de teinte cette fibre sous certaines conditions. L'étude de la cinétique de fixation de trois colorants dispersés sur la fibre de PLA à permis d'établir une relation entre la structure du colorant et ses propriétés tinctoriales. / The risk of exhaustion of fossil natural resources from which count of polymers are made, allowed the development of new polymer materials, renewable 100 % were called biopolymer. The poly acid lactic is doubtless the most promising of them. Of natural origin, this polyester is synthetized from food rich in starch such as the corn, the beet or the potato. His biodegradable character offers him a wide range of applications in many field as medicine, building, car industry, biomedical or textile clothing. This work consists in studying the structure and the texture of the mixed isomer (PDLA) and to determine the incidence of its morphology on the mechanical properties required for textiles applications.We have by spectral methods, characterized the polymer ,in arder to determine, the molecular weight,composition, and monomers distribution, very important parameter, having a strong influence on the mechanical properties of the polymer, in particular the thermal stability or the resistance in the hydrolysis. Our experiments led on the thermal stability of the polymer reveal that the polymer may hydrolyser under the combined effect of temperature, moisture and by the pH, then, a decrease of the molecular weight, thus, a Joss ofmechanical properties of the fiber.The PLA is also a polymer which can be dye only with certain disperses dyes under particulars conditions.The study of the kinetics of fixation of three disperses dyes scattered on PLA fiber permit to establish a relation between the structure of the disperses dyes and its dyeing properties.

Os corantes são utilizados pelo homem há mais de 20 mil anos, com emprego nas indústrias têxteis, farmacêuticas, alimentícias, cosméticas, fotográficas, entre outras. Contudo, apesar de sua importância, os corantes podem ser tóxicos, mutagênicos e resistentes a muitos processos de degradação utilizados em estações de tratamento de águas residuais. Dentro deste contexto, o objetivo desta pesquisa foi avaliar os efeitos ecotoxicológicos dos corantes têxteis Disperse Red 60 (DR 60), Disperse Red 73 (DR 73) e Disperse Red 78 (DR 78) por meio de testes de toxicidade em três organismos de diferentes níveis tróficos: a bactéria Vibrio fischeri, o microcrustáceo Daphnia similis e o peixe Danio rerio (zebrafish), além da mutagenicidade na bactéria Salmonella typhimurium. Nossos resultados mostraram que os corantes DR 73 e DR 78 induzem toxicidade aguda em Vibrio fischeri e Daphnia similis, reduzindo a luminescência da bactéria e causando imobilidade no microcrustáceo, ao passo que o corante Disperse Red 60 não altera esses endpoints. No entanto, todos os corantes causam efeitos tóxicos em embriões e larvas de Danio rerio. O corante DR 60 ocasionou edemas oculares, alteração no comportamento e indução de efeitos pró-oxidantes em zebrafish. O corante DR 73 reduziu a inflação da bexiga natatória, induziu edemas do pericárdio, promoveu escoliose e alteração no saco vitelínico. Além disso, os corantes DR 73 e DR 78 alteraram o comportamento e balanço energético, induziram efeitos pró-oxidantes e neurotoxicidade. Quanto à mutagenicidade, o corante DR 73 induziu deslocamento do quadro de leitura e substituição de pares de base, enquanto o corante DR 78 causou apenas deslocamento do quadro de leitura e o corante DR 60 não induziu mutagenicidade. Em conclusão, os corantes Disperse Red 73 e Disperse Red 78 foram os mais tóxicos para os organismos avaliados, uma vez que alteraram maior número de endpoints, assim como causaram efeitos em menores concentrações, a partir de 1 ?g/L. Este estudo também demonstra a importância do uso de organismos testes de diferentes níveis tróficos, bem como a necessidade de uma maior atenção quanto ao registro e liberação para uso de corantes, visando prevenir danos ao ambiente e à saúde humana / Dyes have been used for more than twenty thousand years in the textile, pharmaceutical, food, cosmetic, and photographic industry, among others. Despite their importance in these applications, dyes can be toxic, mutagenic and resistant to many degradation processes used in wastewater treatment plants. In this context, the aim of this research was to evaluate the ecotoxicological effects of the Disperse Red 60 (DR 60), Disperse Red 73 (DR 73) and Disperse Red 78 (DR 78) textile dyes by means of toxicity tests on three organisms of different trophic levels: the bacterium Vibrio fischeri, the microcrustacean Daphnia similis and the fish Danio rerio (zebrafish). In addition, the mutagenicity of these dyes to the bacterium Salmonella typhimurium was evaluated. Our results demonstrate that the dyes DR 73 and DR 78 induce acute toxicity to V. fischeri (luminescence reduction) and D. similis (immobility), whereas the DR 60 did not alter these endpoints at the concentrations tested. However, all dyes caused toxic effects on embryos and larvae of D. rerio. DR 60 caused ocular edema, altered behavior and induced pro-oxidant effects in zebrafish. DR 73 reduced swim bladder inflation, induced pericardial edema, promoted scoliosis and changes in yolk sacs. In addition, DR 73 and DR 78 altered the zebrafish juvenile behavior and energy balance, and induced pro-oxidant effects and neurotoxicity. As for the mutagenicity test, DR 73 induced frameshift and base pair substitution, whereas DR 78 caused only frameshift and DR 60 did not induce any mutagenic effects. In conclusion, DR 73 and DR 78 were the most toxic for the organisms tested since they altered a greater number of endpoints and caused toxic effects at lower concentrations, i.e. from 1 ?g/L onwards. These results indicate the importance of using a battery of test organisms from different trophic levels when evaluating the environmental risks of dyes, as well as the need for greater attention regarding the Registration and authorization of the use of dyes in order to prevent unacceptable risks to the environment and human health.

Atualmente, a questão ambiental envolvendo a indústria têxtil, de modo principal, o segmento de beneficiamento têxtil vem sendo discutida em estudos e pesquisas. Dentro deste contexto, os corantes dispersos utilizados no tingimento de fibras de acetato de celulose, poliamida e poliéster podem ser considerados de grande grau de impacto ambiental devido sua grande utilização e sua alta toxicidade. O objetivo principal deste trabalho é avaliar a qualidade de malhas de poliéster fabricados com fios standard (167f48 dtex) e microfibra (167f144 dtex), tintas com corantes dispersos C.I Disperse Red 60 e C.I Disperse Blue 79 com a reutilização dos banhos de tingimento. Foram avaliadas a reprodutibilidade da cor (espectrofotômetro), a solidez à lavagem e à fricção. Os valores experimentais obtidos nos tingimentos do primeiro banho (água limpa) foram usados como referência para analisar a qualidade dos tecidos tintos nos banhos subsequentes. As análises dos resultados experimentais foram feitas usando a análise de variância (ANOVA) com um intervalo de confiança de 95%. Os resultados mostraram os tipos de fios e de corantes utilizados nas tingimentos influenciam significativamente na reprodutibilidade da cor. Entretanto, estes mesmos fatores não foram significativos para as análises de solidez à lavagem e à fricção. O fator banho não foi significativo para as características de qualidade verificadas nos tecidos tintos, indicando que existe viabilidade na reutilização dos banhos de tingimento destes corantes / Actually, the environmental issue involving the textile industry, mainly, the segment of textile processing has been discussed in studies and research. Within this context, disperse dyes used in the dyeing of cellulose acetate, polyamide and polyester fibers can be considered environmental high impact due to their big demand and high toxicity. The main objective of this work is to evaluate the quality of polyester fabrics made with standard yarns (167f48 dtex) and microfiber (167f144 dtex), disperse colorants C.I Disperse Red 60 and C.I Disperse Blue 79 with the reuse of the dyeing baths. Color reproducibility (spectrophotometer), washing fastness and friction fastness were evaluated. Experimental values obtained on dyeings from the first bath (clean water) were used as reference to analyze the quality of the red tissues in the subsequent baths. Analyzes of the experimental results were done using analysis of variance (ANOVA) with a confidence interval of 95%. The results showed the types of yarns and dyes used in dyeing significantly influence color reproducibility. However, these same factors were not significant for the wash and friction fastness analyzes. The bath factor was not significant for the quality characteristics verified in the red tissues, indicating that there is viability in the reuse of the dyeing baths of these dyes

Atualmente, a questão ambiental envolvendo a indústria têxtil, de modo principal, o segmento de beneficiamento têxtil vem sendo discutida em estudos e pesquisas. Dentro deste contexto, os corantes dispersos utilizados no tingimento de fibras de acetato de celulose, poliamida e poliéster podem ser considerados de grande grau de impacto ambiental devido sua grande utilização e sua alta toxicidade. O objetivo principal deste trabalho é avaliar a qualidade de malhas de poliéster fabricados com fios standard (167f48 dtex) e microfibra (167f144 dtex), tintas com corantes dispersos C.I Disperse Red 60 e C.I Disperse Blue 79 com a reutilização dos banhos de tingimento. Foram avaliadas a reprodutibilidade da cor (espectrofotômetro), a solidez à lavagem e à fricção. Os valores experimentais obtidos nos tingimentos do primeiro banho (água limpa) foram usados como referência para analisar a qualidade dos tecidos tintos nos banhos subsequentes. As análises dos resultados experimentais foram feitas usando a análise de variância (ANOVA) com um intervalo de confiança de 95%. Os resultados mostraram os tipos de fios e de corantes utilizados nas tingimentos influenciam significativamente na reprodutibilidade da cor. Entretanto, estes mesmos fatores não foram significativos para as análises de solidez à lavagem e à fricção. O fator banho não foi significativo para as características de qualidade verificadas nos tecidos tintos, indicando que existe viabilidade na reutilização dos banhos de tingimento destes corantes / Actually, the environmental issue involving the textile industry, mainly, the segment of textile processing has been discussed in studies and research. Within this context, disperse dyes used in the dyeing of cellulose acetate, polyamide and polyester fibers can be considered environmental high impact due to their big demand and high toxicity. The main objective of this work is to evaluate the quality of polyester fabrics made with standard yarns (167f48 dtex) and microfiber (167f144 dtex), disperse colorants C.I Disperse Red 60 and C.I Disperse Blue 79 with the reuse of the dyeing baths. Color reproducibility (spectrophotometer), washing fastness and friction fastness were evaluated. Experimental values obtained on dyeings from the first bath (clean water) were used as reference to analyze the quality of the red tissues in the subsequent baths. Analyzes of the experimental results were done using analysis of variance (ANOVA) with a confidence interval of 95%. The results showed the types of yarns and dyes used in dyeing significantly influence color reproducibility. However, these same factors were not significant for the wash and friction fastness analyzes. The bath factor was not significant for the quality characteristics verified in the red tissues, indicating that there is viability in the reuse of the dyeing baths of these dyes

The production of polyethylene terephthalate (PET) textiles, commonly known as polyester, is an energy and water-intensive process, particularly during the dyeing and finishing stages, leading to significant carbon emissions and wastewater filled with toxic chemicals. Conventional dyeing processes consume large volumes of water and energy, making them environmentally harmful. Innovative methods like hydraulic spray atomizer offer a more sustainable alternative by reducing water and chemical usage, thus minimizing waste and environmental impact. This study explores the hydraulic spray dyeing process parameters, including pre-treatment, dyeing, pre-drying, and fixation steps for three different polyester fabrics. The objective is to achieve resource-efficient dyeing with comparable results to traditional methods, and to compare effectiveness of a combined pre-treatment and dyeing approach with a two-step spray application of pre-treatment and dyeing. Pre-treatment of the polyester fabrics with chemical hydrophilizing agents by spray application showed to improve the hydrophilic character and wetting capacity of three polyester fabrics—P75, P600, and Kibo based on reduced water contact angle measurements and increased vertical wicking rates. A pre-treatment also showed to enhance the K/S values of the three different polyester fabrics. The addition of a pre-drying step showed some indication of reducing disperse dye migration, and enhanced color strength of the Kibo fabrics. Spray dyed samples maintained dyeing quality comparable to padded samples. One-step spray processes demonstrated comparable or improved color properties and durability to fastness to washing and abrasion in comparison to two-step processes. The results demonstrate that the hydraulic spray atomizing system is viable for both dyeing and pre-treatment of polyester fabrics. Furthermore, this lays the groundwork for innovation in wet textile processes of polyester fabrics using this resource-efficient alternative, aiming towards sustainable textile production and dyeing.

The parcel shelf in a car is one of the things that are most exposed to ultraviolet light and heat. The sunlight causes ultraviolet radiation and excessive heat to this area. This can cause the material to degrade, fade or drift in colour. The parcel shelf production is today divided between three producers. This requires a good contact and cooperation between the different actors. As the automobile industry is a very complex industry, high demand is required of everyone involved. The goal of this study was to find improvements that could lead to a better ultraviolet and heat protection. Volvo Cars provided material and the experiments were held on their test facility. The tests were conducted based on the Volvo Cars requirements and methods. A Weather-Ometer is used to simulate the ultraviolet light and heat, the same way a parcel shelf is exposed to outdoors. Chemical analyses are used to determine whether there is any difference in the material when it is aged in a Weather-Ometer or not. The parcel shelf is made of needle punched, dispersed dyed polyester. The results showed that the present parcel shelf material does indeed show a colour shift after ageing. The authors present a number of suggestions to improve the material's characteristics. For example, Volvo could consider using an acrylic non-woven instead of polyester. Dyes that withstand ultraviolet radiation better can also be chosen and a variety of ultraviolet absorbers can be added. 2-(2-hydroxy-5-carboxy-phenyl)-2H-benzotriazole, Tinuvin P, 327 [2-(2-hydroxy-5-methyl-phenyl) 2H-benzotriazole, 2-(3,5-butyl-6-hydroxy)-2H-2-chloro-benzotriazole respectively] and 2,4-dihydroxy-benzophenone are example of absorbers that can be added to make the ultraviolet resistance better. / Program: Textilingenjörsutbildningen

Submitted by JEFFERSON HONORIO FRANCO null (jeffersonhfranco@gmail.com) on 2016-12-01T15:16:17Z No. of bitstreams: 1 TESE FINAL-IMPRESSÃO CD.pdf: 4568825 bytes, checksum: 666b30b163102c69eb93110502678419 (MD5) / Approved for entry into archive by Felipe Augusto Arakaki (arakaki@reitoria.unesp.br) on 2016-12-05T12:50:59Z (GMT) No. of bitstreams: 1 franco_jh_dr_araiq_par.pdf: 1149871 bytes, checksum: 4c942fc016c94499d690f6474dda7078 (MD5) / Made available in DSpace on 2016-12-05T12:50:59Z (GMT). No. of bitstreams: 1 franco_jh_dr_araiq_par.pdf: 1149871 bytes, checksum: 4c942fc016c94499d690f6474dda7078 (MD5) Previous issue date: 2016-11-21 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Corantes sintéticos do tipo azo têm sido um assunto de grande preocupação ambiental devido ao potencial genotóxico e mutagênico dos produtos de biotransformação. Deste modo, nos últimos anos a consequência da ingestão destes corantes presentes na agua potável servida à população é discutida por diversos autores. Este estudo avalia a ação de microssomas de fígado de rato, enzimas redutoras produzidas pela bactéria Escherichia coli (E. coli) e nitroredutase imobilizada na biotransformação de três corantes dispersos que possuem grupos azo, Disperse Red 73 (DR 73), Disperse Red 78 (DR 78) e Disperse Red 167 (DR 167). A técnica de Espectrofotometria de absorção molecular na região do Uv- visível, Cromatografia Líquida de Alta Eficiência com detector de arranjo de diodos (CLAE-DAD) e Cromatografia líquida acoplada à espectrometria de massas (LC-MS/MS) foram técnicas usadas para identificar os principais produtos gerados após os processos de degradação dos corantes. Polímeros de impressão molecular magnéticos (MMIPs) foram investigados usando reações de polimerização por precipitação para pré-concentração do corante DR 73, juntamente com a degradação por fotoeletrocatálise e subsequente análise dos produtos por LC-MS/MS. Os estudos in vitro do metabolismo de biotransformação dos corantes têxteis com microssoma de fígado de rato mostraram que as reações ocorreram preferencialmente no grupo azo e nitro dos corantes, indicando a redução destes grupos pelas enzimas do citocromo P-450. Foram obtidos dois produtos de degradação para cada corante após reação com a bactéria E. coli; o corante DR 73 originou os produtos 3-((4-aminofenil)(etil)amino)propanitrila e 4-nitroanilina, os produtos 3-((4-aminofenil)(etil)amino)propanitrila e 2-cloro-4-nitroanilina foram obtidos após reação com o corante DR78 e o DR 167 originou dimetil 3,3`-((3-acetamido-4aminofenil)azanediyl)dipropanoato e 2-cloro-4-nitroanilina, indicando a clivagem do grupo azo, possivelmente, pela enzima azoredutase, produzida pela bacteria. A enzima nitroredutase, imobilizada em partículas magnéticas modificadas com tosil, mostrou que a redução dos corantes ocorreu preferencialmente no grupo nitro, enquanto que a enzima livre no meio reacional resultou em mais de um produto de biotransformação para cada corante, atuando em mais de um sítio da molécula, comprovando a eficácia da imobilização enzimática para estudos de biotransformação e formação de produtos majoritários. A mutagenicidade dos corantes foi avaliado pelo ensaio de Salmonella/microssoma realizado nas estirpes TA 98 e TA 100, com e sem S9. De acordo com este ensaio, DR 73 foi o mais mutagênico. O MMIP para o corante DR 73 apresentou excelentes valores de religação (16 mg g−1 e 6 mg g−1, para MMIP e MNIP, respectivamente) indicando que o polímero molecularmente impresso formou cavidades específicas para retenção do corante. Através dos resultados obtidos por LCMS/MS, observou-se 100% de degradação do corante em apenas 60 min de tratamento via fotoeletrocatálise para soluções mais diluidas do mesmo, comprovando a eficiência da técnica na degradação de poluentes. Sendo assim, estes resultados sugerem que o MMIP mostrou uma excelente especificidade e seletividade para o corante DR 73 e uma técnica promissora na captação de corantes mutagênicos de águas superficiais, com grande potencial de aplicação e exploração na pré-concentração antes do tratamento. Além disso, a redução destes corantes por sistemas biológicos representa uma grande preocupação ambiental devido ao aumento da genotoxicidade para os seres vivos, em especial a seres humanos, produzindo compostos nocivos, tais como aminas condenadas pela Agência Internacional de Pesquisa sobre o Câncer. / Synthetic azo dyes have been a matter of great concern due to the genotoxic and mutagenic potential of the products originating from azo dye biotransformation. Thus, in recent years the result of the intake of these dyes present in drinking water supplied to a population is discussed by several authors. This work evaluates the action of rat liver microsomes, reducing enzymes produced by the Escherichia coli (E. coli) and nitroreductase immobilized on biotransformation of three disperse dyes bearing azo groups, namely Disperse Red 73 (DR 73), Disperse Red 78 (DR 78), and Disperse Red 167 (DR 167). UV-Vis spectrophotometry, high-performance liquid chromatography with diode array detector (HPLC-DAD), and liquid chromatography coupled to mass spectrometry (LC-MS/MS) were techniques used to identify the main products generated after the process degradation of dyes. Magnetic molecularly imprinted polymers (MMIPs) were investigated using precipitation polymerization reactions for preconcentration of the dye DR 73, together with the photoelectrocatalysis degradation and subsequent analysis of the products by LC-MS/MS. In vitro studies of biotransformation metabolism of textile dyes with rat liver microsome showed that the reactions occur preferentially in the group of azo and nitro dyes, indicating the reduction of these groups by enzymes of the cytochrome P-450. There were obtained two degradation products for each dye after reaction with E. coli; the dye DR 73 gave the product 3 - ((4-aminophenyl) (ethyl) amino) propanitrila and 4-nitroaniline, the product 3 - ((4-aminophenyl) (ethyl) amino) propanitrila and 2-chloro-4-nitroaniline were obtained after reaction with the dye DR78 and DR 167 gave 3,3`-dimethyl-((3-acetamido-4-aminophenyl) azanediyl) dipropanoato and 2chloro-4-nitroaniline; indicating cleavage of the azo group, possibly by azoredutase enzyme produced by bacteria. The nitroreductase enzyme immobilized on modified magnetic particles Tosyl showed that the reduction of dyes occurred preferentially in the nitro group, while the free enzyme in the reaction medium resulted in more than a product of biotransformation for each dye, acting in more than one site of the molecule, proving the efficacy of enzyme immobilization for biotransformation studies and formation of major products. The mutagenicity of the dyes was evaluated by the Salmonella/microsome assay performed on strains TA 98 and TA 100, with and without S9. According to this assay, DR 73 was the most mutagenic. The MMIP to the dye DR 73 showed excellent rebinding values (16 mg g−1 and 6 mg g−1, for MMIP and MNIP, respectively) indicating that the molecularly imprinted polymer formed cavities for specific dye retention. Through the results obtained by LC-MS/MS, it was observed 100% dye degradation in 60 min treatment for more dilute solutions thereof, proving the efficiency of technique in pollutant degradation. Thus, these results suggest that MMIP showed excellent specificity and selectivity for the dye DR 73 and a promising technique in capturing mutagenic dyes of surface water, with great potential for application and operation in the pre-concentration before treatment. Moreover, the reduction of these dyes by biological systems is a major environmental concern due to increased of genotoxicity for living beings, especially humans, producing harmful compounds, such as condemned amines by the International Agency for Research on Cancer.