Os corantes que apresentam grupos cromóforos do tipo azo (N=N) são amplamente empregados em numerosas aplicações na indústria, para colorir vários bens de consumo, dentre eles os têxteis. Entretanto, pelo fato de formarem aminas aromáticas carcinogênicas, quando a ligação N=N é rompida, seu uso está sujeito à legislação. Levando em consideração o potencial carcinogênico das aminas aromáticas, a quantificação das mesmas em produtos destinados à exportação se faz necessária. A técnica padrão para o monitoramento da presença dessas aminas em bens de consumo como os têxteis é a cromatografia líquida de alta eficiência, entretanto como alternativa tem-se a eletroforese capilar. Assim, neste trabalho 20 aminas aromáticas oriundas de azo corantes, banidas pela Comunidade Européia por meio da Diretiva 2002/61/EC, foram separadas por meio de eletroforese capilar (CE), com detecção no UV-Vis, e, a confirmação da presença dessas aminas em matrizes têxteis foi realizada por um método confirmatório de LC-MS, adaptado da literatura. Em CE o conhecimento das constantes de dissociação ácido-base se faz necessário para a otimização do pH ideal de corrida, assim estas, bem como mobilidades iônicas para cada uma das aminas aromáticas foram determinadas por meio de curvas de mobilidade efetiva em função do pH. O pH ótimo de separação de 2,50 foi determinado por meio do simulador de separação desenvolvido no grupo (SIMLACE). Dos métodos de separação estudados, o que apresentou maior número de aminas separadas (16 aminas) em linha de base em menor tempo (12 min) foi empregando um BGE composto apenas de 70 mmol/L de dihidrogenofosfato de sódio ajustado a pH 2,50 com ácido fosfórico, considerando um condicionamento de capilar de início de trabalho de 10 minutos de flush com BGE (dihidrogenofosfato de sódio 70 mmol/L ajustado a pH 2,50 com ácido fosfórico, contendo trietilamina 12,3 mmol/L) a uma pressão de 950 mbar, seguido da aplicação de uma tensão de +30 kV por 10 minutos; e um condicionamento entre réplicas de corrida eletroforética de 1 minuto de HCl 0,1mol/L (950 mbar) seguidos de 1 minuto de H2O (950 mbar). A extração das aminas da matriz têxtil envolve três etapas: a redução da ligação N=N, extração das aminas formadas e um posterior clean up e pre-concentração, sendo que para este último o sistema que apresentou melhor resposta em termos de eficiência de extração (da ordem de 100%) foi com o uso de extração em fase sólida com resina de troca catiônica. Por outro lado, a extração das aminas 1, 7 e 8 da matriz têxtil foi obtida por ultrassom após o estudo de um planejamento fatorial de superfície de resposta, a uma temperatura de 52 ºC, tempo de ultrassom de 5 minutos e concentração de HCl de 0,77 mol/L, com recuperações de 105 a 115%. Como figuras de mérito do método otimizado tem-se: linearidade no intervalo de 50,11 409,1 mmol/L (R2 > 0,98), LD (2,43 6,70 mmol/L) e LQ (8,10 22,3 mmol/L), precisão (0,23 27,6%), robustez (por planejamento fatorial), seletividade, especificidade (estudos de estresse com extrato da amostra) e recuperação (valores acima). O método validado foi aplicado a sete amostras adquiridas no mercado local. Dentre elas, duas apresentaram picos com tempos de migração e espectros semelhantes às aminas 5, 7 e 15, sendo que as aminas 7 e 15 foram confirmadas por meio do método de LC-MS/MS adaptado da literatura o qual permitiu a caracterização dessas aminas nas matrizes têxteis analisadas. / The dyes which have chromophoric groups like azo (N = N) are widely used in numerous applications in industry to color various consumer goods, including textiles. However, because of carcinogenic aromatic amines formed when N=N bond is broken, its use is subject to the legislation. Considering the carcinogenic potential of aromatic amines, to quantify them in products intended for export, is needed. The standard technique for monitoring the presence of these amines in consumer goods such as textiles is a high performance liquid chromatography, however the capillary electrophoresis technique can be a good alternative. In this work 20 aromatic amines derived from azo dyes, banned by the European Community by Directive 2002/61/EC, were separated by capillary electrophoresis (CE) with UV-Vis detection, and confirmation of the presence these amines textile matrix was conducted by a method confirmatory LC-MS, adapted from the literature. The knowledge of the dissociation constant acid-base (pKa) in CE technique is necessary to obtain the optimum pH for the separation. In these way the pKa as well as the ionic mobilities for each aromatic amines were determined by curves of effective mobility as a function of pH. The optimum pH for the separation was 2.50 as determined by the simulator separation developed in the group (SIMLACE). About the separation methods studied, which had a higher number of separate amines (16 amines) in the baseline in a shorter time (12 min) employing a BGE composed only of 70 mmol/L sodium dihydrogen phosphate adjusted to pH 2.50 with phosphoric acid, with a conditioning capillary either at the beginning of the working day (10 minutes flush with BGE (sodium dihydrogen 70 mmol/L adjusted to pH 2.50 with phosphoric acid, triethylamine containing 12.3 mmol/L) at a pressure 950 mbar followed by applying a voltage of +30 kV for 10 minutes) and among replicas (1 minute of HCl 0.1 mol/L (950 mbar) followed by 1 minute of H2O (950 mbar)). The extraction of amines textile matrix involves three steps: reduction of N = N bond, extraction of the amines formed and a subsequent clean up and pre-concentration. About the latter step, the best response in terms of extraction efficiency (about 100%) was obtained using solid phase extraction (SPE) with cationic exchange resin. In addition, the best condition for ultrasound extraction of the amines 1, 7 and 8, was determined by means of a response surface factorial design with three variables and two levels. The optimum condition was: temperature of 52 °C, application of ultrasound for 5 min and HCl concentration of 0.77 mol/L, with recoveries of 105% to 115%. Figures of merit for optimized method include: linearity in the range from 50.11 to 409.1 mmol/L (R2> 0.98), LD (limit of detection, 2.43 to 6.70 mmol/L) and LQ (limit of quantification, 8.10 to 22.3 mmol/L), precision (0.23 to 27.6%), robustness (established by a factorial design), selectivity, specificity (stress studies with real sample extracts) and recovery (listed above). The validated method was applied to seven samples purchased at local markets. Among them, two presented peaks with migration times and spectra similar the amines 5, 7, 12 and 15. But, in only one sample the amines 7 and 15 were confirmed by LC-MS/MS.

Os corantes que apresentam grupos cromóforos do tipo azo (N=N) são amplamente empregados em numerosas aplicações na indústria, para colorir vários bens de consumo, dentre eles os têxteis. Entretanto, pelo fato de formarem aminas aromáticas carcinogênicas, quando a ligação N=N é rompida, seu uso está sujeito à legislação. Levando em consideração o potencial carcinogênico das aminas aromáticas, a quantificação das mesmas em produtos destinados à exportação se faz necessária. A técnica padrão para o monitoramento da presença dessas aminas em bens de consumo como os têxteis é a cromatografia líquida de alta eficiência, entretanto como alternativa tem-se a eletroforese capilar. Assim, neste trabalho 20 aminas aromáticas oriundas de azo corantes, banidas pela Comunidade Européia por meio da Diretiva 2002/61/EC, foram separadas por meio de eletroforese capilar (CE), com detecção no UV-Vis, e, a confirmação da presença dessas aminas em matrizes têxteis foi realizada por um método confirmatório de LC-MS, adaptado da literatura. Em CE o conhecimento das constantes de dissociação ácido-base se faz necessário para a otimização do pH ideal de corrida, assim estas, bem como mobilidades iônicas para cada uma das aminas aromáticas foram determinadas por meio de curvas de mobilidade efetiva em função do pH. O pH ótimo de separação de 2,50 foi determinado por meio do simulador de separação desenvolvido no grupo (SIMLACE). Dos métodos de separação estudados, o que apresentou maior número de aminas separadas (16 aminas) em linha de base em menor tempo (12 min) foi empregando um BGE composto apenas de 70 mmol/L de dihidrogenofosfato de sódio ajustado a pH 2,50 com ácido fosfórico, considerando um condicionamento de capilar de início de trabalho de 10 minutos de flush com BGE (dihidrogenofosfato de sódio 70 mmol/L ajustado a pH 2,50 com ácido fosfórico, contendo trietilamina 12,3 mmol/L) a uma pressão de 950 mbar, seguido da aplicação de uma tensão de +30 kV por 10 minutos; e um condicionamento entre réplicas de corrida eletroforética de 1 minuto de HCl 0,1mol/L (950 mbar) seguidos de 1 minuto de H2O (950 mbar). A extração das aminas da matriz têxtil envolve três etapas: a redução da ligação N=N, extração das aminas formadas e um posterior clean up e pre-concentração, sendo que para este último o sistema que apresentou melhor resposta em termos de eficiência de extração (da ordem de 100%) foi com o uso de extração em fase sólida com resina de troca catiônica. Por outro lado, a extração das aminas 1, 7 e 8 da matriz têxtil foi obtida por ultrassom após o estudo de um planejamento fatorial de superfície de resposta, a uma temperatura de 52 ºC, tempo de ultrassom de 5 minutos e concentração de HCl de 0,77 mol/L, com recuperações de 105 a 115%. Como figuras de mérito do método otimizado tem-se: linearidade no intervalo de 50,11 409,1 mmol/L (R2 > 0,98), LD (2,43 6,70 mmol/L) e LQ (8,10 22,3 mmol/L), precisão (0,23 27,6%), robustez (por planejamento fatorial), seletividade, especificidade (estudos de estresse com extrato da amostra) e recuperação (valores acima). O método validado foi aplicado a sete amostras adquiridas no mercado local. Dentre elas, duas apresentaram picos com tempos de migração e espectros semelhantes às aminas 5, 7 e 15, sendo que as aminas 7 e 15 foram confirmadas por meio do método de LC-MS/MS adaptado da literatura o qual permitiu a caracterização dessas aminas nas matrizes têxteis analisadas. / The dyes which have chromophoric groups like azo (N = N) are widely used in numerous applications in industry to color various consumer goods, including textiles. However, because of carcinogenic aromatic amines formed when N=N bond is broken, its use is subject to the legislation. Considering the carcinogenic potential of aromatic amines, to quantify them in products intended for export, is needed. The standard technique for monitoring the presence of these amines in consumer goods such as textiles is a high performance liquid chromatography, however the capillary electrophoresis technique can be a good alternative. In this work 20 aromatic amines derived from azo dyes, banned by the European Community by Directive 2002/61/EC, were separated by capillary electrophoresis (CE) with UV-Vis detection, and confirmation of the presence these amines textile matrix was conducted by a method confirmatory LC-MS, adapted from the literature. The knowledge of the dissociation constant acid-base (pKa) in CE technique is necessary to obtain the optimum pH for the separation. In these way the pKa as well as the ionic mobilities for each aromatic amines were determined by curves of effective mobility as a function of pH. The optimum pH for the separation was 2.50 as determined by the simulator separation developed in the group (SIMLACE). About the separation methods studied, which had a higher number of separate amines (16 amines) in the baseline in a shorter time (12 min) employing a BGE composed only of 70 mmol/L sodium dihydrogen phosphate adjusted to pH 2.50 with phosphoric acid, with a conditioning capillary either at the beginning of the working day (10 minutes flush with BGE (sodium dihydrogen 70 mmol/L adjusted to pH 2.50 with phosphoric acid, triethylamine containing 12.3 mmol/L) at a pressure 950 mbar followed by applying a voltage of +30 kV for 10 minutes) and among replicas (1 minute of HCl 0.1 mol/L (950 mbar) followed by 1 minute of H2O (950 mbar)). The extraction of amines textile matrix involves three steps: reduction of N = N bond, extraction of the amines formed and a subsequent clean up and pre-concentration. About the latter step, the best response in terms of extraction efficiency (about 100%) was obtained using solid phase extraction (SPE) with cationic exchange resin. In addition, the best condition for ultrasound extraction of the amines 1, 7 and 8, was determined by means of a response surface factorial design with three variables and two levels. The optimum condition was: temperature of 52 °C, application of ultrasound for 5 min and HCl concentration of 0.77 mol/L, with recoveries of 105% to 115%. Figures of merit for optimized method include: linearity in the range from 50.11 to 409.1 mmol/L (R2> 0.98), LD (limit of detection, 2.43 to 6.70 mmol/L) and LQ (limit of quantification, 8.10 to 22.3 mmol/L), precision (0.23 to 27.6%), robustness (established by a factorial design), selectivity, specificity (stress studies with real sample extracts) and recovery (listed above). The validated method was applied to seven samples purchased at local markets. Among them, two presented peaks with migration times and spectra similar the amines 5, 7, 12 and 15. But, in only one sample the amines 7 and 15 were confirmed by LC-MS/MS.

by Chung Ho Yan. / Thesis (M.Phil.)--Chinese University of Hong Kong, 2003. / Includes bibliographical references (leaves 127-141). / Text in English; abstracts in English and Chinese. / by Chung Ho Yan. / Acknowledgments --- p.i / Abstract --- p.ii / Table of Contents --- p.v / List of Figures --- p.xi / List of Plates --- p.xiv / List of Tables --- p.xv / Chapter 1. --- INTRODUCTION --- p.1 / Chapter 1.1 --- Textile-Dyeing Industry in Hong Kong --- p.1 / Chapter 1.2 --- Processes Involved in Dyeing Industry --- p.3 / Chapter 1.2.1 --- Desizing --- p.3 / Chapter 1.2.2 --- Scouring --- p.3 / Chapter 1.2.3 --- Bleaching --- p.3 / Chapter 1.2.4 --- Mercerizing --- p.4 / Chapter 1.2.5 --- Dyeing and Printing --- p.4 / Chapter 1.2.6 --- Finishing --- p.4 / Chapter 1.3 --- Characterization of Wastewater of Dyeing Industry --- p.5 / Chapter 1.4 --- Toxicity of Effluent from Textile-Dyeing Industry --- p.9 / Chapter 1.5 --- Related Environmental Legislation --- p.9 / Chapter 1.6 --- Chemical Specific Approach and Toxicity Based Approach --- p.11 / Chapter 1.7 --- Whole-Effluent Toxicity (WET) Test --- p.13 / Chapter 1.8 --- Toxicity Identification Evaluation --- p.14 / Chapter 1.8.1 --- Phase I - Toxicity Characterization --- p.15 / Chapter 1.8.2 --- Phase II - Toxicity Identification --- p.15 / Chapter 1.8.3 --- Phase III - Toxicity Confirmation --- p.18 / Chapter 1.9 --- Toxicity Identification Evaluation on Effluent from Textile-Dyeing Industry --- p.19 / Chapter 1.10 --- Organisms Used for Toxicity Identification Evaluation --- p.20 / Chapter 1.11 --- Selection of Organisms for Bioassays --- p.20 / Chapter 2. --- OBJECTIVES --- p.24 / Chapter 3. --- MATERIALS AND METHODS --- p.25 / Chapter 3.1 --- Sources of Samples --- p.25 / Chapter 3.2 --- Whole Effluent Toxicity Test - Baseline Toxicity Test --- p.28 / Chapter 3.2.1 --- Microtox® test --- p.28 / Chapter 3.2.2 --- "Survival test of the marine amphipod, Hyale crassicornis" --- p.29 / Chapter 3.2.3 --- "Survival test of the brine shrimp, Artemia franciscana" --- p.33 / Chapter 3.2.4 --- "Survival test of the freshwater water flea, Daphnia magna" --- p.36 / Chapter 3.3 --- Toxicity Identification Evaluation ´ؤ Phase I Toxicity Characterization --- p.40 / Chapter 3.3.1 --- pH adjustment filtration test --- p.41 / Chapter 3.3.2 --- pH adjustment aeration test --- p.42 / Chapter 3.3.3 --- pH adjustment cation exchange test --- p.43 / Chapter 3.3.4 --- pH adjustment anion exchange test --- p.44 / Chapter 3.3.5 --- pH adjustment C18 solid phase extraction (C18 SPE) test --- p.45 / Chapter 3.3.6 --- pH adjustment XAD-2 solid phase extraction (XAD-2 SPE) test --- p.46 / Chapter 3.4 --- Toxicity Identification Evaluation - Phase II Toxicity Identification --- p.47 / Chapter 3.4.1 --- Determination of anions --- p.48 / Chapter 3.5 --- Toxicity Identification Evaluation ´ؤ Phase III Toxicity Confirmation --- p.50 / Chapter 3.5.1 --- Mase balance test --- p.50 / Chapter 3.5.2 --- Spiking test --- p.51 / Chapter 4. --- RESULTS --- p.52 / Chapter 4.1 --- Characteristics of Samples --- p.52 / Chapter 4.2 --- Whole Effluent Toxicity Test - Baseline Toxicity Test --- p.52 / Chapter 4.2.1 --- Toxicity of effluent sample determined by the Microtox® test --- p.52 / Chapter 4.2.2 --- Toxicity of effluent samples determined by Hyale crassicornis survival test --- p.52 / Chapter 4.2.3 --- Toxicity of effluent samples determined by Artemia franciscana survival test --- p.57 / Chapter 4.2.4 --- Toxicity of effluent samples determined by Daphnia magna survival test --- p.51 / Chapter 4.3 --- Toxicity Identification Evaluation - Phase I Toxicity Characterization --- p.57 / Chapter 4.3.1 --- Toxicity characterization of effluent samples determined by Hyale crassicornis survival test --- p.60 / Chapter 4.3.2 --- Toxicity characterization of effluent samples determined by Artemia franciscana survival test --- p.68 / Chapter 4.3.3 --- Toxicity characterization of effluent samples determined by Daphnia magna survival test --- p.68 / Chapter 4.4 --- Toxicity Identification Evaluation ´ؤ Phase II Toxicity Identification --- p.72 / Chapter 4.4.1 --- Baseline anion concentrations in effluent samples --- p.75 / Chapter 4.4.2 --- Sample1 --- p.75 / Chapter 4.4.3 --- Sample2 --- p.75 / Chapter 4.4.4 --- Sample3 --- p.75 / Chapter 4.4.5 --- Sample4 --- p.81 / Chapter 4.4.6 --- Sample5 --- p.81 / Chapter 4.4.7 --- Sample6 --- p.81 / Chapter 4.5 --- Toxicity Identification Evaluation 一 Phase III Toxicity Confirmation --- p.85 / Chapter 4.5.1 --- Mass balance test results --- p.85 / Chapter 4.5.2 --- Spiking test results --- p.96 / Chapter 5. --- DISCUSSION --- p.102 / Chapter 5.1 --- Whole Effluent Toxicity Test ´ؤ Baseline Toxicity Test --- p.102 / Chapter 5.1.1 --- Toxicity of effluent sample determined by the Microtox® test --- p.102 / Chapter 5.1.2 --- Toxicity of effluent samples determined by Hyale crassicornis survival test --- p.103 / Chapter 5.1.3 --- Toxicity of effluent samples determined by Artemia franciscana survival test --- p.104 / Chapter 5.1.4 --- Toxicity of effluent samples determined by Daphnia magna survival test --- p.104 / Chapter 5.2 --- Toxicity Identification Evaluation ´ؤ Phase I Toxicity Characterization --- p.105 / Chapter 5.2.1 --- pH adjustment filtration test --- p.105 / Chapter 5.2.2 --- pH adjustment aeration test --- p.106 / Chapter 5.2.3 --- pH adjustment cation exchange test --- p.106 / Chapter 5.2.4 --- pH adjustment anion exchange test --- p.106 / Chapter 5.2.5 --- pH adjustment C18 solid phase extraction (C18 SPE) test --- p.107 / Chapter 5.2.6 --- pH adjustment XAD-2 solid phase extraction (XAD-2 SPE) test --- p.107 / Chapter 5.3 --- Toxicity Identification Evaluation - Phase II Toxicity Identification --- p.107 / Chapter 5.3.1 --- Efficiency on chemical reduction of pH adjustment filtration test --- p.109 / Chapter 5.3.2 --- Efficiency on chemical reduction of pH adjustment aeration test --- p.109 / Chapter 5.3.3 --- Efficiency on chemical reduction of pH adjustment cation exchange test --- p.109 / Chapter 5.3.4 --- Efficiency on chemical reduction of pH adjustment anion exchange test --- p.109 / Chapter 5.3.5 --- Efficiency on chemical reduction of pH adjustment CI8 SPE test --- p.109 / Chapter 5.3.6 --- Efficiency on chemical reduction of pH adjustment XAD-2 SPE test --- p.110 / Chapter 5.4 --- Toxicity Identification Evaluation - Phase III Toxicity Confirmation --- p.110 / Chapter 5.4.1 --- Mass balance test results --- p.110 / Chapter 5.4.2 --- Spiking test results --- p.114 / Chapter 5.5 --- Comparison of Toxicant(s) Identified in the Six Dyeing Industrial Effluents --- p.117 / Chapter 5.6 --- Toxicant(s) Identified in Textile-Dyeing Industrial Effluent --- p.119 / Chapter 5.7 --- "Sources, Fate and Treatment of Sulfite Ion" --- p.120 / Chapter 5.8 --- Toxicity of Sulfite Ion --- p.121 / Chapter 5.9 --- Effect of Salinity on the Toxicity of Sulfite Ion --- p.122 / Chapter 5.10 --- Recommendation --- p.123 / Chapter 6. --- CONCLUSIONS / Chapter 7. --- REFERENCES / Chapter 8. --- APPENDICES

Pre-Hispanic geometric art forms In Peru and the Andean Area are taken to be an outgrowth of textile techniques. Textiles and fibre arts predate ceramics by several millennia In the Central Andean Area. The artist who created these textiles developed an art style which was to go largely unaltered until the arrival of the Spaniards. The foundations of the Andean art form date to the Pre-ceramic. The restrictive, rather Inflexible nature of the warp and the weft of the cloth (the geometric grid) was to influence the methods of represention that were to follow. Geometric designs were well suited to fit Into the rigid framework. A series of conventions were developed for the representation of symbols. With the development of ceramics, there was leeway for a new style to come Into being. However, this was not to be the case. The potter borrowed extensively from the weaving tradition and Its associated styles (only in Moche times did the potter make a break the highly geometric style developed centuries before, and even then this break with tradition was a short lived one). The pre-Columbian artist often portrayed birds, cats, fish and reptiles. Many of these designs were used frequently and repeatedly throughout the centuries, but none, I would maintain. was represented as frequently as the double-headed serpent, and with so few variants. Andean art Is a truly distinctive art form; very different from European art, and through Its geometricity It conveyed and still conveys a totally different approach to nature and the world surrounding Andean man.

Orientador: João Sinézio de Carvalho Campos / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-27T02:43:28Z (GMT). No. of bitstreams: 1 Louzi_VitorCesardeAlmeida_M.pdf: 3130788 bytes, checksum: 990e3e0e872cccd2ed1287be8d2b6cf8 (MD5) Previous issue date: 2015 / Resumo: Fibras poliméricas sintéticas vêm sendo muito utilizadas em diversas aplicações (medicina, têxtil, etc), especialmente na forma de monofilamentos, com diversos diâmetros, devido às suas características de resistência mecânica. No entanto apresentam baixa hidrofilidade e energia livre de superfície com propriedades adesivas relativamente fracas, limitando assim suas aplicações. Com objetivo de ampliar as aplicações deste material, técnicas estão sendo desenvolvidas no sentido de melhorar estas propriedades, especialmente as de superfície. Dentre as técnicas de modificação de superfície destaca-se a descarga corona a qual pode operar em condições ambientes de temperatura e pressão, sem necessidade de agentes químicos, minimizando a geração de resíduos. Desse modo, o presente trabalho estuda os efeitos promovidos pela descarga corona em três diferentes fibras poliméricas: polipropileno (PP), politereftalato de etileno (PET) e poliamida-6 (PA-6). Amostras desses polímeros foram submetidas à descarga corona sob condições ambientes controladas. O tratamento corona foi realizado em função dos parâmetros: distância entre os eletrodos e tempo de tratamento. Após tratadas, as amostras foram submetidas às técnicas de caracterização: ângulo de contato (Método de Wilhelmy), espectroscopia no infravermelho (FT-IR/ATR), microscopia eletrônica de varredura (MEV), calorimetria exploratória diferencial (DSC), ensaios de tração e absorção de água. Os valores de ângulo de contato dinâmico foram reduzidos em até 29,6%, 27,9% e 18,6% para amostras de PP, PET e PA-6 tratadas, respectivamente. Os valores de energia de superfície aumentaram em 50,3%, 26% e 15% para PP, PET e PA-6. Amostras de PP, PET e PA-6 tratadas por descarga corona (4mm e 120s) apresentaram grau de absorção de água igual a 9,4%, 8,5% e 9,1%. A partir dos resultados obtidos com amostras de monofilamentos de PP, PET e PA-6, sem tratamento e após corona, pode-se concluir que o tratamento corona promove aumento da hidrofilidade e as propriedades térmicas e mecânicas não são afetadas. Palavras-chave: descarga corona, fibras têxteis, monofilamentos poliméricos, polipropileno, politereftalato de etileno, poliamida-6, propriedades de superfície, hidrofilidade, ângulo de contato / Abstract: Synthetic polymer fibers have been widely used in various applications, especially in the form of monofilament and under various diameters, due to its characteristics of mechanical resistance. However synthetic polymer fibers exhibit low hydrophilicity and surface free energy with relatively weak adhesive properties, thus limiting their applications. Aiming to expand the applications of these materials, techniques are being developed to improve these properties, especially the surface. Among modification techniques there is the corona discharge which can operate in ambient temperature and pressure, without the need for chemical agents, minimizing the generation residue. Thus, this research work studies the effects caused by the corona discharge in three different polymeric fibers: polypropylene (PP), polyethylene terephthalate (PET) and polyamide-6 (PA-6). Samples of these polymers were subjected to corona discharge under controlled environmental conditions. The corona treatment was performed on the basis of the parameters: distance between the electrodes and time of treatment. After treated, the samples were subjected to characterization techniques: contact angle (Wilhelmy Method), infrared spectroscopy (FT-IR/ATR), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), tensile and water absorption. The dynamic contact angle values were reduced by up to 29,6%, 27,9% and 18,6% for PP, PET and PA-6 treated samples, respectively. The surface energy values increased by 50,3%, 26% and 15% for PP, PET and PA-6. PP, PET and PA-6 samples treated by corona discharge (4mm and 120s), showed the degree of water absorption equal of 9,4%, 8,5% and 9,1%. From the results obtained with samples of PP, PET and PA-6, without treatment and after treatment, can be concluded that the corona treatment enhances the hydrophilicity and the thermal and mechanical properties are not affected. Keywords: corona discharge, textile fibers, monofilament polymer, polypropylene, polyethylene terephthalate, polyamide-6, surface properties, hydrophilicity, contact angle / Mestrado / Ciencia e Tecnologia de Materiais / Mestre em Engenharia Química

To decrease the environmental footprint, the textile industry needs to become more circular. One company that is trying to close the textile lifecycle loop is the Swedish company Renewcell. In the Renewcell process, discarded clothes and other textile waste are turned into a dissolving pulp that can be used for production of new textiles. For this to work, it is important to generate a non-colored dissolved pulp. Therefore, it is of great interest to be able to optimize the bleaching process and evaluate different starting materials. Today, there are different methods that have been used for quantification of specific dyes and for identification of raw materials in textiles. However, there is no complete method that can be used for all types of dyes and raw materials. This master thesis will therefore investigate the bleaching step and the raw materials used in Renewcell’s recycling process. The aim with this project is to develop a method, to be able to analyse the presence of dyes qualitatively and quantitatively in the dissolved pulp from the recycled cotton-based textiles. To do so, different chemical analysing methods were used. These include kappa number measurements, UV-VIS and FTIR. Nine different types of jeans, one yarn, three raw materials (cotton, PET and elastane), and two pure dyes (indigo and black sulfur dye) were selected for this project. The result from the kappa number measurements shows that only the blue jeans, blue yarn and black jeans could be bleached and measured by using the original kappa number method at 25 degrees C. But when the same procedure was done manually and the temperature was increased to 70 degrees C, almost all materials could be bleached and measured. Therefore, the conclusion is that this method can be a successful quantification method. However, the temperature correction equation needs to be developed further to be able to quantify the exact amount of dyes. The kappa number was also compared with the absorbance factor, i.e. the k-value from the UV-VIS results. A correlation could be seen for the blue jeans, blue yarn, and black jeans. So, the UV-VIS method could also be a possible method for quantification of dyes in textiles. For the qualitative analyses, FTIR was used. The results showed that the raw materials could be identified by comparing the resulting FTIR spectra with a reference spectrum. For the jeans and yarn materials, indigo dye was identified for the blue jeans, blue yarn, and black jeans. However, for the other materials, the amount of dyes was too low to be able to draw conclusions about the chemical structure. With further development, these methods could be used as successful qualitative and quantitative methods for analysing dyes in textiles. This would generate positive consequences in several ways. The usage of bleaching chemicals could be optimized, and the quality of the final textile material could be improved. This would benefit both the manufacturer of these recycled textiles (economically) and the consumer who will buy the final product (quality). Indirectly, this would help to decrease the environmental footprint from the textile industry.

Consumer demands have led to the development of new, more stable textile dyes. These dyes, many of the azo type, are often incompletely degraded/removed in wastewater treatment plants, leading to the discharge of highly colored effluents to rivers and streams. Concerns by downstream users of that water have led to enactment of effluent color and toxicity standards for plants that treat textile dye wastewater. Both anaerobic and aerobic biological degradation of azo dyes have been reported in the literature; the rate and extent of degradation is often quite dye-specific. This research utilized laboratory-scale reactors to investigate the effectiveness of those treatments, both singly and in combination, on two azo dye wastewaters: a textile dyeing and finishing process water and a municipal wastewater consisting predominately of textile dyeing and finishing mill effluents. / Master of Science

In a fiber spinning process molten polymer is extruded into a fiber. The resulting fiber known as as-spun fiber is relatively weak and shows a large plastic central zone in its constitutive behavior. As a result the fiber deforms substantially without a significant change in load thus making it unsuitable for stress bearing applications. The range of plastic deformation is related to the natural draw ratio. In order to improve the mechanical properties of as spun fibers, fiber spinning is followed by a fiber draw process. With multi stage draw the as-spun fiber is drawn beyond the plastic region in various drawing zones which produces greater orientation of the polymer chains in the axial direction of the fiber thus enhancing mechanical strength characteristics of the fiber. The multistage draw process consists of several rollers each rotating at a speed greater than the one prior to it. The objective of this work is to develop a first approximation to model fiber draw in the multistage drawing process, with and without a draw pin. As the first step the slippage of fibers on rollers was analysed by including centrifugal acceleration and acceleration due to stretching. The draw in a free span is also modelled. Several representative draw processes were examined. It was found draw pin localizes the draw significantly although the resulting mechanical unloading complicates the analysis. Draw in the free span is impossible for isothermal draw processes, and anisothermal draw induces thermal unloading in the system. A comprehensive analysis of various draw processes will be examined.

Particles originating from bacteria, fungi (including mold spores, mildew, yeast), pollen, dust mites, and viruses can induce immune responses that trigger allergies and asthma. Carpeting is believed to act as a "sink" where bioparticulates are trapped via adhesive interactions and then are released by foot traffic or cleaning. This scenario can result in an accumulation of contaminants at higher levels than would be found outdoors or in a carpet-less environment. Numerous organizations (school districts, hospitals) have taken steps to remove carpeting, even though this hypothesis remains unproven. While statistical studies exist both in support and denial of the accumulation hypothesis, there is little fundamental understanding of the microscopic-level interactions between carpet and bioparticles. A fundamental understanding of particle affinities with polymers utilized in carpet would help to develop accurate models and address real problems in a rational and productive manner. In addition, a solution to the bioparticulate accumulation problem would have a profound impact on US health, resulting in significant economic savings. More than 20 million people suffer from asthma in the U.S., with children being the most vulnerable. In 2000 there were 9.3 million physician office visits and 1.8 million emergency room visits due to asthma alone, resulting in an estimated $9.4 billion in medical costs and $4.6 billion in lost productivity annually. In this thesis, two measurement techniques were developed to quantify the adhesive interactions between biological particulates and polymeric carpeting materials. Atomic force microscopy (AFM) was used to measure the adhesive interactions of relevant biological particulates (in this case the E. coli bacteria and A. artemisiifolia ragweed pollen grains) with Nylon-6 and Nylon-6,6, polyamide-12 and polystyrene. The adhesion force measurements were modeled using several adhesion theories. We found that the Hamaker models were sufficient for explaining the data, indicating the prominence of van der Waals forces in controlling bioparticle interactions with polyamides. In addition, the geometry of the pollen played a significant role: adhesion forces were approximately a multiple of the number of contact points the grain has with the surface. Forces for E. coli and polyamides were about the same magnitude as polyamide-polyamide surface self-interactions.

A reactive-ionic functional group was incorporated into the structure of fiber finishes and colorants to provide high-yield add-on and permanency. The reactive-ionic group consists of a moderately strained, cyclic ammonium group which undergoes ionic assembly on the surface of negatively charged substrates. The ionic bond is then converted to a covalent bond at elevated temperatures via a ring-opening reaction. A reactive-ionic alkyl (wax) finish was prepared from octadecanol and N-phenyl pyrrolidine then applied to a glass slide to provide a permanent, hydrophobic surface with an average contact angle increase of approximately 40°. A reactive-ionic fluorinated finish was prepared from 1H,1H,2H,2H-perfluoro-1-octanol and N-phenyl pyrrolidine and after application served as a permanent, non-wetting, anti-stain finish for nylon carpet. A reactive-ionic chromophore (dye) was prepared from C.I. Disperse Red 1 and quinuclidine. The reactive-ionic dye was applied to cellophane and nylon films and bleached cotton, nylon and silk fabrics. The percent exhaustion for a 1% owf dyeing of silk fabric was measured to be 98% using visible light absorbance spectrophotometry. K/S values obtained from reflectance spectrophotometric measurements of a 1% owf dyeing of nylon 6,6 fabric showed a 6% color loss after solvent extraction, indicating that the dyeing was indeed permanent.