Corantes e pigmentos são utilizados no mundo todo para alterar a percepção visual de diversos bens de consumo. Dentre esses compostos se destacam os corantes que possuem grupamentos azo ou nitro como cromóforo. Muitas dessas substâncias são potencialmente tóxicas, seja na sua forma original seja após a biotransformação, com ênfase aos efeitos mutagênicos e/ou carcinogênicos. Este trabalho teve como objetivo investigar as rotas metabólicas e avaliar o perfil toxicológico parcial dos corantes Disperso Amarelo 9 e Sudan III. O Sudan III é um corante azóico e que embora tenha estrutura química muito semelhante ao Sudan I, um carcinógeno humano, existem poucos dados na literatura a respeito de sua toxicidade. Vale ressaltar que o Sudan III é um corante de alimentos banido da maioria dos países, porém tem sido repetidamente detectado em alimentos industrializados como adulterante. Já o corante Disperse Yellow 9 é amplamente utilizado principalmente pelas indústrias têxteis, porém não foram encontrados dados na literatura sobre seu potencial tóxico. Foram realizados estudos espectroeletroquimicos capazes de simular reações de oxidação e redução que ocorrem em organismos vivos, além de sistema exógeno de metabolização (S9). A mutagenicidade dos corantes foi avaliada pelo ensaio de Samonella (utilizando as linhagens TA98, TA1535, TA100 e YG1042, com e sem S9) e por meio da avaliação da capacidade de ligação com o DNA e a guanosina in vitro. Ainda, verificou-se a indução de morte celular em condrócitos bovinos. Nossos resultados mostraram que as condições de oxidação (eletroquímica ou após a reação com S9) e redução foram capazes de modificar o grupamento cromóforo tanto do corante Sudan III quanto do Disperso amarelo 9, e esse efeito é esperado em organismos vivos, podendo formar derivados tóxicos. O corante Sudan III é capaz de se ligar ao DNA de forma estável, mais especificamente com a base nitrogenada guanosina, enquanto o Disperso Amarelo 9 se liga fracamente ao DNA e não com a guanosina. O corante Sudam III exibiu fraca mutagenicidade e apenas com a linhagem TA1535. Por outro lado, Disperso Amarelo 9 foi positivo para as linhagens TA1535 e YG1042, e o efeito foi mais pronunciado após a ativação metabólica. Ambos os corantes induziram à morte dos condrócitos de forma tempo e concentração dependente. Assim, ambos os corantes foram considerados tóxicos, tanto na sua forma original quanto após biotransformação e podem levar a riscos à saúde humana e ao ecossistema quando de sua exposição. / Dyes and pigments are applied worldwide to change the visual perception of many products. Among these compounds, dyes containing azo and nitro bond as chromophore are very important groups. A wide range of these substances are potentially toxic either in its original form or after biotransformation leading to mutagenic / or carcinogenic effects. The aim of the present study was to investigate the metabolic pathways involving the chromophore group and also to evaluate the toxicological profile of Disperse Yellow 9 and Sudan III dyes. Sudan III is an azo dye that has a very similar chemical structure to Sudan I a known carcinogen. Despite, there are few data about Sudan III toxicity in the literature. It is important to point out that Sudan III is banned from most worldwide food industry it has been frequently detected as an adulterant in a large amount of processed food. The literature has no information about the toxicity potential of Disperse Yellow although it is widely and mainly used by textile industries. On the present we performed a spectroeletrochemical method capable of simulating bio- reactions able to occur on living organisms such as oxidation and reduction, also exogen metabolization system (S9) were applied. The mutagenicity of the dyes was evaluated by Salmonella assay (using strains TA98, TA1535, TA100 and YG1042, with and without S9). The ability of causing stable bonds to DNA and guanosine were also tested in vitro. Also the capacity of inducing cell death on bovine chondrocytes was investigated. Our results indicated that the oxidation reactions (spectroeletrochemical method or after S9 reaction) and also the reduction reactions were able to modify the chromophore group for the studied dyes Sudan III and Disperse Yellow 9, this effect could be expected in living organisms and may also generate toxic products. Sudan III is capable of binding to DNA and forming stable aducts, specifically to the nitrogenated base guanosine, while Disperse Yellow 9 binds weakly to DNA and does not react with guanosine. Low mutagenicity was observed for strain TA1535 for Sudan III dye. Besides, strains TA1535 and YG1042 gave positive responses for Disperse Yellow, the effect was pronounced after metabolic activation. Death of chondrocytes was observed for both dyes demonstrating time and concentration dependency. Toxicity was observed for both dyes, before and after biotransformation, this effect may lead to risks on human health and also for the environment.

Particulate matter (PM) concentrations in ambient air can be monitored by gravimetric sampling near a source using Federal Reference Method (FRM) samplers. PM is regulated by size, with PM10, which is comprised of particles with aerodynamic equivalent diameters less than or equal to 10 μm, being the main focus of this research. FRM PM10 samplers exhibit sampling errors when sampling dusts with mass median diameters (MMDs) that are larger than the 10 μm sampler cutpoint. For industries to be regulated equitably, these sampler errors must be quantified and understood. This research evaluates the performance of FRM PM10 and low volume total suspended particulate (TSP) samplers under the controlled conditions of a wind tunnel. The performance evaluation was conducted by observing the sampler cutpoints, slopes, and measured concentrations. These measured values were compared to values obtained using a collocated isokinetic reference sampler. The results of this research indicate that PM10 samplers do not operate as intended under all conditions. The cutpoint of the PM10 inlets was significantly higher than the maximum FRM limit of 10.5 μm when sampling dust with MMDs larger than the cutpoint of the sampler. The slope values for the PM10 inlets were significantly higher than the maximum FRM limit of 1.6. MMDs and geometric standard deviations of PM collected by TSP samplers were significantly different than those of PM collected using the collocated isokinetic sampler. The concentrations measured by the TSP samplers were significantly higher than the collocated isokinetic sampler. The results of this research provide a better understanding of the performance of TSP and PM10 samplers operating under different conditions and shows that these samplers are not operating as intended. Because of this, industries may be suffering the consequences of inequitable regulation.

Verweilzeitverteilungen werden zur Charakterisierung verfahrenstechnischer und speziell reaktionstechnischer Prozesse herangezogen. In dispersen Systemen existiert für jede Phase eine Verweilzeitverteilung, die sich stark voneinander unterscheiden können. Verweilzeitverteilungen werden häufig auf der Basis des Dispersionsmodells oder mittels einer Rührkesselkaskade beschrieben, wobei die Anpassung nicht immer gut ist. Deshalb werden zunächst halbempirische Gleichungen vorgestellt, die mittels charakteristischen Parametern (mittlere, minimale, maximale Verweilzeit; Exponent) eine flexible Nachbildung erlauben. Die Brauchbarkeit dieser Gleichungen wird für fluide und disperse Phase anhand der Nachrechnung veröffentlichter Verweilzeitverteilungskurven in unterschiedlichen Apparaten nachgewiesen, wobei auch ein Vergleich mit den Ergebnissen anderer Modelle erfolgt. Unter der Annahme einer stationären Sinkgeschwindigkeit gelingt für stark vereinfachte Fälle die Ableitung analytischer Ausdrücke für die Verweilzeitverteilung der dispersen Phase. Realere Fälle werden mit dem stochastischen Modell ZEMP (Zellenmodell mit Platzerwechselwahrscheinlichkeit), das um die Einbeziehung der Relativgeschwindigkeit der Partikeln erweitert wurde, erfasst. Dadurch wird es möglich, den Einfluss des Dispersionskoeffizienten, der Zugabeart, des Geschwindigkeitsprofils und des Vorliegens von Eigenschaftsverteilungen auf die Verweilzeitverteilung separat auszuweisen. Für das sich entwickelnde Geschwindigkeitsprofil des laminar durchströmten Rohrs und Kanals werden Gleichungen aufgestellt, in die die Werte von Literaturen eingingen. Damit wird der Einfluss der Einlaufstrecke auf die sich ausbildende Verweilzeitverteilung ermittelt.

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

Corantes e pigmentos são utilizados no mundo todo para alterar a percepção visual de diversos bens de consumo. Dentre esses compostos se destacam os corantes que possuem grupamentos azo ou nitro como cromóforo. Muitas dessas substâncias são potencialmente tóxicas, seja na sua forma original seja após a biotransformação, com ênfase aos efeitos mutagênicos e/ou carcinogênicos. Este trabalho teve como objetivo investigar as rotas metabólicas e avaliar o perfil toxicológico parcial dos corantes Disperso Amarelo 9 e Sudan III. O Sudan III é um corante azóico e que embora tenha estrutura química muito semelhante ao Sudan I, um carcinógeno humano, existem poucos dados na literatura a respeito de sua toxicidade. Vale ressaltar que o Sudan III é um corante de alimentos banido da maioria dos países, porém tem sido repetidamente detectado em alimentos industrializados como adulterante. Já o corante Disperse Yellow 9 é amplamente utilizado principalmente pelas indústrias têxteis, porém não foram encontrados dados na literatura sobre seu potencial tóxico. Foram realizados estudos espectroeletroquimicos capazes de simular reações de oxidação e redução que ocorrem em organismos vivos, além de sistema exógeno de metabolização (S9). A mutagenicidade dos corantes foi avaliada pelo ensaio de Samonella (utilizando as linhagens TA98, TA1535, TA100 e YG1042, com e sem S9) e por meio da avaliação da capacidade de ligação com o DNA e a guanosina in vitro. Ainda, verificou-se a indução de morte celular em condrócitos bovinos. Nossos resultados mostraram que as condições de oxidação (eletroquímica ou após a reação com S9) e redução foram capazes de modificar o grupamento cromóforo tanto do corante Sudan III quanto do Disperso amarelo 9, e esse efeito é esperado em organismos vivos, podendo formar derivados tóxicos. O corante Sudan III é capaz de se ligar ao DNA de forma estável, mais especificamente com a base nitrogenada guanosina, enquanto o Disperso Amarelo 9 se liga fracamente ao DNA e não com a guanosina. O corante Sudam III exibiu fraca mutagenicidade e apenas com a linhagem TA1535. Por outro lado, Disperso Amarelo 9 foi positivo para as linhagens TA1535 e YG1042, e o efeito foi mais pronunciado após a ativação metabólica. Ambos os corantes induziram à morte dos condrócitos de forma tempo e concentração dependente. Assim, ambos os corantes foram considerados tóxicos, tanto na sua forma original quanto após biotransformação e podem levar a riscos à saúde humana e ao ecossistema quando de sua exposição. / Dyes and pigments are applied worldwide to change the visual perception of many products. Among these compounds, dyes containing azo and nitro bond as chromophore are very important groups. A wide range of these substances are potentially toxic either in its original form or after biotransformation leading to mutagenic / or carcinogenic effects. The aim of the present study was to investigate the metabolic pathways involving the chromophore group and also to evaluate the toxicological profile of Disperse Yellow 9 and Sudan III dyes. Sudan III is an azo dye that has a very similar chemical structure to Sudan I a known carcinogen. Despite, there are few data about Sudan III toxicity in the literature. It is important to point out that Sudan III is banned from most worldwide food industry it has been frequently detected as an adulterant in a large amount of processed food. The literature has no information about the toxicity potential of Disperse Yellow although it is widely and mainly used by textile industries. On the present we performed a spectroeletrochemical method capable of simulating bio- reactions able to occur on living organisms such as oxidation and reduction, also exogen metabolization system (S9) were applied. The mutagenicity of the dyes was evaluated by Salmonella assay (using strains TA98, TA1535, TA100 and YG1042, with and without S9). The ability of causing stable bonds to DNA and guanosine were also tested in vitro. Also the capacity of inducing cell death on bovine chondrocytes was investigated. Our results indicated that the oxidation reactions (spectroeletrochemical method or after S9 reaction) and also the reduction reactions were able to modify the chromophore group for the studied dyes Sudan III and Disperse Yellow 9, this effect could be expected in living organisms and may also generate toxic products. Sudan III is capable of binding to DNA and forming stable aducts, specifically to the nitrogenated base guanosine, while Disperse Yellow 9 binds weakly to DNA and does not react with guanosine. Low mutagenicity was observed for strain TA1535 for Sudan III dye. Besides, strains TA1535 and YG1042 gave positive responses for Disperse Yellow, the effect was pronounced after metabolic activation. Death of chondrocytes was observed for both dyes demonstrating time and concentration dependency. Toxicity was observed for both dyes, before and after biotransformation, this effect may lead to risks on human health and also for the environment.

We address the problem of the correct description of light-matter coupling for excitons and cavity photons in the case of systems with multiple photon modes or excitons, respectively. In the literature, two different approaches for the phenomenological coupling Hamiltonian can be found: Either one single Hamiltonian with a basis whose dimension equals the sum of photonic modes and excitonic resonances is used. Or a set of independent Hamiltonians, one for each photon mode, is chosen. Both are usually used equivalently for the same kind of multi-photonic systems which cannot be correct. However, identifying the suitable Hamiltonian is difficult when modeling experimental data. By means of numerical transfer matrix calculations, we demonstrate the scope of application of each approach: The first one holds only for the coupling of a single photon state to several excitons, while in the case of multiple photon modes, separate Hamiltonians must be used for each photon mode.

his thesis deals with preparation of transparent ceramic sheets made out of sub-µm alumina powder. Green bodies are prepared by ultraviolet (UV) curing of UV curable resin containing ceramic powder followed by debinding of organic parts at elevated temperature. High relative density of green bodies is essential for reduction of shrinkage during subsequent sintering process. Therefore high solids loading dispersions containing > 57 vol% ceramic particles are used. To reach transparent behaviour, porosity within the sheets must be reduced completely. Therefore hot isostatic pressing (HIP) is used as a final operation. Finally, light transmission and hardness measurements are presented. Possibilities of making high resolution microstructures using maskless lithography and some suggestions for use of the UV curing technique for production of complex-shaped 3D structures are briefly mentioned.

<p> Poly(N-isopropylacrylamide) (PNIPAM) has attracted much attention as a thermo-responsive polymer. However, the molecular weight (MW) dependence of its phase transition temperature is still controversial. This situation is largely due to the difficulty in synthesizing narrow-disperse PNIPAM. We have addressed the challenge and developed an atom transfer radical polymerization (ATRP) method to prepare narrow-disperse PNIPAM with moderate to high conversions, using branched alcohols as solvents. Aqueous solutions of these narrow-disperse PNIPAMs showed a dramatic decrease of the phase transition temperature with increasing molecular weight, as measured by turbidimetry and differential scanning calorimetry. Four other series of narrow-disperse PNIPAM with well-controlled molecular weights and with end groups of varying hydrophobicity were also synthesized by ATRP using the corresponding initiators, which enabled us to resolve the MW and end group effects. All the four series of samples showed an inverse molecular weight (MW) dependence of their phase transition temperature. The magnitude of the MW dependence decreased when using more hydrophobic end groups. The end groups were observed to have effects on the cloud point temperature, on the shape of the cloud point curves, and on the enthalpy of the phase transition.</p> / Thesis / Master of Science (MSc)

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.

Polyetentereftalat, PET, är den vanligaste polymeren i den grupp av syntetiska polymerer som går under det generiska namnet polyester, PES, i textilindustrin. År 2015 producerades cirka 53 miljoner ton PET-fibrer, vilket är 58,6% av alla fibrer som producerades i världen samma år. Användningen av syntetiska fibrer som tillexempel PET förväntas öka eftersom platån för bomullsproduktion är uppnådd. Det är en stor utmaning för samhället att ta tillvara på dessa resurser även när en textil anses vara förbrukad på andra sätt än downcycling, energiutvinning eller deponi. Det kommer att krävas flera olika metoder för att effektivt ta tillvara på förbrukad textil från konsument för att föra in textilen i en cirkulär livscykel. En metod för att minska mängden jungfruligt material som används är återvinning. PET-flaskor återvinns mekaniskt genom att granulera och smälta om till ny spinnmassa och PET-fibrer återvinns genom kemisk återvinning. Vad gäller mekanisk återvinning är ett problem tillsatser som finns i produkten. Detta arbete beskriver olika tillsatser som tillsätts i polyester från garnspinning till slutberedning. Det har inte framkommit hur dessa tillsatser påverkar en mekanisk återvinning. Tillsatser som är kända att skapa problem vid återvinning av PET-flaskor är lim, pappersetiketter och färg. Färg i ingående material resulterar i en missfärgning i återvunnet material. Därför undersöktes möjligheten i detta arbete att ta bort dispersionsfärg från polyesterfibrer för att även kunna återvinna dessa genom omsmältning. Det finns flera patent som har som gemensam metod att avfärga polyester genom att lägga ned materialet i mindre bitar i upphettat lösningsmedel under konstant omrörning. I patenten bryts sedan polyestern ned genom kemisk återvinning och därför är det inte tydligt beskrivet hur resultatet av avfärgningen blir. Ett nyligen publicerat patent från 2016 har studerats närmare då patentet syftar till att avfärga och återvinna polyesterfibrer från använda kläder. I detta arbete har försök utförts genom att modifiera en del av ett exempel som beskrivs i patentet. Syftet var att undersöka och optimera återanvändningen av lösningsmedel samt definiera en optimal avfärgningstid. Resultatet har betydelse eftersom det ger kvantitativ data med avseende på avfärgning inför en återvinningsprocess och skulle kunna bidra till att mekanisk återvinning av textil utvecklas, vilket gynnar ett hållbart samhälle. I studien har en kontrollerad färgning av ett trikåtyg i 100% polyester utförts med dispersionsfärg som enbart innehåller en kromofor grupp, Disperse Blue 56. Tyget har sedan skurits i mindre bitar, 2*2 cm, för att avfärgas i lösningsmedel, 93-95 ℃, under konstant omrörning med badförhållandet 1:20. Lösningsmedlet som används i denna studie är 1,3 dimethyl-2-imidazolidione 98%, vilket har förkortats genomgående till DMI. Det har undersökts om avfärgningstiden kan förkortas till 10 minuter vilket sedan jämfördes med textil som avfärgats under 15 minuter. En förkortning av processtiden kan innebära en mer resurssnål avfärgningsprocess. Vidare har det även undersökts om det går att återanvända samma lösningsmedel till flera omgångar avfärgning, vilket definierats som användningsgrad 1 till 3. Textilen har efter avfärgning tvättats i rumstempererad DMI och rumstempererad etanol innan torkning i 12 timmar. Tygbitar som avfärgats i användningsgrad 1 av DMI under 15 minuter ger lägst värden på kulörthet vilket har säkerställts genom statistiska beräkningar. Det har även visats att optiskt vitmedel, av okänd typ, delvis avlägsnats i samtliga försök. Vikt- och volymförändring har analyserats men det går inte att fastslå att någon förändring sker.