No description available.

An AFM relative stiffness technique was applied to reconstituted Beta vulgaris L. wax films. Consecutive force arrays (n=100) made on the waxy surface at the same locations showed that there was no relative change in surface elasticity and this information was used as a reference to further experimental measurements. A surfactant solution was subsequently dropped on the waxy surface and the same array of indents was made at the same location as the reference test. The plant wax surface showed a reduction in its surface elasticity properties. The study has demonstrated that the AFM technique could be used to undertake a systematic assessment of the plasticising effects of agrochemicals on native and reconstituted plant wax films.

Baigiamajame darbe pateikta: detergentų paplitimas, jų fizikinės, cheminės savybės, klasifikacija ir daroma žala aplinkai. Analizuojami detergentais užterštų nuotekų valymo metodai. Analizuojami dujų burbuliukų susidarymo detergentų tirpaluose ypatumai, aprašomos dinaminės ir statiškai stabilios putos, pateikiama putų aparatų charakteristika. Pateikiamos suspenduoto sluoksnio charakteristikos ir jo galimybės detergentams iš nuotekų valyti. Darbo tikslas – ištirti suspenduoto sluoksnio įtaką valant detergentus iš nuotekų. Darbą sudaro 7 dalys: įvadas; tyrimo objektas ir problemos aprašymas; detergentais užterštų nuotekų valymas, putų burbuliukų ir putų susidarymo ypatumai, putų aparatai; suspenduoto sluoksnio charakteristikos ir jo galimybės panaudojant detergentams iš nuotekų valyti; eksperimentinė dalis; išvados; literatūros sąrašas. Eksperimentinėje dalyje teoriškai apskaičiuoti suspenduoto sluoksnio parametrai, aprašomas eksperimentinis stendas, jo veikimo principas, naudotos matavimo priemonės, pateikta eksperimento atlikimo metodika, pagal gautus eksperimentinius duomenis apskaičiuoti kintamieji suspenduoto sluoksnio parametrai. Darbo pabaigoje analizuojami gauti rezultatai ir pateikiamos darbo išvados. Darbo apimtis – 67 p. teksto be priedų, 21 iliustracija, 4 lentelės, 24 bibliografiniai šaltiniai. Atskirai pridedami darbo priedai. / Thesis submits the spread of detergents, their physical, chemical properties, classification and environmental damage. There are analyzed various waste water cleaning methods of detergents. Froth formation in detergent leaches, dynamic and static stability of foams and basic information about froth devices are given. The characteristics of the suspended layer and its use in water treatment of detergents are given. The aim of this work – is to explore the suspended layer in cleaning waste water of detergents. Final work consists of seven parts: introduction; the subject matter and the problem description; water purification of synthetic detergents, characteristics of froth bubbles and froth formation, froth machines; suspended layer characteristics and the possibility of using it in waste water cleaning of detergents; experimental part; conclusions and references. Experimental part includes theoretically calculated suspended layer parameters, description of the experimental stand, its operating principle, instruments used during the experimental procedures, calculations of suspended layer variable settings according to the experimental data. In the end the results are analyzed and the conclusions are included. Thesis consists of: 67 p. text without appendixes, 21 picture, 4 tables, 24 bibliographical entries. Appendixes included.

Este trabalho tem como objetivo a síntese e a determinação de propriedades micelares de líquidos iônicos tensoativos (LITs) catiônicos. Dentre as características importantes desses compostos destacamos: alta deslocalização da carga e caráter ácido no hidrogênio H2 do anel heterocíclico e a grande flexibilidade estrutural, estas são relevantes para as propriedades de soluções desses tensoativos, e, consequentemente, para suas aplicações. A influência da variação estrutural nas suas propriedades é importante para modular as propriedades micelares e, por consequência suas aplicações. A síntese de LITs foi realizada por aquecimento convencional e irradiação por micro-ondas, o último método foi o mais eficiente. Inicialmente, estudamos a influência do comprimento da cadeia carbônica (fator importante para a energia de formação de micelas), de cloretos de 1-alquil-3-metilimidazólio, tendo a cadeia n-alquílica 10 a 16 átomos de carbonos. Em seguida, comparamos as propriedades dos LITs acima mencionados com as de tensoativos convencionais, cloretos de 1-alquilpiridínio e cloretos 1-alcanoil-amidoetil benzildimetilamônio. Por fim, estudamos a influência do volume da cabeça-polar, utilizando cloretos de 1-alquil-3-hexadecilimidazólio, tendo a cadeia alquílica secundária 1 a 5 átomos de carbono. As propriedades micelares foram investigadas por tensão superficial, condutividade, calorimetria, espalhamento de luz e ressonância magnética nuclear. Os resultados mostraram que ligações de hidrogênio (devido ao H2 ácido do anel imidazólio) e as interações hidrofóbicas são relevantes para a formação de micelas e que o aumento do volume da cabeça-polar favorece a micelização e a formação de agregados pré-micelares / The objective of this work is the synthesis and determination of the micelar properties of cationic surface-active ionic liquids (SAILs). Among the important characteristics of these compounds are: high charge delocalization and acid character of hydrogen H2 of the heterocyclic ring and large structural flexibility, the latter is relevant to solution properties of these surfactants, hence to their applications. Synthesis of SAILs was carried out by conventional heating or by microwave irradiation, the later method was more efficient. Initially, we studied the influence of the chain length of the alkyl group (an important factor for the energy of micelle formation) of 1-alkyl-3-methylimidazolium chlorides, n-alkyl group having 10 to 16 carbon atoms. Then, we compared the properties of the above mentioned SAILs with conventional surfactants, 1-alkylpyridinium chlorides and 1-alkanoyl-amidoethyl benzyldimethylammonium chlorides. Finally, we studied the influence of the head-group volume, by studying 1-alkyl-3-hexadecylimidazolium chlorides, with secondary n-alkyl group having 1 to 5 carbon atoms. The micelar properties were investigated by surface tension, conductivity, calorimetry, light scattering and nuclear magnetic resonance. Our results have shown that hydrogen bonding (due to the acidic H2 of the imidazolium ring) and hydrophobic interactions are relevant to micelle formation; increasing the head-group volume favors micellization and the formation of pre-micellar aggregates

En 2014, le réseau de pipelines à travers le monde est estimé à près de 3 500 000 km. Ces conduites en acier traversent plusieurs continents, régions, climats et donc différents types de sols. Elles sont protégées contre la corrosion externe par des revêtements et une protection cathodique. Néanmoins, il subsiste toujours un risque infime de dégradation de l’acier. Afin d’évaluer le risque de rupture d’une conduite, il est nécessaire d’étudier l’influence du sol sur la corrosion de l’acier nu non protégé composant cette conduite. Les paramètres régissant la corrosion des aciers dans les sols étant nombreux, nous nous sommes focalisés sur l’un des paramètres clés, à savoir « la teneur en eau » qui est directement reliée à d’autres paramètres très influents comme : l’aération ou taux d’oxygène, la résistivité du sol et la surface active. Dans cette thèse, nous nous sommes intéressés aux phénomènes se produisant lors de périodes transitoires de séchage/humidification de plusieurs types de sols : argileux, limoneux argileux et sableux. Une électrode multi-coupons a aussi été utilisée afin d’étudier les phénomènes liés à l’hétérogénéité de surface (formation de piles d’aération différentielle). Pour cela, différents coupons en acier provenant d’une conduite d’Air Liquide ont été enfouis pendant de longues périodes (4, 6 et 12 mois) dans différents types de sols. Les vitesses de corrosion sont estimées par électrochimie via la modélisation des courbes de voltammétrie autour du potentiel d’abandon. La surface active de l’électrode est estimée via la mesure de la résistance d’électrolyte par spectroscopie d’impédance électrochimique. Les échantillons sont ensuite analysés par micro-spectroscopie Raman, diffraction des rayons X et microscopie (optique, confocale et électronique à balayage) afin de déduire les mécanismes de corrosion de l’acier. Les résultats montrent, notamment, qu’en cas d’un fort taux d’humidité et d’une faible aération, les vitesses de corrosion sont très faibles (de l’ordre de 20 à 30 µm.an-1) mais atteignent 200 à 400 µm.an-1 lors des phases de séchage. La mesure de courants de couplage effectuée avec l’électrode multi-coupons ainsi que l’analyse de surface des coupons conventionnels ont confirmé la présence de piles d’aération différentielle et le caractère localisé de la corrosion. / In 2014, the pipelines network extended over 3500000 km worldwide. These pipes are passing through various continents, regions, areas and thus different types of soils. They are protected against external corrosion by coatings and cathodic protection. However, there is always a slight risk of carbon steel degradation. In order to evaluate the pipeline failure threat, it is necessary to study the influence of soil corrosion on the uncoated steel which composes this pipe. There are many parameters governing the steel corrosion in soils. We focused on one of the most important parameter “water content”. It is directly linked to other prominent parameters such as oxygen concentration, soil resistance and active area. In this thesis, we addressed the phenomena occurring at transitory periods of drying and remoistening in different types of soils : clayey, silt-loamy and sandy. A multi-coupon electrode was used as well in order to study the phenomena linked to surface heterogeneity (formation of differential aeration cells). For this aim, several steel coupons were buried in different types of soil for long periods (4, 6 and 12 months). The corrosion rates are estimated via electrochemical methods by fitting with a theoretical law the voltammetric curves acquired around the open circuit potential. The active area of the electrode was estimated via the determination of the soil electrolyte resistance by electrochemical impedance spectroscopy. Afterwards, the coupons were analyzed by micro-spectroscopy Raman, X-rays diffraction and microscopy in order to understand the corrosion mechanisms. Results showed that in case of very high moisture content and deaerated conditions, the corrosion rates were very weak (about 20 to 30 µm.yr-1) but reached 200 to 400 µm.yr-1 in the drying periods. The galvanic current measurements performed with the multi-coupon electrode and the surface analysis of the conventional electrodes both confirmed the presence of differential aeration cells and the localized nature of the corrosion.

High-Gradient Magnetic Separation (HGMS) is a powerful separation process that has great potential for industrial wastewater treatment, particularly for the removal and recovery of paramagnetic colloidal particles. The chief advantages of HGMS are that the separation is reversible and potentially selective. However, these advantages are compromised if non-magnetic filtration mechanisms influence significantly the capture of particles. The objective of this study was to identify the chief mechanisms responsible for the removal of ferric oxide (Fe2O3) from water by an HGMS process. This objective was achieved by measuring the effects of applied magnetic induction, collector radius, and fluid velocity on the removal efficiency (RE) of a stainless-steel filter column. These factors were tested on the removal of bare Fe2O3 particles and particles treated with a surfactant (sodium dodecyl sulfate, SDS). The results were compared to the predictions of a trajectory model which simulates particle capture by a magnetic force. The experimental results show that non-magnetic force mechanisms are primarily responsible for the removal of bare Fe2O3 particles for the experimental conditions used in this work. For these particles, the three factors tested had no significant effect on the RE, and 90.1% of the particles were removed without a magnetic force. These results differed sharply from modeling predictions. However, the magnetic force mechanism is primarily responsible for the removal of surfactant-treated Fe2O3 particles. The three factors investigated had a marked effect on the RE, and only 10.8% of the particles were removed without a magnetic force. An increase in magnetic induction from 0.2 to 0.5 T increased the RE from 79.9 to 93.4 %; a decrease in wire radius from 49 to 15 Ym increased the RE from 60.2 to 93.4%, and a decrease in fluid velocity from 0.5 to 0.1 cm/s increased the RE from 69.5 to 95.3%. These results agreed closely with the model predictions.This study demonstrates that by reducing the effect of attractive non-magnetic forces on filtration, surfactant treatment of colloidal particles can potentially preserve and enhance these two key advantages, i.e., regeneration and selectivity of HGMS processes.

In many countries around the world, municipal sewage and industrial wastewaters are typically treated, or sometimes only partially treated, prior to their discharge into surface waters. A major anionic surfactant, Linear Alkyl benzene Sulfonate (LAS), and a degraded product of a non-ionic surfactant, Nonylphenol (NP), are frequently found in municipal wastewaters. When wastewater containing such surfactants and their degraded products is used for irrigation, it can have an effect on the sorption/desorption and movement of pesticides in soils. Therefore, a lysimeter study was conducted, in summer 2004, to assess the effect of LAS and NP on the movement of agricultural herbicides through a sandy loam soil. The degradation of the herbicides was studied in lysimeters over a ninety-day period. Irrigation water with a concentration of 12 mg L -1 of LAS and NP was used to assess their effect on the leaching of atrazine, metolachlor, and metribuzin. Moreover, a laboratory sorption experiment was undertaken to estimate the partition coefficients (kd) of the three herbicides with water containing the same concentrations of LAS and NP. Irrigation water containing low concentrations of surfactants (LAS and NP) did not increase leaching of the three herbicides. Therefore, these results would reduce the concerns regarding pesticide leaching through sandy soil brought on by LAS and NP in wastewaters for irrigation, which is becoming more important due to increasing water scarcity in the dry climate regions of the world. / Beside the lysimeter study, mathematical models can be used effectively and economically in a very short period of time for simulating herbicide concentrations into soil. PESTFADE, a one dimensional transient flow model, was used, in this study, to simulate the fate of the three herbicides in sandy soils. Another model, Artificial Neural Network (ANN), was also used over mathematical modeling due to its faster execution period and less input parameter requirements, for predicting the concentrations of the three herbicides in a sandy loam soil. The predicted concentrations, from both models were compared with the experimental results from the lysimeter study. Although slight overestimations and underestimations were observed, both models simulated herbicide concentrations in the soil profile satisfactorily.

The present work was undertaken to develop a composite osmotic distillation (OD) membrane consisting of a thin hydrogel coating on a microporous hydrophobic substrate for the concentration of aqueous feeds containing surface-active agents. The range of OD applications using the hydrophobic membrane alone have been severely limited by the propensity for membrane wet-out when contacted by amphiphilic agents such as oils, fats and detergents. Wet-out allows the feed solution to track freely through the membrane pores with a resulting loss of solutes and a decrease in selectivity. The rationale for the approach taken was based on the hypothesis that the high water selectivity of the hydrophilic coating would maintain good water mass transfer to the underlying hydrophobic substrate but exclude other components including surface-active agents. The first stage of this work involved the identification of potential coating materials and the fabrication and structural characterization of films of these materials to determine their suitability. The second stage involved the development of techniques to facilitate adhesion of the hydrophilic coatings to the hydrophobic substrate, and the testing of the resulting composite membranes for OD performance and resistance to wet-out by surface-active agents. Sodium alginate was selected as the major coating component on the basis of its non-toxicity and its potential for stable hydrogel formation. Structural characterization of noncrosslinked films and films crosslinked using a water-soluble carbodiimide (WSC) was carried out using differential scanning calorimetry (DSC), Fourier Transform infrared spectroscopy (FT-IR) and swelling measurements. Maximum crosslinking through esterification of hydroxyl and carboxylic acid groups on adjacent polymer strands using the film immersion method was achieved with a non-solvent (ethanol) concentration of 60 vol % and a WSC concentration of 100 mM at pH 4. These conditions resulted in a hydrogel with an equilibrium water content of 60 wt %. DSC measurements of noncrosslinked and crosslinked alginate films showed an increase in crystallinity and hence rigidity on crosslinking. Therefore, several coatings were prepared as blends of sodium alginate and amorphous highly flexible carrageenan gum in order to meet the flexibility requirements of a membrane subjected to varying operating pressures in an industrial OD plant. Structural characterization with respect to polymer blend ratio was carried out using scanning electron microscopy (SEM), DSC, X-ray diffraction (XRD). The optimisation for crosslinking conditions was undertaken as for sodium alginate alone. Optimum conditions for film preparation were 20 wt % carrageenan content and a crosslinking medium containing 60 vol % non-solvent (ethanol) and 120 mM WSC at pH 4. These conditions produced a hydrogel with an equilibrium water content of 85 wt %. Two different techniques were employed to anchor the coatings on substrate PTFE membranes. For membranes with a nominal diameter of 0.2 µm, the technique involved surface tension adjustment of the coating solution by ethanol addition in order to enhance penetration of the coating solution meniscus into the substrate pores. This was followed by polymer precipitation by the selective removal of water using OD to provide structural interlocking. T-peel strength measurements showed that this technique resulted in a ten-fold increase in adhesion strength when compared with a coating cast without surface tension adjustments. For membranes with a nominal diameter of 0.1µm, an interfacial bonding agent, myristyltrimethylammonium bromide (MTMA), was used. This technique gave a three-fold increase in adhesion strength relative to that of coating cast without the use of MTMA. The composite membranes were tested in extended OD trials using pure water and feeds containing limonene, the major surface-active components of orange oil. The sodium alginate-carrageenan blend membrane, which was the preferred membrane based on flexibility and water sorption considerations, was also tested against full-cream milk and an industrial detergent, sodium dodecylbenzene sulfonate (DBS). The results indicated that the coatings offered little resistance to water transport and were effective in providing protection against membrane wet-out. Durability trials showed that the composite membranes retained their integrity in water for a minimum of 30 days. Overall, this study has expanded the potential applications of OD to include many important industrial concentration steps that are currently being undertaken by conventional processes with unsatisfactory results. These include the concentration of citrus juices, full-cream milk and nuclear power plant liquid waste. These feeds contain limonene, fats and detergents respectively, all of which wet out unprotected hydrophobic membranes.

Orientadores: Watson Loh, Antonio Carlos Bannwart / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-09T07:38:37Z (GMT). No. of bitstreams: 1 Santos_RonaldoGoncalvesdos_D.pdf: 3351599 bytes, checksum: e5f17ac5f9d0db6db39884f2b5c5ec78 (MD5) Previous issue date: 2007 / Resumo: Emulsões óleo em água (o/a) têm sido propostas como alternativa aos métodos convencionais para redução dos problemas associados ao escoamento, causados pela alta viscosidade destes óleos. Nestas emulsões, o óleo se encontra disperso na fase aquosa sob a forma de gotículas e pode ser bombeado sem necessariamente entrar em contato com as paredes do duto, reduzindo os efeitos viscosos e ampliando a capacidade de transferência. Neste trabalho, realizou-se um estudo experimental sobre a aplicação de emulsões de óleo em água (o/a) no transporte de óleos pesados brasileiros. Emulsões contendo 50-70% de óleo disperso foram preparadas sob diferentes parâmetros da formulação fisico-química, permitindo adequação de suas propriedades às exigência da aplicação. Eficaz protocolo de preparação produziu gotas com diâmetro médio de Sauter D3,2da ordem de 10-50 micrômetros e com distribuição de diâmetros obedecendo a uma distribuição lognormal. A reologia e a estabilidade das emulsões foram dependentes do diâmetro médio de gota e da distribuição de tamanhos. Emulsões mostraram alta estabilidade sob condições severas de avaliação. A emulsificação reduziu a viscosidade de 1.000 cP do óleo original para 30-150 cP da emulsão o/a, produzindo decréscimo de cerca de 30 vezes na viscosidade do óleo. As emulsões mostraram comportamento pseudoplástico descrito pela lei de potência (modelo de Ostwald-de Waele), apresentando influência do envelhecimento. O óleo cru pode.ser recuperado pela quebra da emulsão utilizando desemulsificantes comerciais, produzindo BS&W de cerca de 5%. Um sistema' de fluxo experimental em escala piloto com comprimento reto de teste de 3 m foi constiuído com tubulação de aço API com % in d.i. para ensaios de escoamento das emulsões. A viscosidade foi calculada a partir de dados de queda de pressão. A viscosidade de emulsões óleo em água com 50%, 60% e 70% de óleo disperso foi adequadamente prevista pela lei de potência, mostrando valores até 100 vezes menor que a viscosidade do óleo em escoamento a 500 S.I. As perdas de carga observadas durante o escoamento de emulsões são até 20 vezes inferior às do óleo em fluxo monofásico, o que também se verifica através da estimativa da potência requerida de bombeio. As emulsões óleo em água produzidas neste estudo mostram a viabilidade técnica da aplicação de emulsões óleo em água para o escoamento de óleos pesados, incluindo operações de elevação e transporte em oleodutos convencionais. / Abstract: Use of oil-in-water (o/w) emulsions for transportation of heavy crude oils has been proposed as altemative means of reducing problems associated with difficulties in transport of these fluids for their high viscosity, with some advantages over the currently used methodologies. In these emulsions, oil is dispersed as stabilized droplets allowing its transportation with low pressure drops and avoiding oil contact with the pipeline walls. This study involved the experimental evaluation of o/w emulsions for the transportation of Brazilian crude oils. Emulsions containing 50-70% oi! were prepared with different formulations. An efficient methodology of preparation produced emulsions with droplet diameters (Sauter diameter, D3,2) in the range of 10-50 micrometers and a log-normal size distribution. Rheology and stability of these emulsions depend on their average diameters and size distributions. These emulsions displayed high stability under severe conditions (centrifugation). Using this approach, oil viscosity of around 1 000 cP was reduced to 30-150 cP. These emulsions display a pseudoplastic rheological behavior following the power law described by the Ostwald-de Waele model, which changed with their aging. Crude oil could be recovered after emulsification using commercial additives, producing BS&W values of 5 %, which could be further reduced with more severe treatments (down to 0.5 %). An experimental set-up was built for flow assays in pilot scale with 3 m length for measurements made of API steel with :;4 in (i.d.). Viscosity was obtained from drop pressure data. The power law adequately adjusted emulsions containing several oil contents. Emulsions viscosity was found to. be up to 100 times lower tIutn the oil viscosityat 500 S-I and drop pressure in the emulsion flow was 20 times lower than q,il monophasic flow. In summary, all of these measurements confirm the viability of these emulsions for use in transportation of heavy crude oils, induding their lift and transportation in conventional pipelines. / Doutorado / Engenharia de Processos / Doutor em Engenharia Química

Este trabalho tem como objetivo a síntese e a determinação de propriedades micelares de líquidos iônicos tensoativos (LITs) catiônicos. Dentre as características importantes desses compostos destacamos: alta deslocalização da carga e caráter ácido no hidrogênio H2 do anel heterocíclico e a grande flexibilidade estrutural, estas são relevantes para as propriedades de soluções desses tensoativos, e, consequentemente, para suas aplicações. A influência da variação estrutural nas suas propriedades é importante para modular as propriedades micelares e, por consequência suas aplicações. A síntese de LITs foi realizada por aquecimento convencional e irradiação por micro-ondas, o último método foi o mais eficiente. Inicialmente, estudamos a influência do comprimento da cadeia carbônica (fator importante para a energia de formação de micelas), de cloretos de 1-alquil-3-metilimidazólio, tendo a cadeia n-alquílica 10 a 16 átomos de carbonos. Em seguida, comparamos as propriedades dos LITs acima mencionados com as de tensoativos convencionais, cloretos de 1-alquilpiridínio e cloretos 1-alcanoil-amidoetil benzildimetilamônio. Por fim, estudamos a influência do volume da cabeça-polar, utilizando cloretos de 1-alquil-3-hexadecilimidazólio, tendo a cadeia alquílica secundária 1 a 5 átomos de carbono. As propriedades micelares foram investigadas por tensão superficial, condutividade, calorimetria, espalhamento de luz e ressonância magnética nuclear. Os resultados mostraram que ligações de hidrogênio (devido ao H2 ácido do anel imidazólio) e as interações hidrofóbicas são relevantes para a formação de micelas e que o aumento do volume da cabeça-polar favorece a micelização e a formação de agregados pré-micelares / The objective of this work is the synthesis and determination of the micelar properties of cationic surface-active ionic liquids (SAILs). Among the important characteristics of these compounds are: high charge delocalization and acid character of hydrogen H2 of the heterocyclic ring and large structural flexibility, the latter is relevant to solution properties of these surfactants, hence to their applications. Synthesis of SAILs was carried out by conventional heating or by microwave irradiation, the later method was more efficient. Initially, we studied the influence of the chain length of the alkyl group (an important factor for the energy of micelle formation) of 1-alkyl-3-methylimidazolium chlorides, n-alkyl group having 10 to 16 carbon atoms. Then, we compared the properties of the above mentioned SAILs with conventional surfactants, 1-alkylpyridinium chlorides and 1-alkanoyl-amidoethyl benzyldimethylammonium chlorides. Finally, we studied the influence of the head-group volume, by studying 1-alkyl-3-hexadecylimidazolium chlorides, with secondary n-alkyl group having 1 to 5 carbon atoms. The micelar properties were investigated by surface tension, conductivity, calorimetry, light scattering and nuclear magnetic resonance. Our results have shown that hydrogen bonding (due to the acidic H2 of the imidazolium ring) and hydrophobic interactions are relevant to micelle formation; increasing the head-group volume favors micellization and the formation of pre-micellar aggregates