Praguicidas são substancias capazes de prevenir, destruir, repelir ou mitigar uma praga e por isso desempenham um papel de grande importância na agricultura moderna. A elevada utilização destes compostos visa atender à crescente demanda de produção de alimentos, e para isso pesquisas vem sendo realizadas para o desenvolvimento de novas formulações. Entretanto a utilização descontrolada destes compostos pode levar à contaminação de alimentos, solo, águas superficiais e subterrâneas. Os Hidróxidos Duplos Lamelares (HDL) ou argilas aniônicas apresentam estrutura lamelar na qual uma variedade de ânions podem ser intercalados entre as lamelas através de interações eletrostáticas, incluindo praguicidas ácidos. Estes materiais apresentam propriedades interessantes como blindagem das moléculas intercaladas e capacidade de liberação lenta das mesmas. Assim, os principais objetivos deste trabalho foram: estudar a intercalação dos herbicidas ácidos Triclopir, Fluroxipir e Quinclorac, utilizados na agricultura nacional, em HDL de dois sistemas diferentes; estudar a liberação dos herbicidas intercalados em soluções aquosas e em suspensões solo/água; estudar o comportamento dos materiais obtidos quanto à lixiviação em colunas de solo; e comparar a eficácia herbicida dos híbridos com os herbicidas livres através de bioensaios com plantas. Os resultados obtidos demonstraram que os herbicidas ácidos foram intercalados nos HDL dos sistemas Mg/Al e Zn/Al, resultando em sólidos lamelares com boa organização estrutural ainda desconhecidos da literatura. Os híbridos liberaram os herbicidas de forma lenta e contínua para a solução aquosa, diferentemente do observado para o caso dos herbicidas livres, que apresentaram liberação praticamente instantânea para a solução. O tipo de solo também não interferiu na liberação dos princípios ativos. Os estudos de lixiviação em colunas de solo demonstraram que os HDL são bons suportes para a liberação dos herbicidas, pois apresentam liberação lenta do ingrediente ativo, atrasando sua passagem através do solo e diminuindo as concentrações obtidas nos lixiviados. Os híbridos apresentaram a mesma eficácia herbicida que os princípios ativos em forma livre, regulando o crescimento das plantas de agrião nos testes de bioensaios, utilizando as doses de aplicação recomendadas no campo. / Pesticides are substances that prevent, destroy, repel, or mitigate a plague; hence, they play a crucial role in modern agriculture. The widespread use of these compounds aims to meet the growing demand for food production, and this research has focused on the development of new pesticides formulations. However, the uncontrolled use of these compounds can lead to food, soil, surface, and groundwater contamination. Layered Double Hydroxides (LDH) or anionic clays present a lamellar structure in which a variety of anions can intercalate via electrostatic interactions, including acid pesticides. These materials offer interesting properties such as shielding and slow release of intercalated molecules. In this contest, the main objectives of this work were: to study the intercalation of the acid herbicides Triclopyr, Fluroxypyr, and Quinclorac, employed in the Brazilian agriculture, into LDH of two different systems; to study the release of these herbicides into aqueous solutions and soil/water suspensions; to study the behavior of the obtained materials as to their leaching in soil columns; and to compare the herbicidal efficacy of the hybrids with free herbicides through bioassays with plants. Our results showed that acidic herbicides intercalated into the Mg/Al and Zn/Al LDH systems, to yield in lamellar solids with good structural organization, which are yet unknown in the literature. The hybrids released the herbicides slowly and continuously into the aqueous solution, in contrast with free herbicides, which presented virtually instantaneous release into the solution. The soil type did not interfere in the release of active ingredients. Leaching studies in soil columns showed that the LDH are good carriers for herbicides release - they feature slow release of the active ingredient, delaying its passage through the soil and decreasing the concentrations obtained in the leachate. The hybrids displayed the same herbicide effectiveness as the active ingredients in the free form; they regulated the growth of plants in bioassays, when the doses recommended for field use were applied.

Hidróxidos duplos lamelares (HDL) ou compostos lamelares do tipo da hidrotalcita, são materiais com estrutura formada pelo empilhamento de camadas de hidróxidos mistos de cátions divalentes e trivalentes contendo ânions hidratados nos espaços entre essas camadas. Os HDL apresentam uma grande diversidade de aplicações podendo ser utilizados como catalisadores ou suporte para catalisadores, trocadores iônicos, antiácidos, adsorventes. A adsorção de tensoativos em interfaces sólido/líquido é um fenômeno amplamente estudado devido à sua relação direta com estabilidade de colóides. A adsorção de tensoativo em superfícies de óxidos minerais é um processo importante no estudo de detergência, flotação de minerais, dispersão/floculação, crescimento de partículas em suspensão, melhoria na recuperação de óleos, lubrificação, cromatografia, entre outros processos. Mesmo sendo a adsorção um processo muito estudado em sólidos como carvão mineral, resinas poliméricas, polímeros, fibras naturais e sintéticas e em óxidos minerais, os trabalhos que tratam da adsorção de tensoativos em HDLs são escassos. Este projeto teve como principais objetivos a síntese e caracterização de HDL de magnésio e alumínio intercalado com ânion carbonato e o estudo das propriedades de adsorção de tensoativos aniônicos sulfonados, dodecilbenzenosulfonato e octilbenzenosulfonato, na superfície deste HDL, investigando o efeito da temperatura, do pH e da força iônica do meio e a influência do tamanho da cadeia hidrofóbica, no processo de adsorção. Para a síntese do HDL foi utilizado o método de coprecipitação a pH variável seguido de tratamento hidrotérmico. O material obtido foi caracterizado através das técnicas de difração de raios-X no pó, espectroscopia no infravermelho, análise termogravimétrica, análise térmica diferencial, adsorção de nitrogênio, análise elementar, e espalhamento de luz. A adsorção foi realizada pelo método de batelada, com o controle dos parâmetros envolvidos. Os resultados de adsorção mostraram que para ambos os tensoativos, as variáveis afetam a adsorção de maneira semelhante. Uma diminuição na quantidade de tensoativo adsorvida é observada em maiores temperaturas e em maiores valores de pH. Quando a adsorção é realizada em maior força iônica, uma maior quantidade adsorvida é observada para ambos os tensoativos estudados, exceto para o caso da adsorção de SDBS em concentrações acima da CMC. Uma competição entre a formação de micelas e a adsorção explica estes resultados. / Layered double hydroxides (LDH) or the hydrotalcite-like compounds are a class of material with structure formed by the stacking of positively charged layers of mixed divalent and trivalent cations hydroxides, containing in the interlayer spaces solvated anions. According to their chemical composition, crystallinity, thermal stability and other physical-chemical properties, the LDH can be used in a wide variety of application areas as catalysts or catalysts support, as antacid, as anionic exchanger, as adsorbents. The adsorption of surfactants at the solid/liquid interfaces has been extensively studied due to its direct relationship with colloids stability. The surfactant adsorption on mineral oxides is an important process in the study of detergency, mineral flotation, dispersion/flocculation, particles growth in suspension, oil recovery enhanced, lubrication and chromatography, among others. Even though this is an extensively studied process, few reports concerning to the adsorption of surfactants on LDH are available in the literature. The aim of this project was the synthesis and characterization of HDL of magnesium and aluminum containing carbonate as the intercalated anions and the adsorption study of sulfonated anionic surfactants, dodecylbenzenesulfonate and octylbenzenesulfonate, on this HDL, investigating the influence of the temperature, of the pH, of the ionic strength media and of the hydrophobic chain length on the adsorption process. The adsorbent was synthesized by the co precipitation method and characterized by PXRD analysis, infrared spectroscopy, TG/DT analysis, specific surface area, zeta potential measurements, and elemental chemical analysis. The adsorption was carried out by the batch method, with the control of the involved parameters. The results of the adsorptions showed that for both surfactants the variables affect the adsorption in a similar way. A decrease in the amount of adsorbed surfactant is observed at higher temperature and higher pH values. At higher ionic strength medium, the amount of adsorption increase for both surfactants, except for SDBS at equilibrium concentration higher than CMC. A competition between the micelle formation and adsorption can explain these results.

The current clinical treatment for bone deficiencies in clinics includes autografts, allografts and bone graft substitutes. All these treatments, however, still have various limitations. Therefore, in this project, we aim to design, synthesise and characterise a new series of novel polymer networks (PNs) to promote bone formation and offer a new therapeutic solution. An innovative polymerisation technique was used to synthesise the novel polymer-based materials. Various lactone monomers were applied with layered double hydroxides (LDHs) as the initiator for the polymerisation. Copolymerisation was used to control the final product degradation rate, microstructure and biocompatibility. SEM and XRD were used to confirm the formation of the 3D polymer microstructure, PNs indicated interconnected fibrous microstructure (thickness of the fibre ranged from 50-150 nm). Up to 90% polymer yield was achieved using thermogravimetric analysis. Both 1H and 13C nuclear magnetic resonance (NMR) were used to understand the effects of monomer combinations in the polymerisation. The effects of the materials on osteosarcoma cell line Saos-2 were investigated. Representative material compositions and their determined mass concentrations were applied using osteogenic culture medium with Saos-2. The PNs have indicated enhanced osteogenesis using varied assays. A poly(lactide-co-caprolactone) PN (monomer mass ratio 1:1) at 6.25 mg/ml, in particular, resulted in enhanced alkaline phosphate activity not only in growth medium but also in osteogenic medium. Moreover, it indicated the highest bone nodule production in area percentage compared to the other PN samples using Saos-2. Mg-substituted calcified extracellular matrix was formed by the use of PN materials. Therefore, this novel PN could have the possibility to be used as an acellular scaffold or a sprinkle-on powder local to defect site to enhance bone formation in vivo. In addition, this novel technology could be used as a scaffold for tissue engineering.

Submitted by Maria Aparecida (cidazen@gmail.com) on 2017-11-16T12:37:19Z No. of bitstreams: 1 ANTONIO DE JESUS DOS SANTOS FERNANDES JÚNIOR.pdf: 2676930 bytes, checksum: 6ea43214cce79a1ebadd7cae50663205 (MD5) / Made available in DSpace on 2017-11-16T12:37:19Z (GMT). No. of bitstreams: 1 ANTONIO DE JESUS DOS SANTOS FERNANDES JÚNIOR.pdf: 2676930 bytes, checksum: 6ea43214cce79a1ebadd7cae50663205 (MD5) Previous issue date: 2017-09-05 / In this work,a nevel material heterostructured based on the assembly of double layered double hydroxide (LDH) suported in magadiite, was synthesized. For this purpose, layered double hydroxides of MgAl and ZnAl,both in the proportion 2:1 was synthesized by the method of coprecipitation in situ in the presence of magadiite.Diverse physicochemical techniques (DRX,FTIR,DTA,ICP-OES,MEV E TEM ) were employed to caractherize the materials syntehesized with the aim of verifying the existence of interactions in the interface of both components. Results gotten by DRX show plans of reflection typical of magadiite,confirming the formation o HDL in the surface of silicate. Nanocrystalline interactions among the groups of hydroxyl of each component. Metalic Oxide nanoparticles were supported in magadiite employing the thermic decomposition (calcination) of the component HDL present in the hetero-structure MAG/HDL,with the aim of getting catalyst formed by metalic oxides highly dispersed supported in magadiite. Calcined materials and non-calcined were evaluated as photocatalysts, using blue dye of methylene as a standard molecule. Photocatalytic analyses were made with “heterostructure” MAG/HDL and MAG/ODL showed a catalytic activity improved in order to degradate the dye,,where the concentration decreased considerablly in a short interlude of exposition to irradiation of uv light in camparison to the photlysis test.These results were gotten probably thanks to the resulting synergistic effect of textured properties interesting,charactheristics of synthesized heterostructured ,turning them in photocatalytic promising in the degradation of organic compounds. / Neste trabalho, um novo material heteroestruturado baseado na síntese de hidróxidos duplos lamelares suportados em magadiíta, foi sintetizado. Para este fim, hidróxidos duplos lamelares (HDL) de MgAl e ZnAl, ambos nas proporções 2:1, foram sintetizados pelo método de coprecipitação in situ em presença do silicato alcalino lamelar. Diversas técnicas físico-químicas (DRX, FTIR, DTA, ICP-OES, MEV e TEM) foram empregados para caracterizar os materiais sintetizados com o objetivo de verificar a existência a existência de interações na interface dos dois componentes. Resultados obtidos por DRX mostram planos de reflexão típicos de magadiíta, confirmando a formação de HDL na superfície do silicato. Interações nanocristalinas entre as porções foram evidenciadas por estudos de espectroscopia onde ocorrem interações entre os grupos hidroxilas de cada componente. Nanopartículas de óxidos metálicos foram suportados em magadiíta empregando a decomposição térmica (calcinação) do componente HDL presente na heteroestrutura MAG/HDL, com o objetivo de obter-se materiais catalisadores formados por óxidos metálicos altamente dispersos suportados em magadiíta. Os materiais calcinados e não calcinados foram avaliados como fotocatalisadores, usando o corante azul de metileno como molécula modelo. Testes fotocatalíticos realizados com as heteroestruturas MAG/HDL e MAG/ODL mostraram uma atividade catalítica melhorada para a degradação do corante, onde a concentração diminuiu consideravelmente em um curto intervalo de tempo de exposição à irradiação de luz UV em comparação ao teste de fotólise. Estes resultados foram obtidos provavelmente devido ao efeito sinérgico resultante das propriedades texturais interessantes, características das heteroestruturas sintetizadas, tornando-os fotocatalisadores promissores na degradação de compostos orgânincos.

Trijų sudėčių sluoksniuoti dvigubi hidroksidai (SDH) Mg/Al, Co/Mg/Al ir Ni/Mg/Al susintetinti bendro nusodinimo esant mažoms koncentracijoms metodu. Šie SDH buvo termiškai suskaidyti, ir gautieji mišrūs metalų oksidai reformuoti vandenyje ir pirmą kartą magnio nitrato tirpale. Naudojant XRF ir TG duomenis pasiūlytos susintetintų bendro nusodinimo metodu SDH formulės. XRD analizės rezultatai parodė, kad SDH ir mišrių metalų oksidų faziniai kitimai reformavimo metu priklauso nuo proceso temperatūros ir terpės prigimties. Co ir Ni turinčių SDH mėginių sluoksninės struktūros atstatymas kambario temperatūros vandenyje vyksta nepilnai, tačiau pakėlus temperatūrą iki 80 °C pašalinės oksidų fazės reformuotuose pavyzdžiuose nebelieka. Kai SDH atstatymui buvo naudojamas magnio nitrato tirpalas, katijonų sudėtis pakito dėl padidėjusio sluoksninėje struktūroje magnio kiekio. Ryškus temperatūros ir vandeninės terpės poveikis stebimas ne tik reformavimui, bet ir gautų SDH kristalitų dydžiams. Iškaitinus SDH gautų oksidų morfologija priklauso nuo jų sudėtyje esančio pereinamojo metalo ir reformavimui naudoto tirpalo prigimties. Praktiniai panaudojimai reformuotų SDH tirti NOx pašalinimo reakcijose ir gazifikacijos metu gaunamų dujų valyme. / Three layered double hydroxides Mg/Al, Co/Mg/Al and Ni/Mg/Al were successfully synthesized by the low supersaturation method, thermally decomposed and derived mixed metal oxides reformed to layered structures in water and for first time to our knowledge in magnesium nitrate media. XRD measurements provided direct evidence for phase transformation processes during calcination and reformation of layered structure at different temperatures. From XRF and TG analyses data the formulas of synthesized LDH were proposed. Incomplete regeneration of Co and Ni containing LDH samples at room temperature in aqueous media has been observed. However, with increasing temperature up to 80 °C the reconstitution process of LDH proceeds fully. Changes of cations composition after reformation could be explained by the increase of magnesium content when the reconstitution in magnesium nitrate solution followed. The hydration causes the formation of LDH with higher crystallite size in comparison with the LDH samples reformed in magnesium nitrate media. In most of the cases, with increasing the temperature of reconstitution media to 80ºC the crystallite size also increased. Reformation media had a considerable influence to the morphology of mixed metal oxides. Moreover, the effects for nickel or cobalt containing samples were found to be different. Catalysts prepared from LDH containing cobalt were tested in the removal of NOx and nickel containing LDH were tested in gasification gas cleaning.

abstract: The central theme of this dissertation is to understand the chemical processing science of advanced ceramic materials for biomedicine, including therapy and imaging. The secondary component focuses on the chemical processing of energy materials. Recently, layered double hydroxide (LDH) nanoparticles (NPs) with various intercalated compounds (e.g. fluorescent molecules, radio-labeled ATP, vitamins, DNA, and drugs) have exhibited versatility and promise as a combined therapeutic and diagnostic (i.e. theranostic) vector. However, its eventual acceptance in biomedicine will be contingent on understanding the processing science, reproducibly synthesizing monodispersed NPs with controlled mean particle size (MPS), and ascertaining the efficacy of the NPs for drug delivery and imaging. First, statistical design of experiments were used to optimize the wet chemistry synthesis of (Zn, Al)-LDH NPs. A synthesis model, which allows the synthesis of nearly monodispersed NPs with controlled MPS, was developed and experimentally verified. Also, the evolution of the nanostructure was characterized, from coprecipitation to hydrothermal treatment, to identify the formation mechanisms. Next, the biocompatibility, cellular uptake and drug delivery capability of LDH NPs were studied. In an in vitro study, using cultured pancreatic adenocarcinoma BXPC3 cells, valproate-intercalated LDH NPs showed an improved efficacy (~50 fold) over the sodium valproate alone. Finally, Gd(DTPA)-intercalated LDH NPs were synthesized and characterized by proton (1H) nuclear magnetic resonance. The longitudinal relaxivity (r1) of 28.38 s-1 mM-1, which is over 6 times higher than the clinically approved contrast agent, Gd(DTPA), demonstrated the potential of this vector for use in magnetic resonance imaging. Visible light-transparent single metal-semiconductor junction devices, which convert ultraviolet photon energy into high open circuit voltage (Voc>1.5-2 V), are highly desirable for transparent photovoltaics that can potentially power an electrochromic stack for smart windows. A Schottky junction solar cell, comprised of sputtered ZnO/ZnS heterojunction with Cr/Au contacts, was fabricated and an Voc of <em>f</em>î1.35 V was measured. Also, a low-cost route to form ZnO/ZnS heterojunctions by partial sulfurization of solution-grown ZnO thin films (350 nm-5 <em>f</em>Ým thick; conductivity comparable to phosphorus-doped Si) was demonstrated. A final study was on a cathode material for Li-ion batteries. Phase-pure LiFePO4 powders were synthesized by microwave-assisted sol-gel method and characterized. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2014

abstract: As selenium is toxic at low levels, treatment methods to remove selenium from industrial waste waters are needed. In this work, three groups of sorbent materials were investigated in detail for their effectiveness for selenium and arsenic removal from water: 1) nanostructured carbon-based materials, 2) layered double hydroxide (LDH)-based materials, and 3) biopolymer-based sorbents. The materials were investigated in spiked de-ionized water and waters collected from different locations at Salt River Project’s (SRP) Santan Generating Station in Gilbert, AZ. The results show that nanostructured carbon-based materials removed ~80% and up to 100% selenium and arsenic, respectively in spiked DI water. Heat treated layered double hydroxides removed close to 100% removal in selenium and arsenic spiked DI water. Isotherms conducted in spiked DI water fit the Langmuir model and showed a maximum selenate adsorption capacity of 67 mg/g for the calcined LDH powder. Results from SRP waters showed that certain LDH sorbents were effective for removing the selenium, but that higher pH and existence of competing ions affected the removal efficiencies. The functionalized biopolymer sorbent from Crystal Clear Technologies: CCT-149/OCI-B showed good removal efficiencies for both selenate and selenite in DI water. Isotherms conducted in spiked DI water for CCT-149 fit the Langmuir model and showed a maximum selenate adsorption capacity of 90.9 mg/g. Column tests using spiked DI water and waters obtained from SRP wells were investigated using both LDH and CCT-149/OCI-B. Removal of sulfate using chemical pre-treatment of the water with barium chloride resulted in about three times higher selenate loading onto the granular LDH and doubled the water volume that can be treated using CCT-149/OCI-B. The results from the column tests are being used to guide the pilot testing investigating the implementation of LDH sorbents at pilot scale at the Santan plant. The good results in the cooling tower #5 blowdown water and combined discharge waste water of SRP provide valuable information about the efficacy and efficiency of adsorptive media for the removal of selenium. Composites comprising LDH nanosheets with different substrates were successfully synthesized that were able to retain the performance in removing selenate of nanosheet LDH. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2017

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / Os corantes sintÃticos sÃo um dos poluentes mais comuns e frequentemente encontrados na indÃstria tÃxtil. A destinaÃÃo de esgoto contendo corantes para corpos de Ãgua à extremamente importante do ponto de vista ambiental, jà que mesmo em baixas concentraÃÃes os corantes podem ser altamente tÃxicos para sistemas aquÃticos. A elevada toxicidade à um dos grandes problemas de Ãguas residuais contendo corantes. Este estudo examinou como adsorventes nanoporosos trÃs materiais sendo um HidrÃxido Duplo Lamelar (HDL â Mg/Al), uma argila pilarizada (Al-PILC) e um carbono ativado comercial (GAC-Norit 1240) avaliando seus comportamentos na remoÃÃo dos corantes Reativo Preto 5 (RP5), Azul de Metileno (AM) e Ãcido Azul 25 (AA25). Os materiais baseados em argilas naturais e sintetizadas em laboratÃrio, assim como o carbono ativado, foram caracterizados por difraÃÃo de raios X, BET e FTIR, a fim de se obter informaÃÃo sobre suas caracteristicas estruturais e texturais. Experimentos em batelada utilizando um sistema de tanques agitados foram realizados para averiguar o efeito do pH do meio, da concentraÃÃo inicial de corante, do tempo de contato e da forÃa iÃnica do meio na adsorÃÃo dos corantes. Para o sistema de tanques agitados foram utilizados um agitador rotatÃrio orbital e tubos de acrÃlico contendo 20 mL de soluÃÃes de corantes em contato com 0,015 g dos adsorventes. As concentraÃÃes de equilÃbrio de cada corante foram determinadas em espectrofotÃmetro UV/Vis. A fim de descrever o comportamento das isotermas de adsorÃÃo, os dados de equilÃbrio foram correlacionados com o modelo de Langmuir (L). A contribuiÃÃo dos parÃmetros de transferÃncia de massa na cinÃtica de adsorÃÃo dos corantes RP5, AA25 e AM em carbono ativado tambÃm foi investigada. Estes dados fundamentais forneceram uma melhor compreensÃo dos mecanismos de transferÃncia de massa e dinÃmica difusional do sistema. O comportamento do pH e da forÃa iÃnica do meio foi de suma importÃncia para o entendimento dos processos de adsorÃÃo nos respectivos materiais para cada corante analisado. O pH das soluÃÃes aquosas foi bastante diferenciado, o qual foi dependente das caracterÃsitcas aniÃnicas e catiÃnicas dos materiais e dos corantes. De acordo com a anÃlise estatÃstica, o modelo de Langmuir foi adequado para representar os dados de adsorÃÃo dos corantes comprovado pela combinaÃÃo das constantes de ligaÃÃo do modelo, evidenciando uma forte interaÃÃo adsorvente-adsorbato. Pode-se notar que as cinÃticas de adsorÃÃo de corantes seguem um comportamento semelhante, com uma queda brusca da concentraÃÃo inicial de corante no sobrenadante nos primeiros momentos de contato, atingindo o equilÃbrio em aproximadamente 60 minutos, do que se pode inferir uma difusÃo molecular intrapartÃcula. As quantidades adsorvidas dos trÃs materiais indicaram um melhor desempenho obtido para o carbono ativado. / Synthetic dyes are one of the most common pollutants and often found in the textile industry. The disposal of wastewater containing dyes on water bodies is extremely important from an environmental standpoint, since the dyes even at low concentrations can be highly toxic to aquatic systems. The high stability and toxicity are the major problem in the treatment of wastewater containing dyes. This study examined three nanoporous adsorbents materials: a lamellar double hydroxide (LDH-Mg/Al), pillared clay (Al-PILC) and a commercial activated carbon (Norit GAC-1240), assessing hair performance in the removal of dyes Reactive Black 5 (RB5), Methylene Blue (MB) and Acid Blue 25 (AB25) used in the textile industry. The materials based on natural clays synthesized in the laboratory, and activated carbons were characterized by XRD, BET and FTIR, in order to obtain information about their structural and textural characteristics. Experiments using a batch stirred tank system were performed to investigate the effect of pH, the initial concentration of dye, contact time and ionic strength through adsorption of the dyes. For the system of stirred tanks a rotary shaker and acrylic tubes were used containing 20 mL of dye solutions in contact with 0.015 g of adsorbent. The equilibrium concentration of each dye was determined with a spectrophotometer UV/Vis. In order to describe the behavior of adsorption isotherms, the equilibrium data were correlated with the Langmuir model (L). The contribution of mass transfer parameters on the kinetics of adsorption of dyes RP5, AB25 and MB on activated carbon was also investigated. These data provide a basic understanding of mechanisms of mass transfer and dynamic diffusional system. The behavior of pH and ionic strength of the medium was very important for understanding of adsorption processes in the respective materials for each dye examined. The pH of the aqueous solutions was greatly different, which was dependent on characteristics anionic and cationic materials and colorants. According to statistical analysis, the Langmuir model was adequate to represent the data of adsorption of dyes shown. It may be noted that the kinetics of adsorption of dyes follow a similar behavior, with a sharp drop of the dye initial concentration in the supernatant in the first moments of contact, reaching the equilibrium in approximately 100 minutes. The adsorbed amounts of the three materials showed a revealed better performance obtained for activated carbon.

Hidróxidos duplos lamelares (HDL) ou compostos lamelares do tipo da hidrotalcita, são materiais com estrutura formada pelo empilhamento de camadas de hidróxidos mistos de cátions divalentes e trivalentes contendo ânions hidratados nos espaços entre essas camadas. Os HDL apresentam uma grande diversidade de aplicações podendo ser utilizados como catalisadores ou suporte para catalisadores, trocadores iônicos, antiácidos, adsorventes. A adsorção de tensoativos em interfaces sólido/líquido é um fenômeno amplamente estudado devido à sua relação direta com estabilidade de colóides. A adsorção de tensoativo em superfícies de óxidos minerais é um processo importante no estudo de detergência, flotação de minerais, dispersão/floculação, crescimento de partículas em suspensão, melhoria na recuperação de óleos, lubrificação, cromatografia, entre outros processos. Mesmo sendo a adsorção um processo muito estudado em sólidos como carvão mineral, resinas poliméricas, polímeros, fibras naturais e sintéticas e em óxidos minerais, os trabalhos que tratam da adsorção de tensoativos em HDLs são escassos. Este projeto teve como principais objetivos a síntese e caracterização de HDL de magnésio e alumínio intercalado com ânion carbonato e o estudo das propriedades de adsorção de tensoativos aniônicos sulfonados, dodecilbenzenosulfonato e octilbenzenosulfonato, na superfície deste HDL, investigando o efeito da temperatura, do pH e da força iônica do meio e a influência do tamanho da cadeia hidrofóbica, no processo de adsorção. Para a síntese do HDL foi utilizado o método de coprecipitação a pH variável seguido de tratamento hidrotérmico. O material obtido foi caracterizado através das técnicas de difração de raios-X no pó, espectroscopia no infravermelho, análise termogravimétrica, análise térmica diferencial, adsorção de nitrogênio, análise elementar, e espalhamento de luz. A adsorção foi realizada pelo método de batelada, com o controle dos parâmetros envolvidos. Os resultados de adsorção mostraram que para ambos os tensoativos, as variáveis afetam a adsorção de maneira semelhante. Uma diminuição na quantidade de tensoativo adsorvida é observada em maiores temperaturas e em maiores valores de pH. Quando a adsorção é realizada em maior força iônica, uma maior quantidade adsorvida é observada para ambos os tensoativos estudados, exceto para o caso da adsorção de SDBS em concentrações acima da CMC. Uma competição entre a formação de micelas e a adsorção explica estes resultados. / Layered double hydroxides (LDH) or the hydrotalcite-like compounds are a class of material with structure formed by the stacking of positively charged layers of mixed divalent and trivalent cations hydroxides, containing in the interlayer spaces solvated anions. According to their chemical composition, crystallinity, thermal stability and other physical-chemical properties, the LDH can be used in a wide variety of application areas as catalysts or catalysts support, as antacid, as anionic exchanger, as adsorbents. The adsorption of surfactants at the solid/liquid interfaces has been extensively studied due to its direct relationship with colloids stability. The surfactant adsorption on mineral oxides is an important process in the study of detergency, mineral flotation, dispersion/flocculation, particles growth in suspension, oil recovery enhanced, lubrication and chromatography, among others. Even though this is an extensively studied process, few reports concerning to the adsorption of surfactants on LDH are available in the literature. The aim of this project was the synthesis and characterization of HDL of magnesium and aluminum containing carbonate as the intercalated anions and the adsorption study of sulfonated anionic surfactants, dodecylbenzenesulfonate and octylbenzenesulfonate, on this HDL, investigating the influence of the temperature, of the pH, of the ionic strength media and of the hydrophobic chain length on the adsorption process. The adsorbent was synthesized by the co precipitation method and characterized by PXRD analysis, infrared spectroscopy, TG/DT analysis, specific surface area, zeta potential measurements, and elemental chemical analysis. The adsorption was carried out by the batch method, with the control of the involved parameters. The results of the adsorptions showed that for both surfactants the variables affect the adsorption in a similar way. A decrease in the amount of adsorbed surfactant is observed at higher temperature and higher pH values. At higher ionic strength medium, the amount of adsorption increase for both surfactants, except for SDBS at equilibrium concentration higher than CMC. A competition between the micelle formation and adsorption can explain these results.

Praguicidas são substancias capazes de prevenir, destruir, repelir ou mitigar uma praga e por isso desempenham um papel de grande importância na agricultura moderna. A elevada utilização destes compostos visa atender à crescente demanda de produção de alimentos, e para isso pesquisas vem sendo realizadas para o desenvolvimento de novas formulações. Entretanto a utilização descontrolada destes compostos pode levar à contaminação de alimentos, solo, águas superficiais e subterrâneas. Os Hidróxidos Duplos Lamelares (HDL) ou argilas aniônicas apresentam estrutura lamelar na qual uma variedade de ânions podem ser intercalados entre as lamelas através de interações eletrostáticas, incluindo praguicidas ácidos. Estes materiais apresentam propriedades interessantes como blindagem das moléculas intercaladas e capacidade de liberação lenta das mesmas. Assim, os principais objetivos deste trabalho foram: estudar a intercalação dos herbicidas ácidos Triclopir, Fluroxipir e Quinclorac, utilizados na agricultura nacional, em HDL de dois sistemas diferentes; estudar a liberação dos herbicidas intercalados em soluções aquosas e em suspensões solo/água; estudar o comportamento dos materiais obtidos quanto à lixiviação em colunas de solo; e comparar a eficácia herbicida dos híbridos com os herbicidas livres através de bioensaios com plantas. Os resultados obtidos demonstraram que os herbicidas ácidos foram intercalados nos HDL dos sistemas Mg/Al e Zn/Al, resultando em sólidos lamelares com boa organização estrutural ainda desconhecidos da literatura. Os híbridos liberaram os herbicidas de forma lenta e contínua para a solução aquosa, diferentemente do observado para o caso dos herbicidas livres, que apresentaram liberação praticamente instantânea para a solução. O tipo de solo também não interferiu na liberação dos princípios ativos. Os estudos de lixiviação em colunas de solo demonstraram que os HDL são bons suportes para a liberação dos herbicidas, pois apresentam liberação lenta do ingrediente ativo, atrasando sua passagem através do solo e diminuindo as concentrações obtidas nos lixiviados. Os híbridos apresentaram a mesma eficácia herbicida que os princípios ativos em forma livre, regulando o crescimento das plantas de agrião nos testes de bioensaios, utilizando as doses de aplicação recomendadas no campo. / Pesticides are substances that prevent, destroy, repel, or mitigate a plague; hence, they play a crucial role in modern agriculture. The widespread use of these compounds aims to meet the growing demand for food production, and this research has focused on the development of new pesticides formulations. However, the uncontrolled use of these compounds can lead to food, soil, surface, and groundwater contamination. Layered Double Hydroxides (LDH) or anionic clays present a lamellar structure in which a variety of anions can intercalate via electrostatic interactions, including acid pesticides. These materials offer interesting properties such as shielding and slow release of intercalated molecules. In this contest, the main objectives of this work were: to study the intercalation of the acid herbicides Triclopyr, Fluroxypyr, and Quinclorac, employed in the Brazilian agriculture, into LDH of two different systems; to study the release of these herbicides into aqueous solutions and soil/water suspensions; to study the behavior of the obtained materials as to their leaching in soil columns; and to compare the herbicidal efficacy of the hybrids with free herbicides through bioassays with plants. Our results showed that acidic herbicides intercalated into the Mg/Al and Zn/Al LDH systems, to yield in lamellar solids with good structural organization, which are yet unknown in the literature. The hybrids released the herbicides slowly and continuously into the aqueous solution, in contrast with free herbicides, which presented virtually instantaneous release into the solution. The soil type did not interfere in the release of active ingredients. Leaching studies in soil columns showed that the LDH are good carriers for herbicides release - they feature slow release of the active ingredient, delaying its passage through the soil and decreasing the concentrations obtained in the leachate. The hybrids displayed the same herbicide effectiveness as the active ingredients in the free form; they regulated the growth of plants in bioassays, when the doses recommended for field use were applied.