No description available.

This study focused on molten salt purification processes to effectively reduce or eliminate the corrosive contaminants without altering the salt's chemistry and properties. The impurity-driven corrosion behavior of HAYNES® 230® alloy in the molten KCl-MgCl2-NaCl salt was studied at 800 ºC for 100 hours with different salt purity conditions. The H230 alloy exhibited better corrosion resistance in the salt with lower concentration of impurities. Furthermore, it was also found that the contaminants along with salt's own vaporization at high temperatures severely corroded even the non-wetted surface of the alloy. The presence of Mg in its metal form in the salt resulted in an even higher mass-loss possibly due to Mg-Ni interaction. The study also investigated the corrosion characteristics of several nickel and ferrous-based alloys in the molten KCl-MgCl2-NaCl salt. The average mass-loss was in the increasing order of C276 < SS316L < 709-RBB* < IN718 < H230 < 709-RBB < 709-4B2. The corrosion process was driven by the outward diffusion of chromium. However, other factors such as the microstructure of the alloy i.e. its manufacturing, refining, and heat-treatment processes have also shown to influence the corrosion process. Lowering the Cr content and introducing W and Mo in the alloy increased its resistance to corrosion but their non-uniform distribution in the alloy restricted its usefulness. To slow-down the corrosion process, and enhance the material properties, selected alloys were boronized and tested for their compatibility in the molten KCl-MgCl2-NaCl salt. The borided alloys exhibited better resistance to molten salt attack, where the boride layer in the exposed alloy was still intact, non-porous, and strongly adhered to the substrate. The alloys also did not show any compensation in their properties (hardness). It was also found that the boride layer always composed of an outermost silicide composite layer, which is also the weakest and undesired layer as it easily cracks, breaks, or depletes under mechanical and thermal stresses. Various different grades of "virgin" nuclear graphites were also tested in the molten KF-UF4-NaF salt to assist in the selection of tolerable or impermeable graphites for the MSR operational purposes. It was found that molten salt wettability with graphite was poor but it still infiltrated at higher pressure. Additionally, the infiltration also depended on the pore-size and porosity of the graphite. The graphite also showed severe degradation or disintegration of its structure because of induced stresses. / Doctor of Philosophy / Molten salts are considered as potential fuel and coolant candidates in MSRs because of their desirable thermophysical properties and heat-transfer capabilities. However, they pose grave challenges in material selection due to their corrosive nature, which is attributed to the impurities and their concentration (mostly moisture and oxygen-based) in the salt. This study focused on purifying the salt to reduce these contaminants without compromising its composition and properties. The influence of purification processes on the corrosion behavior of HAYNES® 230® alloy was studied in the molten chloride salt with different purity conditions. Various nickel and ferrous-based alloys were also studied for their compatibility in the molten chloride salt. This will assist in expediting the material selection process for various molten salt applications. It was observed that several factors such as alloy composition, its microstructure, impurities in the salt attribute to molten salt corrosion. It was also quite evident that corrosion in molten salts is inevitable and hence, the focus was shifted on slowing down this process by providing protective barriers in the form of coatings (i.e. boronization). The borided (coated) alloys not only improved the corrosion resistance but also enhanced and retained their properties like hardness after exposure to molten salts. Since these studies were conducted under static conditions, a more detailed investigation is needed for the selected alloys by subjecting them to extreme flow-conditions and for longer a duration of time. To achieve this objective, a forced circulation molten salt loop was designed and fabricated to conduct flow corrosion studies for alloys in molten chloride salt. Graphite is another critical component of the MSR where it is used as a moderator or reflector. Generally, molten salts exhibit poor wettability with graphite, but they can still infiltrate (graphites) at higher applied pressures, and result in the degradation or disintegration of graphite's structure, and eventually its failure in the reactor. This study provides infiltration data, and understanding of the degradation of various 'virgin' nuclear graphite grades by the molten fluoride salt. This should assist in the selection of tolerable or impermeable graphite grades for MSR operational purposes.

M.Tech. (Department of Chemistry, Faculty of Applied Sciences), Vaal University of Technology / Many oxidic iron compounds—iron oxides; oxy-hydroxides and hydroxides—not only play an important role in a variety of disciplines but also serve as a model system of reduction and catalytic reactions. There are more than 16 identifiable oxidic iron compounds. The reduction of these compounds has been investigated for centuries. Despite this, the reduction behavior of the oxides is not fully understood as yet. To date the reduction mechanism is still plagued with uncertainties and conflicting theories, partly due to the complex nature of these oxides and intermediates formed during the reduction. Thermodynamically, the reduction of iron oxide occurs in steps. For example, during the reduction of hematite (a-Fe2O3) magnetite (Fe3O4) is first formed followed by non-stoichiometric wüstite (Fe1-yO) and lastly metallic iron (a-Fe). The rate of transformation depends on the reduction conditions. Further, this reduction is accompanied by changes in the crystal structure. The reduction behavior of iron oxides using graphite under ball-milling conditions was investigated using Planetary mono mill (Fritsch Pulverisette 6), Mössbauer Spectroscopy (MS), X-ray Diffraction (XRD), Scanning electron microscopy (SEM) and Transmission Electron Microscopy (TEM). It was found that hematite transformed into magnetite, Wüstite and or cementite depending on the milling conditions. The study shows that by increasing the milling time, the rotational speed and / or the ball to powder ratio, the extent of the conversion of hematite to its reduction products increased. Further investigations are required for the elucidation of the reduction mechanism. The reaction og magnetite and graphite at different milling conditions lead to the formation of Fe2+ and Fe3+ species, the former increasing at the expense of Fe3O4. Fe3O4 completely disappeared after a BPR of 50:1 and beyond. The Fe2+ species was confirmed to be due to FeO using XRD analysis. HRSEM images Fe2O3 using scanning electron microscopy prior to and after milling at different times showed significant changes while the milling period was increased, HRSEM images showed that the once well defined hematite particles took ill-defined shapes and also became smaller in size, which was a results of the milling action that induced reaction between the two powders to form magnetite. EDX spectra at different milling times also confirmed formation of magnetite. EDX elemental analysis and quantification confirmed the elemental composition of starting material consisting mainly of iron. Similarly, HRSEM images of Fe3O4 using Scanning electron microscopy (SEM) prior to and after milling at different BPR showed significant changes when the milling period was increased. EDX spectra at different milling times also confirmed formation of partial FeO and EDX elemental analysis and quantification confirmed the elemental composition of starting material consisting mainly of iron than Fe2O3. TEM images of both Fe2O3 and Fe3O4 particles at different milling conditions displayed observable particle damages as a function of milling period.The once well - defined particles (Fe2O3 and Fe3O4 ) successively took ill – defined shapes, possibly accompanied by crystallite size reduction. MAS showed that the reactive milling of α- Fe2O3 and C resulted in reduction to Fe3O4 , FeO and or cementite depending on the milling conditions etc Time, milling speed and BPR variation which influenced the reduction. The study shows that by increasing the milling time, the rotational speed and / or the ball to powder ratio, the extent of the conversion of hematite to its reduction products increased. XRD study investigations even though were unable to detect spm species (Fe2+ and Fe3+ ) which has smaller crystallites below detection limits ,the variation in time showed an increment in the magnetite peaks accompanied by recession of hematite and graphite peaks as the milling time was increased which relates to the MAS observation.XRD also corroborated the data obtained from MAS that showed that the main constituent was magnetite and further evidence in support of the reduction of hematite to magnetite under reactive milling was obtained using XRD . Overall, the work demonstrated selective reduction of Fe2O3 to Fe3O4 and Fe3O4 to FeO by fine tuning the milling conditions. It is envisaged that the reduction of FeO to Fe and possible carburization to FexC could also be achieved.

There exist large number of techniques for the preparation of nanostructured materials. Among them the preparation of nanopowders by gas/vapour condensation is a popular one. Because of very high level of surface to volume ratio, powders of metals which may or may not be reactive in the bulk form undergo vigorous oxidation. Oxidation once initiated continues in an auto catalytic fashion leading to a rise in temperature further increasing the oxidation rate. Therefore, the nanopowders are consolidated in situ under high vacuum. Alternatively a thin passivating oxide layer of few nm can be produced by slow exposure to air. Such powders lend themselves to be handled in further processing in ambient atmosphere. The main objective of the present research is to understand the various scientific and technological issues involved in preparing such passivated nanopowders by levitational gas condensation (LGC) technique, a relatively less explored vapour condensation process and their subsequent consolidation by the powder metallurgical route of compaction and sintering. The nanopowders systems studied are Fe and Fe-Cu (4 wt. %Cu). In chapter 1 a brief review of the gas condensation process and the consolidation behavior of nanopowders produced by this method were carried out. Existing knowledge on various topics relevant for the present study like formation of nanoparticles, agglomeration during gas condensation, physical, structural and chemical nature of the passive layer formed during passivation, compaction and sintering behaviour of this passivated nanopowders were discussed. Chapter 2 details the synthesis of Fe nanopowders by levitational gas condensation process and its physical and structural characteristics. The nanopowders in the as synthesized condition showed extremely low packing density due to loosely packed weakly interlocked agglomerates. The nanoparticles manifest as three dimensional reticulated spongy structure composed of chains of these nanoparticles. Heat transfer calculation carried out to determine the particle temperature at different distance from the levitating drop indicates that the nanoparticles can be ferromagnetic at a distance of less than 2 mm away from the levitation drop and hence the magnetic nature of the materials plays an important role in the formation of nanoparticle chains and spongy agglomerates. Passivation of the nanopowders by slow exposure to air produces 3-4 nm thick oxide layer (Fe3O4) over α-Fe and the volume of these oxides was around 45%. The 3rd chapter presents and discusses the results of Fe-Cu alloy nanopowder synthesized by levitating gas condensation process. While synthesis of elemental nanopowders by gas condensation is straight forward as the operating conditions only influence the particle size, alloys require careful control of the levitating drop composition. Although initially we start the process with levitated drop of required composition, the vapour generated will be richer in more volatile element (Cu in our case). Thus the composition of the levitated drop progressively becomes deficient in Cu which in turn reduces Cu in the vapour. Composition of the drop can be stabilised by continuous feeding of the alloy of required composition that can be estimated from the knowledge of equilibrium relation. To establish the equilibrium relationship between composition of the liquid and vapour in evaporation and condensation, phase diagram in the liquid and vapour region was calculated and was validated by determining composition of the drops. Good agreement between the drop composition and the composition predicted by the phase diagram were observed. Various physical, chemical and structural properties of the Fe-Cu nanopowders are characterized in detail using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy (XPS) and thermogravimetry (TG) analysis. The overall chemical composition of the Fe-Cu alloy nanopowders and of the individual agglomerates is same as the composition of feed materials used. However, Cu was found to segregate to the surface of the nanopowders which is attributed to minimization of surface energy with Cu at the surface. The total weight loss observed in TG in flowing hydrogen indicates that the surface passive layer of Fe-Cu appears to be very thin compared to Fe. The consolidation behaviour of both Fe and Fe-Cu nanopowders was studied by both conventional and spark plasma sintering (SPS) and are discussed in chapter 4. The as collected nanopowders from the apparatus have extremely low apparent density. The powders were further subjected to soft milling in a ball mill under ethanol to disentangle the agglomerates there by improving the pack density. A tenfold improvement was achieved thus making it suitable for consolidation. Uniaxial compaction of these powders for conventional sintering at pressure below 200 MPa yielded compacts free from defects. However, at higher pressure the compacts cracks and delaminates during ejection stage. Analysis of the compaction curves helped us to understand various processes involved during compaction as well as providing explanation for lower green density of Fe-Cu powder compared to Fe. Conventional sintering of the nanopowders compacts were carried out in the flowing hydrogen atmosphere in a laboratory vacuum furnace over wide range of temperatures. Instrumented sintering experiments were also carried out in a dilatometer under hydrogen atmosphere to evaluate shrinkage rate at different temperatures. SPS were carried out under 10 Pa vacuum at a compaction pressure of 250 MPa in WC-Co die cavity. The stability, density and residual oxygen content of the sintered compacts were quantified. Detailed microstuctural analysis of the sintered samples were also carried out using optical microscopy, atomic force microscopy, scanning electron microscopy, transmission electron microscopy, scanning transmission electron microscopy and quantitative composition analysis by EDS. Conventionally sintered compacts of both the powders showed stability only when sintered at 700°C and beyond. The maximum shrinkage/densification occured around 450°C for both the powders and the densification rate observed in Fe-Cu is three times higher than Fe. This enhanced densification in Fe-Cu is attributed to an enhanced diffusivity of Fe atoms in the transient liquid Cu layer formed at the interfaces. The microstructure of Fe-Cu is completely free from any separate oxide phase unlike in samples of Fe sintered at 700°C that contain ultrafine oxide grains. This was explained on the basis of role played by acrawax, a lubricant, admixed to increase the green density. Based on the sintered densities of both SPS and conventional sintered compacts, residual oxide content of the compacts sintered at different temperature and experimentally observed shrinkage rate a phenomenological model has been proposed for the possible sequence of processes occurring during sintering of these nanopowders. The major findings of this work are summarized in chapter 6 and chapter 7 details the scope for the future work.

[pt] Este trabalho tem como objetivo efetuar um estudo arqueometalúrgico de objetos ferrosos e não-ferrosos resgatados de sítios históricos do Rio de janeiro. A pesquisa experimental desenvolveu uma metodologia de análise utilizando-se de técnicas destrutivas como Microscopia Ótica (MO), Microscopia Eletrônica de Varredura (MEV), Microscopia Eletrônica de Transmissão e não destrutivas como Fluorescência de Raio X (FRX) e Emissão de Raios-X por Indução de Partículas (PIXE). Os objetos foram analisados com o intuito de caracterizar sua composição, estrutura e método de elaboração. Estes correspondem a seis artefatos de natureza metálica não-ferrosa e um de natureza metálica ferrosa. O objeto metálico ferroso corresponde a uma enxada. As características microestruturais dos objetos estão correlacionadas com a função que esses desempenhavam na época e indicativa de que a enxada possa ter sido feita no Brasil por escravos africanos. A análise da enxada permite concluir que é constituída de um ferro pudlado e que foi processada por fundição e forjamento. Quanto aos objetos não-ferrosos, o rosário é constituído de um latão monofásico mais rico em cobre. Com relação à fabricação do rosário pode-se concluir de que seja de origem européia, sendo decorrente de um minério pirítico. As medalhas são de procedência européia constituídas de latão. Historicamente, pode-se deduzir que são referentes ao século XVIII. Conclui-se que as duas moedas do Sítio Rochedo sejam originárias de fontes diferentes, constatado pelas análises químicas. Porém, as concentrações químicas da moeda de 1821 são próximas a uma das moedas de 40 réis. A presente tese permitiu evidenciar a importância da sistemática de trabalho experimental de caracterização, a partir de técnicas destrutivas e nãodestrutivas de materiais, de objetos arqueológicos para estabelecer seu contexto histórico. / [en] This work undertakes an archeometallurgical study of ferrous and non-ferrous artifacts recovered from historical sites of Rio de Janeiro. The experimental research developed an analytical methodology based on destructive techniques, such as Optical Microscopy (OM), Scanning Electronic Microscopy (SEM) and Transmission Electronic Microscopy (TEM); as well as non- destructive techniques, namely X-Ray Fluorescence (XRF) and Particle Induction X-Ray Emission (PIXE). These artifacts were analyzed in order to characterize their composition, structure and elaboration/processing methods. There are six artifacts with a non-ferrous metallic nature and one with a ferrous metallic nature. The ferrous metallic artifact was a hoe. The microstructure characteristics is related to the usage of this object at that time, and indicates that the hoe could have been made in Brazil by African slaves. The analysis of the hoe indicates that it was elaborated from puddle iron and that it had been processed by foundry and forging. The rosary, one of the non-ferrous artifacts, is formed by singlephase brass riche in copper; and according to historical research it is of European origin, deriving from pyrite ore. The medals are also of European origin and are based on brass. Historically one can deduce that they are dated from the 18th century. The two coins from the Rochedo site most probably came from distinct sources, as validated by the chemical analysis. However, the chemical composition of the 1821 coin is close to that of the 40 réis coin. The present thesis has shown the importance of a systematic methodology to characterize ancient objects combining both destructive and non- destructive techniques.

No description available.

Ce travail de recherche vise à mettre au point la première gamme de sondes magnétogéniques à base de Fer(II) répondant à un analyte biochimique. L’objectif est de créer les premières sondes résolument silencieuses en IRM qui ne génèrent un signal qu’après leur rencontre avec l’analyte, une caractéristique hautement désirable dans le domaine de l’IRM moléculaire. Au cours d’un travail doctoral précédent, une paire de complexes ferreux modèles, hydrosolubles et chargés positivement, a été identifiée et a permis de valider l’idée de ce concept OFF-ON in vitro. Dans un premier temps nous avons démontré qu’un tel concept pouvait être également validé in vivo chez la souris. Ceci a nécessité le développement de stratégies de synthèse organique inédites et notamment la mise au point de synthons tétrazolyleméthyle protégés. Une telle méthodologie a notamment démontré son efficacité dans la synthèse du premier analogue totalement azoté de l’EDTA. Par la suite nous avons démontré qu’il était possible sous certaines conditions, non physiologiques, de réaliser les exigences du concept de magnétogénèse. En particulier nous avons démontré que des unités amidines peuvent être modifiées, en ayant recours à des concepts de type prodrogue, et utilisées pour éteindre et allumer le spin électronique du Fer(II) après rencontre avec l’analyte. Enfin nous avons également démontré au cours de ce travail, avec une seconde stratégie, que le concept de magnétogénèse était possible dans des conditions physiologiques et constantes et avons construit un modèle biologique afin d’évaluer une molécule candidate prometteuse in cellulo. / This PhD project aims to develop the first line of Iron(II) based magnetogenic probes that respond to bio-chemical analytes. It sets out to address one of the main limitations of responsive probes by rendering the initial probe completely MRI silent. During the previous investigations of the Bio-organic chemistry group, a duo of Iron(II) low spin-high spin parent complexes has been identified as the basis for a magnetogenic design. In the current work we have validated this OFF-ON approach, in vivo, by ensuring the electroneutrality of the final contrast agent. Such a feature required the development of protected synthons for the convergent introduction of tetrazolylmethyl chelating motifs. And such a synthetic methodology was also applied for the synthesis of the first full nitrogen analog of EDTA. In a second part of this work, a first magnetogenic concept was explored exploiting amidine moieties to silence or awaken the electronic spin of ferrous complexes. We demonstrated that this magnetogenic concept was valid, after a short chemical stimulation, though at the expense of harsh acidic conditions to trigger the paramagnetism of the final complex. Finally we successfully explored a second magnetogenic concept operating in physiological conditions and responding to bio-chemical stimulations.We then evaluated the most promising candidate in cellulo by developing a biological model expressing the nitroreductase enzyme.

La mise au jour du mobilier archéologique ferreux s'accompagne de dégradations si ce dernier n'est pas rapidement stocké en atmosphère inerte ou traité. Dans le cas des objets provenant de fouilles sous-marines, la présence de produits de corrosion chlorurés instables au contact de l'air accélère les phénomènes de reprise de corrosion. Afin de limiter ces dégradations et de stabiliser l'objet, il est nécessaire d'extraire les ions chlorure piégés au sein du système de corrosion. Divers traitements de déchloruration ont été développés par les ateliers de conservation (immersion dans des solutions alcalines, polarisation cathodique, plasma d'hydrogène, fluide subcritique…). Ces traitements ont une efficacité certaine mais une meilleure compréhension des mécanismes de déchloruration (évolution des phases chlorurées durant le traitement, phénomènes de transport dans la couche, cinétiques d'extractions des chlorures…) permettrait de les optimiser (temps de traitement, fiabilité, reproductibilité…). Les objectifs de cette thèse sont multiples. En un premier temps la caractérisation fine du système de corrosion développé en milieu marin puis lors de son abandon à l'air a été réalisée à l'aide de techniques multi-échelles sur un corpus expérimental composé de lingots en fer forgé provenant de frégates gallo-romaines découvertes au large des Saintes-Maries-de-la-Mer (Bouches-du-Rhône, France) immergées durant 2000 ans. Il a notamment été mis en évidence que ce faciès de corrosion est principalement composé d'hydroxychlorure de fer (β-Fe2(OH)3Cl), phase chlorurée contenant près de 20% en masse de chlore. En un second temps l'évolution du système de corrosion développé en milieu marin a été suivi lors des étapes constituant un traitement de déchloruration : l'étape de traitement à proprement parlé qui consiste en la circulation d'une solution de NaOH aérée ou désaérée, l'étape de lavage puis l'étape de séchage. Ce second axe s'est déroulé en deux temps. Tout d'abord le suivi in situ de l'évolution de la couche de corrosion lors de l'étape de traitement a été réalisé sous rayonnement synchrotron par diffraction des rayons X. Puis le système de corrosion a été caractérisé à l'ssu des étapes de lavage et de séchage. Ainsi le comportement de la couche de corrosion a pu être appréhendée et une meilleure compréhension des mécanismes de déchloruration proposée. Les objectifs de cette étude sont d'une part de suivre in situ l'évolution du faciès de corrosion d'objets archéologiques lors d'un traitement en solution aérée d'hydroxyde de sodium (NaOH) et d'autre part de caractériser le faciès de corrosion après lavage et séchage de l'objet (…) / The excavation of archaeological iron artefacts are accompanied by degradation if they are not readily stored in an inert atmosphere or treated. In the case of artifacts from underwater excavations, the presence of chlorinated volatile corrosion products on contact with air accelerates the recovery of corrosion phenomena. To limit this degradation and stabilize the object, it is necessary to remove chloride ions trapped in the corrosion pattern. Various dechlorination treatments have been developed by conservation workshops (immersion in alkaline solutions, cathodic polarization, hydrogen plasma, subcritical fluid ...). Despite a genuine efficiency, these treatments need to be optimized (processing time, reliability, reproducibility ...) by a better understanding of dechlorination mechanisms (structural evolution of corrosion pattern during treatment, transport phenomena in the layer, kinetics of extraction of chlorides ...). The objectives of this study are multiple. At first the detailed characterization of the corrosion pattern developed in the marine environment and then when it was abandoned in air was performed using multiscale techniques on an experimental corpus consists of wrought iron ingots from Gallo-Roman ships discoveries off the Saintes-Maries-de-la-Mer (Bouches-du-Rhone, France) submerged for over 2000 years. In particular it was shown that the corrosion pattern of an freshly excavated object is mainly composed of the ferrous hydroxychloride β-Fe2(OH)3Cl, chlorinated phase containing about 20 wt% chlorine. In a second time the evolution of the corrosion pattern was followed during the treatment steps constituting dechlorination: the step of processing, strictly speaking, which consists of the circulation of a NaOH solution aerated or deaerated, step then washing the drying step. The second axis was conducted in two stages. First, the in situ monitoring of the corrosion layer's evolution in the step of processing was carried out under synchrotron radiation by X-ray diffraction coupled to the determination of chloride ions in solution extracts. Then the corrosion pattern was characterized ex situ, elementarily and structurally, from the steps of washing and drying. The whole data allowed us firstly to refine processes structural evolution of the corrosion layer at each stage and also discuss models of chloride extraction proposed in the literature

O chorume é um líquido produzido na decomposição dos resíduos sólidos e apresenta riscos ambientais, devido à variedade de substancias poluentes presentes na matriz. O chorume in natura utilizado neste trabalho foi proveniente do aterro sanitário de Cachoeira Paulista - SP, sendo caracterizado com elevadas concentrações de COT (1233,33 mgL-1), DQO (3565,0 mgL-1) e DBO5/DQO = 0,099. Diante da baixa biodegradabilidade do chorume (DBO5/DQO < 0,2), utilizou-se a ozonização catalítica, em presença de ferro, em sistema contínuo, como uma alternativa para viabilizar o tratamento deste efluente. Diversas configurações de reatores foram avaliadas, sendo utilizados, inicialmente, reatores contínuos rudimentares (PVC). As avaliações reacionais e operacionais dos protótipos possibilitaram a elaboração de um reator construído com bases conceituais de engenharia, confeccionado em vidro borosilicato, e em dois módulos: o corpo do reator com duas entradas, sendo uma de alimentação, localizada acima, e a outra de introdução de ozônio, que foi feita por meio de um difusor de vidro sinterizado na base do reator. O segundo módulo foi feito para garantir que a espuma formada durante a reação fosse eliminada pela quebra da tensão através de ar comprimido, retornando-a, sob a forma líquida, ao sistema. As avaliações iniciais da ozonização catalítica do chorume in natura, para a verificação da potencialidade deste tratamento, foram realizadas sem o uso de um planejamento experimental, sendo o melhor resultado obtido na ordem de 72,64 % para a redução de COT. Após a seleção do reator de ozonização para o processo contínuo e a escolha do íon ferroso como catalisador, foi elaborado um planejamento fatorial fracionado (24-1) para avaliação das variáveis (potência, vazão de saída do reator, concentração de Fe2+, pH), no qual, o melhor resultado para a redução de COT foi de 59,38%. Este desempenho inferior para a redução de COT pode ser atribuído à substituição do gás de oxigênio puro por ar comprimido, reduzindo a vazão mássica de ozônio disponível para o tratamento. Entretanto, este processo pode ser viabilizado no tratamento prévio do chorume, pois a ozonização proporcionou uma elevada redução de DQO na ordem de 82,3 % e um aumento de 74,4% na biodegradabilidade (DBO5/DQO = 0,389) do chorume, podendo torná-lo potencialmente tratável por processos convencionais. / Leachate is a liquid produced in the decomposition of solid waste and presents environmental risks due to the variety of polluting substances existing in the matrix. The in natura leachate used in this work was from the landfill of the city Cachoeira Paulista in the state of São Paulo, which was characterized with high concentrations of TOC (1233.33 mgL-1) COD (3565.0 mg.L-1) and BOD5/COD = 0.099. Due to the low biodegradability of leachate (BOD5/COD < 0.2), the catalytic ozonation in the presence of iron in a continuous system was used as a viable alternative for the treatment of this effluent. Several configurations of reactors were evaluated, and, initially, rudimentary continuous reactors (PVC) were used. The reactional and operational evaluations of the prototypes enabled the creation of a reactor built on conceptual foundations of engineering, that was made of borosilicate glass, and in two modules: the body of the reactor with two entries, one for feeding, located above, and the other one for ozone introduction, made through a sintered glass diffuser at the bottom of the reactor. The second module was made to ensure that the foam formed during the reaction is eliminated by breaking the tension via compressed air, returning it, in liquid form, to the system. Initial assessments of the catalytic ozonation of the in natura leachate, to verify the potential of this treatment, were performed without the use of an experimental design, and the best result obtained was to reduce TOC on about 72.64 %. After selecting the ozonation reactor for continuous process and choosing ferrous ion as catalyst, a fractional factorial design (24-1) was prepared to evaluation the selected variables (potency, output flow of reactor, Fe2+ concentration, pH) in which the best result for the TOC reduction was 59.38%. This inferior performance for the TOC reduction can be associated to the replacement of pure oxygen gas by compressed air, reducing the ozone mass flow available to the treatment. However, this process can be made possible in the pretreatment of leachate, because the ozonation provided a high reduction of COD on about 82.3% and an increase of 74.4% on the biodegradability (BOD5/COD = 0.389) of leachate, and that can make it potentially treatable by conventional methods.

O chorume é um líquido produzido na decomposição dos resíduos sólidos e apresenta riscos ambientais, devido à variedade de substancias poluentes presentes na matriz. O chorume in natura utilizado neste trabalho foi proveniente do aterro sanitário de Cachoeira Paulista - SP, sendo caracterizado com elevadas concentrações de COT (1233,33 mgL-1), DQO (3565,0 mgL-1) e DBO5/DQO = 0,099. Diante da baixa biodegradabilidade do chorume (DBO5/DQO < 0,2), utilizou-se a ozonização catalítica, em presença de ferro, em sistema contínuo, como uma alternativa para viabilizar o tratamento deste efluente. Diversas configurações de reatores foram avaliadas, sendo utilizados, inicialmente, reatores contínuos rudimentares (PVC). As avaliações reacionais e operacionais dos protótipos possibilitaram a elaboração de um reator construído com bases conceituais de engenharia, confeccionado em vidro borosilicato, e em dois módulos: o corpo do reator com duas entradas, sendo uma de alimentação, localizada acima, e a outra de introdução de ozônio, que foi feita por meio de um difusor de vidro sinterizado na base do reator. O segundo módulo foi feito para garantir que a espuma formada durante a reação fosse eliminada pela quebra da tensão através de ar comprimido, retornando-a, sob a forma líquida, ao sistema. As avaliações iniciais da ozonização catalítica do chorume in natura, para a verificação da potencialidade deste tratamento, foram realizadas sem o uso de um planejamento experimental, sendo o melhor resultado obtido na ordem de 72,64 % para a redução de COT. Após a seleção do reator de ozonização para o processo contínuo e a escolha do íon ferroso como catalisador, foi elaborado um planejamento fatorial fracionado (24-1) para avaliação das variáveis (potência, vazão de saída do reator, concentração de Fe2+, pH), no qual, o melhor resultado para a redução de COT foi de 59,38%. Este desempenho inferior para a redução de COT pode ser atribuído à substituição do gás de oxigênio puro por ar comprimido, reduzindo a vazão mássica de ozônio disponível para o tratamento. Entretanto, este processo pode ser viabilizado no tratamento prévio do chorume, pois a ozonização proporcionou uma elevada redução de DQO na ordem de 82,3 % e um aumento de 74,4% na biodegradabilidade (DBO5/DQO = 0,389) do chorume, podendo torná-lo potencialmente tratável por processos convencionais. / Leachate is a liquid produced in the decomposition of solid waste and presents environmental risks due to the variety of polluting substances existing in the matrix. The in natura leachate used in this work was from the landfill of the city Cachoeira Paulista in the state of São Paulo, which was characterized with high concentrations of TOC (1233.33 mgL-1) COD (3565.0 mg.L-1) and BOD5/COD = 0.099. Due to the low biodegradability of leachate (BOD5/COD < 0.2), the catalytic ozonation in the presence of iron in a continuous system was used as a viable alternative for the treatment of this effluent. Several configurations of reactors were evaluated, and, initially, rudimentary continuous reactors (PVC) were used. The reactional and operational evaluations of the prototypes enabled the creation of a reactor built on conceptual foundations of engineering, that was made of borosilicate glass, and in two modules: the body of the reactor with two entries, one for feeding, located above, and the other one for ozone introduction, made through a sintered glass diffuser at the bottom of the reactor. The second module was made to ensure that the foam formed during the reaction is eliminated by breaking the tension via compressed air, returning it, in liquid form, to the system. Initial assessments of the catalytic ozonation of the in natura leachate, to verify the potential of this treatment, were performed without the use of an experimental design, and the best result obtained was to reduce TOC on about 72.64 %. After selecting the ozonation reactor for continuous process and choosing ferrous ion as catalyst, a fractional factorial design (24-1) was prepared to evaluation the selected variables (potency, output flow of reactor, Fe2+ concentration, pH) in which the best result for the TOC reduction was 59.38%. This inferior performance for the TOC reduction can be associated to the replacement of pure oxygen gas by compressed air, reducing the ozone mass flow available to the treatment. However, this process can be made possible in the pretreatment of leachate, because the ozonation provided a high reduction of COD on about 82.3% and an increase of 74.4% on the biodegradability (BOD5/COD = 0.389) of leachate, and that can make it potentially treatable by conventional methods.