[ES] La normativa ambiental potencia la revalorización de los residuos industriales y motiva su utilización como materias primas para la obtención de nuevos materiales útiles, en lugar de que dichos residuos sean depositados en rellenos, que a la postre pueden generar pasivos ambientales. Dentro de este contexto se planificó la síntesis de la zeolita NaP1 código GIS, de amplia utilización en el campo ambiental para la descontaminación de aguas residuales, particularmente polutas con metales pesados y, la síntesis de la zeolita A código LTA, con aplicaciones en la industria de detergentes en reemplazo de los fosfatos, causantes de acelerar la eutrofización del agua de lagos; esto utilizando como materia prima los residuos industriales provenientes de los procesos y operaciones unitarias del pasivado del aluminio por oxidación electrolítica anódica. La presente investigación se enfoca en la recuperación indirecta del aluminio presente en los residuos industriales de anodizado de aluminio, transfiriéndolo a la estructura cristalina de las zeolitas. El residuo contiene elevadas concentraciones de aluminio, tal como lo prueban los resultados obtenidos mediante microscopía electrónica de barrido SEM (38.9% - 40.42%) y por espectroscopia de absorción atómica con llama AAS (37.16 g/100g); pero es pobre en contenido de silicio (0.93% - 0.74%) determinado por SEM y 1.83 g/100g determinado por AAS. Además, el residuo de anodizado de aluminio contiene concentraciones menores de cationes alcalinos y alcalinotérreos. El contenido de humedad del lodo es de 69.84% (n=28) y su pH cae en el rango 7.7 a 8.3 (1:5 w/v), que lo hace ligeramente alcalino. Se observó que la relación molar Si/Al es significativamente menor que la unidad, de lo cual se infiere que los residuos industriales tal como salen de la planta de tratamiento, no se pueden utilizar para la síntesis de zeolitas. La caracterización de los residuos industriales deshidratados a 100°C por 4 y 24 horas mediante microscopia electrónica de barrido (SEM) y difracción de rayos-X muestran un material básicamente amorfo, sin morfología externa apreciable. La composición fisicoquímica en términos del contenido de aluminio en los lodos de anodizado, permite plantear la recuperación del aluminio y cationes a través de la síntesis de zeolitas, utilizando como materia prima el residuo industrial, enriquecido con silicio proveniente de fuentes externas. Así para sintetizar la zeolita NaP1, código GIS, se enriqueció el lodo de anodizado con silicio proveniente de una solución de silicato de sodio grado analítico. Con la finalidad de identificar la concentración a la que se tiene los mejores resultados, se utilizó como agente de mineralización soluciones de NaOH en concentraciones 0.5M; 1.0M; 1.5M; 2.0M; 2.5M y 3.0M. Se instrumentó el método hidrotermal de síntesis a una temperatura constante de 100°C y 48 horas de tiempo de reacción, utilizando los residuos industriales húmedos. Los materiales obtenidos a las diferentes condiciones de síntesis se han caracterizado mediante difracción de rayos-X y SEM. Así, las concentraciones 1.5M, 2.0M, 2.5M y 3.0M del agente de mineralización NaOH conducen a la síntesis de la zeolita NaP1 código GIS. Sin embargo, el producto obtenido utilizando como agente de mineralización NaOH 1.5M presenta cristales con morfología externa muy bien definida, en forma de esferas de tamaño homogéneo. Este material presenta una relación molar Si/Al de 2.44 y una fórmula teórica 0.98Na2O•Al2O3•4.88SiO2•yH2O. Los materiales obtenidos con concentraciones más altas del agente de mineralización, aun presentando un difractograma de rayos-X correspondiente a la zeolita NaP1, en el microscopio electrónico muestran cristales poco formados y de tamaños muy diferentes. De esto se infiere que el agente de mineralización NaOH 1.5M presenta los mejores resultados en términos de morfología. Utilizando como fuente de enriquecimiento de silicio el silicato de sodio comercial, se sintetizó la zeoli / [CA] La normativa ambiental potència la revaloració dels residus industrials i motiva la seua utilització com a matèries primeres per a l'obtenció de nous materials útils, en lloc que aquests residus siguen depositats en farciments, que fet i fet poden generar passius ambientals. Dins d'aquest context es va planificar la síntesi de la zeolita NaP1 codi GIS, d'àmplia utilització en el camp ambiental per a la descontaminació d'aigües residuals, particularment contaminades amb metalls pesants i, la síntesi de la zeolita A codi LTA, amb aplicacions en la indústria de detergents en reemplaçament dels fosfats, causants d'accelerar l'eutrofització de l'aigua de llacs; això utilitzant com a matèria primera els residus industrials provinents dels processos i operacions unitàries del passivat de l'alumini per oxidació electrolítica anòdica. La present investigació s'enfoca en la recuperació indirecta de l'alumini present en els residus industrials d'anoditzat d'alumini, transferint-ho a l'estructura cristal·lina de les zeolites. El residu conté elevades concentracions d'alumini, tal com ho proven els resultats obtinguts mitjançant microscòpia electrònica d'escombratge SEM (38.9% - 40.42%) i per espectroscòpia d'absorció atòmica amb flama AAS (37.16 g/100g); però és pobre en contingut de silici (0.93% - 0.74%) determinat per SEM i 1.83 g/*100g determinat per AAS. A més, el residu d'anoditzat d'alumini conté concentracions menors de cations alcalins i alcalinoterris. El contingut d'humitat del llot és de 69.84% (n=28) i el seu pH cau en el rang 7.7 a 8.3 (1:5 w/v), que ho fa lleugerament alcalí. Es va observar que la relació molar Si/A l'és significativament menor que la unitat, de la qual cosa s'infereix que els residus industrials tal com ixen de la planta de tractament, no es poden utilitzar per a la síntesi de zeolites. La caracterització dels residus industrials deshidratats a 100 °C per 4 i 24 hores mitjançant microscòpia electrònica d'escombratge (SEM) i difracció de raigs-X mostren un materials bàsicament amorfs, sense morfologia externa apreciable. La composició fisicoquímica en termes del contingut d'alumini en els llots d'anoditzat, permet plantejar la recuperació de l'alumini i cations a través de la síntesi de zeolites, utilitzant com a matèria primera el residu industrial, enriquit amb silici provinent de fonts externes. Així per a sintetitzar la zeolita NaP1, codi GIS, es va enriquir el llot d'anoditzat amb silici provinent d'una solució de silicat de sodi grau analític. Amb la finalitat d'identificar la concentració a la qual es té els millors resultats, es va utilitzar com a agent de mineralització soluciones de NaOH en concentracions 0.5M; 1.0M; 1.5M; 2.0M; 2.5M i 3.0M. Es va instrumentar el mètode hidrotermal de síntesi a una temperatura constant de 100 °C i 48 hores de temps de reacció, utilitzant els residus industrials humits. Els materials obtinguts a les diferents condicions de síntesis s'han caracteritzat mitjançant difracció de raigs-X i SEM. Així, les concentracions 1.5M, 2.0M, 2.5M i 3.0M de l'agent de mineralització NaOH condueixen a la síntesi de la zeolita NaP1 codi GIS. No obstant això, el producte obtingut utilitzant com a agent de mineralització NaOH 1.5M presenta cristalls amb morfologia externa molt ben definida, en forma d'esferes de grandària homogènia. Aquest material presenta una relació molar Si/Al de 2.44 i una fórmula teòrica 0.98Na2O•Al2O3•4.88SiO2•yH2O. Els materials obtinguts amb concentracions més altes de l'agent de mineralització, encara presentant un difractograma de raigs-X corresponent a la zeolita NaP1, en el microscopi electrònic mostren cristalls poc formats i de grandàries molt diferents. D'això s'infereix que l'agent de mineralització NaOH 1.5M presenta els millors resultats en termes de morfologia. Utilitzant com a font d'enriquiment de silici el silicat de sodi comercial, es va sintetitzar la zeolita Linde Tipus A, Codi estructural HISSA (Associació International de zeolite / [EN] Environmental regulations promote the revaluation of industrial waste and encourage its use as raw materials to obtain new valuable materials, instead of such waste being deposited in landfills, which can ultimately generate environmental liabilities. Within this context, the synthesis of the GIS code NaP1 zeolite, widely used in the environmental field for the decontamination of wastewater, particularly polluted with heavy metals, and the synthesis of the LTA code zeolite A, with applications in industry. detergents to replace phosphates, which cause the eutrophication of lake water to accelerate, were planned using as raw material the industrial residues from the processes and unitary operations of aluminum passivation by anodic electrolytic oxidation. This research focuses on the indirect recovery of aluminum present in industrial waste from aluminum anodizing, transferring it to the crystalline structure of zeolites. The residue contains high concentrations of aluminum, as proven by the results obtained by scanning electron microscopy SEM (38.9% - 40.42%) and by atomic absorption spectroscopy with AAS flame (37.16 g/100g); but it is poor in silicon content (0.93% - 0.74%) determined by SEM and 1.83 g/100g determined by AAS. In addition, the aluminum anodizing residue contains lower concentrations of alkali and alkaline earth cations. The moisture content of the mud is 69.84% (n=28) and its pH falls in the range of 7.7 to 8.3 (1:5 w/v), which makes it slightly alkaline. It was observed that the Si/Al molar ratio is significantly less than unity, from which it is inferred that industrial waste as it leaves the treatment plant has to be modified to be used for the synthesis of zeolites. SEM and X-ray diffraction characterization of the aluminum-containing industrial waste dehydrated at 100°C for 4 and 24 hours show basically amorphous materials without appreciable external morphology. The physicochemical composition in terms of the aluminum content in the anodizing sludge allows us to propose the recovery of aluminum through the synthesis of zeolites, using industrial waste as raw material, and enriching it with silicon from external sources. Thus, to synthesize the zeolite NaP1, code GIS, the anodizing sludge was enriched with silicon from an analytical grade sodium silicate solution. To identify the concentration at which the best results are obtained, NaOH solutions at 0.5M concentrations were used as mineralization agents; 1.0M; 1.5M; 2.0M; 2.5M and 3.0M. The hydrothermal synthesis method was implemented at a constant temperature of 100°C and 48 hours of reaction time, using wet industrial waste. The materials obtained at the different synthesis conditions were characterized by X-ray diffraction and SEM. Thus, concentrations of 1.5M, 2.0M, 2.5M, and 3.0M of the mineralizing agent NaOH lead to the synthesis of the zeolite NaP1 code GIS. However, the product obtained using 1.5M NaOH as the mineralization agent presents crystals with a very well-defined external morphology in the form of spheres of homogeneous size. This material has a Si/Al molar ratio of 2.44 and a theoretical formula of 0.98Na2O•Al2O3•4.88SiO2•yH2O. The materials obtained with higher concentrations of the mineralization agent, even presenting an X-ray diffractogram corresponding to zeolite NaP1, show poorly formed crystals of very different sizes. From this, it is inferred that the 1.5M NaOH mineralization agent presents the best results in terms of morphology. Using commercial sodium silicate as the source of silicon enrichment, the Linde Type A zeolite, structural code IZA (International Zeolite Association) LTA, was synthesized. This product is obtained with a weight ratio of wet industrial residue to commercial sodium silicate of 2.6 to 1, using 1.5M NaOH as a mineralization agent at 85°C and a reaction time of 4 hours, resulting in a zeolite A code LTA with Si/Al molar ratio, 1.04 (sample 1A) and Si/Al 1.05 (sample 2A). Taking into account the r / Peñafiel Villarreal, F. (2022). Revalorización de lodos resultantes del pasivado de aluminio por oxidación anódica mediante su utilización en la síntesis de zeolitas NaP1 y LTA [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/183230

Submitted by Johnny Rodrigues (johnnyrodrigues@ufcg.edu.br) on 2018-04-06T20:12:23Z No. of bitstreams: 1 TACIANA REGINA DE GOUVEIA - TESE PPG-CEMat 2014..pdf: 4953603 bytes, checksum: ea581c261908041111cd0d411a551545 (MD5) / Made available in DSpace on 2018-04-06T20:12:23Z (GMT). No. of bitstreams: 1 TACIANA REGINA DE GOUVEIA - TESE PPG-CEMat 2014..pdf: 4953603 bytes, checksum: ea581c261908041111cd0d411a551545 (MD5) Previous issue date: 2014-08-28 / Capes / Os polímeros derivados do petróleo têm provocado impactos ambientais devido ao descarte inadequado. Uma alternativa para esse problema é a utilização de polímeros biodegradáveis ou a produção de blendas a partir destes polímeros. Neste trabalho, foram preparadas blendas de poli (ácido lático) - PLA, poli (caprolactona) - PCL, com três copolímeros diferentes: EMA, E-GMA e o EMAGMA que são copolímeros de etileno-acrilato de metila, etileno-metacrilato de glicidila e o terpolímero etileno-acrilato de metila-metacrilato de glicidila, respectivamente. As composições utilizadas para as blendas foram as seguintes: PLA/PCL (90/10), PLA/PCL (80/20), PLA/Copolímeros (90/10) e PLA/PCL/Copolímeros (80/10/10). Estas foram preparadas por fusão em uma extrusora de rosca dupla corrotativa e, em seguida, moldadas por injeção sob a forma de corpos de prova de tração, impacto e HDT. Todas as composições foram caracterizadas por: ensaios mecânicos de tração e impacto, temperatura de distorção térmica - HDT, calorimetria exploratória diferencial - DSC, difração de raios X - DRX, análise térmica dinâmica-mecânica - DMTA, espectroscopia na região do infravermelho por transformada de Fourier - FTIR, microscopia eletrônica de varredura - MEV, reometria de torque, ensaio reológico e reometria capilar. As propriedades mecânicas apresentaram redução nos valores do módulo e da resistência à tração e um aumento no alongamento e na resistência ao impacto para todas as composições quando comparadas com o PLA puro, com destaque para as composições que continham o copolímero EMA-GMA. A HDT não apresentou mudanças significativas para as diferentes composições em comparação com o PLA puro. O comportamento térmico e termomecânico foi avaliado por DSC e por DMTA e foi possível observar a transição térmica das blendas. Por DRX foi possível observar as fases cristalinas das blendas de PLA. A morfologia da superfície de fratura observada por MEV ilustrou que ocorreram mudanças significativas em função da composição. Os resultados de reometria de torque não apresentaram mudanças significativas no comportamento do PLA, enquanto que os resultados obtidos no ensaio reológico ilustraram aumento no módulo de armazenamento em todas as composições. A partir do ensaio de reometria capilar foi visto que houve redução da viscosidade aparente e da tensão de cisalhamento sob altas taxas de cisalhamento para todas as composições. / The polymers derived from petroleum have caused environmental impacts due to improper disposal. An alternative to this problem is the use of biodegradable polymers or blends production from these polymers. In this work, blends of poly (lactic acid) - PLA, poly (-caprolactone) - PCL, were prepared with three different copolymers: EMA, E-GMA and EMA-GMA are copolymers the ethylene-methyl acrylate, ethylene-glycidyl methacrylate and terpolymer ethylene-methyl acrylate-glycidyl methacrylate respectively. The compositions used in the blends were as follows: PLA/PCL (90/10) PLA/PCL (80/20) PLA/ Copolymer (90/10) and PLA/PCL/Copolymer (80/10/10). These were prepared by melting in an extruder twin screw co-rotating and then injection molded in the form of specimens tensile, impact and HDT. All compositions were characterized by: mechanical tensile and impact , heat distortion temperature - HDT, differential scanning calorimetry - DSC, X-ray diffraction - XRD, dynamic mechanical thermal analysis – DMTA, spectroscopy in the infrared region by transform Fourier - FTIR, scanning electron microscopy - SEM, torque rheometer, rheological testing and capillary rheometer. The mechanical properties showed reduced values of modulus and tensile strength and an increase in elongation and impact resistance for all compositions when compared with pure PLA, especially for compositions containing copolymer EMA-GMA. The HDT showed no significant changes for the different compositions compared with pure PLA. The thermal and thermomechanical behavior was evaluated by DSC and DMTA and it was possible to observe the thermal transition of the blends. XRD was possible to observe the crystalline phases of the blends of PLA. The morphology of the fracture surface was observed by SEM illustrated that significant changes as a function of composition. The torque rheometer results showed no significant change in the behavior of PLA, while the rheological test results illustrate the increase in storage modulus in all compositions. From the test capillary rheometer was seen that there was a reduction in the apparent viscosity and shear stress at high shear rates for all compositions.

The majority of UK’s intermediate level radioactive waste is currently stored in 316L and 304L austenitic stainless steel containers in interim storage facilities for permanent disposal until a geological disposal facility has become available. The structural integrity of stainless steel canisters is required to persevere against environmental degradation for up to 500 years to assure a safe storage and disposal scheme. Hitherto existing severe localised corrosion observances on real waste storage containers after 10 years of exposure to an ambient atmosphere in an in-land warehouse in Culham at Oxfordshire, however, questioned the likelihood occurrence of stress corrosion cracking that may harm the canister’s functionality during long-term storage. The more corrosion resistant duplex stainless steel grade 2205, therefore, has been started to be manufactured as a replacement for the austenitic grades. Over decades, the threshold stress corrosion cracking temperature of austenitic stainless steels has been believed to be 50-60°C, but lab- and field-based research has shown that 304L and 316L may suffer from atmospheric stress corrosion cracking at ambient temperatures. Such an issue has not been reported to occur for the 2205 duplex steel, and its atmospheric stress corrosion cracking behaviour at low temperatures (40-50°C) has been sparsely studied which requires detailed investigations in this respect. Low temperature atmospheric stress corrosion cracking investigations on 2205 duplex stainless steel formed the framework of this PhD thesis with respect to the waste storage context. Long-term surface magnesium chloride deposition exposures at 50°C and 30% relative humidity for up to 15 months exhibited the occurrence of stress corrosion cracks, showing stress corrosion susceptibility of 2205 duplex stainless steel at 50°C.The amount of cold work increased the cracking susceptibility, with bending deformation being the most critical type of deformation mode among tensile and rolling type of cold work. The orientation of the microstructure deformation direction, i.e. whether the deformation occurred in transverse or rolling direction, played vital role in corrosion and cracking behaviour, as such that bending in transverse direction showed almost 3-times larger corrosion and stress corrosion cracking propensity. Welding simulation treatments by ageing processes at 750°C and 475°C exhibited substantial influences on the corrosion properties. It was shown that sensitisation ageing at 750°C can render the material enhanced susceptible to stress corrosion cracking at even low chloride deposition densities of ≤145 µm/cm². However, it could be shown that short-term heat treatments at 475°C can decrease corrosion and stress corrosion cracking susceptibility which may be used to improve the materials performance. Mechanistic understanding of stress corrosion cracking phenomena in light of a comprehensive microstructure characterisation was the main focus of this thesis.

Within the collaborative research center SFB 920 “Multifunctional Filters for Metal Melt Filtration”, the thermally induced formation of metastable aluminum oxides and related microstructural changes were investigated. It was confirmed that the γ-Al₂O₃ phase possesses a defective spinel structure containing Al vacancies that preserve the stoichiometry of this phase. The presence of vacancies fragments apparently the γ-Al₂O₃ crystallites into nanocrystalline domains, which are separated by non-conservative antiphase boundaries (APBs) of the type {100} ¼<110>. These APBs form a 3D network that is randomly distributed over all crystallographically equivalent lattice planes. This phenomenon causes a starlike (and hkl-dependent) broadening of the reciprocal lattice points that correspond to the aluminum sublattice. It was shown that the extent of the broadening of the reciprocal lattice points can be predicted by employing the phase shift factors. With increasing degree of the APBs ordering, the initial streaks representing the broadened reflections start to split, forming superstructure reflections. This superstructure of γ-Al₂O₃ is commonly known as δ-Al₂O₃. Between the ordered APBs, the crystal structure of δ-Al₂O₃ is closely related to the crystal structure of monoclinic θ-Al₂O₃. The phase transition of γ-Al₂O₃/δ-Al₂O₃ to θ-Al₂O₃ proceeds via migration of just three Al³⁺ cations to the neighboring tetrahedral and octahedral sites in the cubic close packed (ccp) oxygen sublattice. The general migration vector is ⅛<111> (γ-Al₂O₃). Diffraction effects associated with different intermediate states can be explained by an improper long-range ordering of equivalent APBs or certain Al³⁺ cations and the local formation of θ-Al₂O₃ within the δ-Al₂O₃ superstructure. The formation of θ-Al₂O₃ is accompanied by an increase of the occupancy of the tetrahedral sites in the oxygen sublattice by the Al³⁺ cations. In surrounding local γ-Al₂O₃ domains, however, some cations migrate from the tetrahedral to the octahedral sites. Thus, the local formation of θ-Al₂O₃ is nearly invisible for the ²⁷Al 1D magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. Still, it was recognized by the 2D multiple quantum (MQ) MAS NMR spectroscopy. A continuous formation of the θ-Al₂O₃ domains was confirmed by the Raman spectroscopy, X-ray diffraction (XRD) and selected area electron diffraction (SAED). The proposed microstructure and transformation models helped to explain the thermal stabilization of the metastable alumina phases by Si-doping. For investigation of the thermally induced phase transitions in metastable alumina phases, boehmite (γ-AlO(OH)) was chosen as the starting compound. However, the metastable alumina phases were also observed in endogenous inclusions present in solidified steel melts. For identification of these phases, a procedure for reconstruction of spherical Kikuchi maps from recorded EBSD patterns was developed.